CN1053330C - A germ-destroying treatment method using isothiocyanate vapors - Google Patents

Abstract

An isothiocyanate vapor-generating agent containing a solution of an isothiocyanate dissolved in an oily liquid having a vapor pressure of 2 mmHg or less at 30 DEG C. A germ-desroying treatment method using vapors of an isothiocyanate and a germ-destroying treatment apparatus are also disclosed.

Description

Utilize isothiocyanates steam to carry out sterilization treatment method

The present invention relates to solution of isothiocynate vapor-generating agent, and utilize this steam to carry out sterilization treatment method and implement the equipment that this sterilization is used.

Various foods, the glassware of lens one class, leather boots, the leather and fur products of leather jacket and fur cover and so on, and by starching coating or the glue goods that glue or cellulose are formed, often mouldy easily.Mouldy meeting is shortened the article effective life greatly or is caused article processing repeatedly.

Except mouldy, the harmful microbe excessive increase often also shortens the article effective life greatly or causes article processing repeatedly.For example concerning food, because the excessive growth of bacterium, can occur fermenting or the problem of the class of poisoning by food.

Article and oxygen absorbent are packed together with sealing and packing material, and make oxygen concentration in the packing maintain 1% or lower level, in case the method that article go mouldy is a known technology.Though this method can prevent effectively that by going mouldy that aerobe causes it is not the effective measures that prevent to cause the anaerobic bacteria excessive increase of poisoning by food or fermenting.

Ethanol cast charge and article are packed together, and make alcohol vapour be full of package interior to prevent the excessive increase of common bacteria and the generation of going mouldy, also be a kind of known technology.And comparatively speaking, otherwise amount is used expensive ethanol, otherwise this method can not obtain gratifying effect.

In addition, some anti-agent and bactericidal agents of going mouldy are also known already.Because the great majority in this class chemical substance are harmful to human body, so the use of this class chemical substance is strictly controlled.

Some have the natural prodcuts of antibacterial action and also early know for people.People know that scurvy grass has fine bactericidal action.Utilizing isothiocyanate to come food is carried out sterilization treatment, also is a kind of known technology.(hereinafter isothiocyanates abbreviates ISOTC as), a kind of main component of its Shi Eutrema yunnanense.The patent No. of for example having announced is the unexamined Japan Patent of clear-57-99182, disclose a kind of in containing the water of emulsifying agent the emulsification disperse be dissolved in ISOTC solution in the oil, and the composition of a kind of aqueous emulsions that obtains.This aqueous emulsions is mixed with food and make this food sterilization.But because not only food taste degenerates, and the ISOTC that sneaks in the food can make food spoilage, and therefore the ISOTC aqueous emulsions being sneaked into food is not the best way.The published patent No. is that the uncensored Japan Patent of clear-58-63348 discloses a kind of method of storing vegetables and fruit.In the method, vegetables and fruit are packed into artificial zeolite in a kind of container of sealing, and this artificial zeolite has the micropore that diameter is 5～10 , and are to soak in 5% the ISOTC solution in its concentration by weight.This zeolite does not give out the ISOTC steam of effective quantity in air, relative humidity be 90% or higher high humidity under, when generation was adsorbed onto the steam of ISOTC of the inside, zeolite absorbed airborne moisture content.The problem of this known method is, with having diameter is that the zeolite of the micropore of 5-10 costs an arm and a leg as the adsorbent of ISOTC, and the amount of the ISOTC that adsorbs in zeolite is significantly less than 5% of its weight, as you know, the artificial zeolite that has adsorbed ISOTC also has a shortcoming, be exactly only under high-temperature condition very, artificial zeolite just can distribute ISOTC steam.Therefore, adsorb the artificial zeolite of ISOTC, can not effectively be used as common ISOTC vapor-generating agent.

From top introduction as can be known, people have known that several to utilize the main component of scurvy grass (Wasabi) be the technology that ISOTC carries out the sterilization matchmaker.But from simple and easy to do this viewpoint, it is gratifying not having a kind of in these technology.

Main purpose of the present invention provides a kind of easy manufacturing, utilizes the ISOTC vapor-generating agent of the main component ISOTC of scurvy grass (Wasabi), and the various goods that contain this propellant.

Another object of the present invention provides a kind of ISOTC of utilization steam and carries out sterilization treatment method.

Another object of the present invention is to implement to utilize ISOTC to carry out the equipment of sterilization treatment.

In order to finish the foregoing invention purpose, the present invention has carried out various researchs.Found that, notice that with this fact of ISOTC be foundation, by the concentration of control ISOTC in solution, can make things convenient for and the amount of the ISOTC that accurate control produces, this solution is when ISOTC being dissolved in 30 ℃ of temperature, and steam pressure is to make in a kind of fluid under 2mmHg (mercury column) or the lower situation.The sterilization treatment of also finding various goods can make things convenient for and carry out effectively, can obviously not degenerating owing to the working environment that various goods is contacted with ISOTC steam from solution recruit.

The present invention also finds, by the porous adsorbate being immersed in the above-mentioned ISOTC solution, can produce the ISOTC vapor-generating agent that can produce the ISOTC steam of necessarily controlling the size easily.

The present invention also finds, by above-mentioned ISOTC solution is mixed frozen glue sample material or is encapsulated into capsule, can easily produce the ISOTC vapor-generating agent that can produce the ISOTC steam of necessarily controlling the size.

The present invention also finds, uses above-mentioned ISOTC vapor-generating agent, can produce various goods with sterilization functions.

The present invention also finds, concerning ISOTC steam, very highly-breathable arranged as the plastic foil of polyethylene and polypropylene one class, with the seal-packed article of this class plastic sheeting, when they contact with ISOTC steam, can effectively carry out sterilization treatment.

Article are carried out sterilization treatment method according to a kind of being used for provided by the invention, it is characterized in that making article to contact with ISOTC steam, ISOTC steam is by being dissolved in the fluid, its concentration by weight is 0.01～50% ISOTC solution generation, or by the ISOTC vapor-generating agent generation that contains this solution, this fluid its steam pressure in the time of 30 ℃ is 2mmHg (mercury column) or lower.

According to ISOTC vapor-generating agent provided by the invention, be to contain the porous mass that soaked with above-mentioned ISOTC solution.

According to ISOTC vapor-generating agent provided by the invention, form by the material of the usefulness encapsulated that contains above-mentioned ISOTC solution.

According to ISOTC vapor-generating agent provided by the invention, form by the gel-like substance that contains above-mentioned ISOTC solution.

According to various products provided by the invention, contain above-mentioned ISOTC vapor-generating agent, and have sterilization functions.

Various goods are carried out sterilization treatment method according to a kind of being used for provided by the invention, it is characterized in that goods are used permeable material of ISOTC steam and ISOTC steam are packaged together.

A kind of goods are carried out sterilization treatment method according to the invention provides, it is characterized in that this method follows these steps to carry out: ISOTC is imported the sterilization treatment chamber with the form of steam or liquid particle, so that in process chamber, form the gas that contains ISOTC steam; Pending goods are put into process chamber, the gas that contains ISOTC steam in goods and the process chamber is contacted, thereby carry out sterilization treatment, behind the sterilization treatment end-of-job, from the sterilizing chamber, discharge air, from discharge air, remove ISOTC steam.

According to the equipment that is used for goods are carried out sterilization treatment provided by the invention, it is characterized in that this equipment has a sterilization treatment chamber, this chamber is furnished with the air inlet pipe that ISOTC steam is fed, and the discharge pipe that the air that contains ISOTC steam is discharged from the sterilizing chamber; The reservoir of the ISOTC that links to each other with air inlet pipe and hold; A device that is used to remove ISOTC steam that links to each other with blast pipe.

The term of Shi Yonging " sterilization functions " refers to " anti-microbial effect " in the present invention, and it has bactericidal action and two kinds of connotations of bacteria growing inhibiting." bacterium " term refers to bacterium, mould, spore as used herein, algae and other detrimental microorganisms.

Since the strong sterilization functions of the ISOTC steam that produces, ISOTC vapor-generating agent of the present invention, other industry that can be applicable to food service industry and run into harmful microorganism undue growth trouble.For example, this propellant can be used for preventing food to go mouldy, or is used to prevent at the various surfaces of solids, as glass, and mildew on the concrete walls wall.In addition, this propellant also can be used for the rotting of food, fermentation and freshness and degenerates.This propellant also can be used for eliminating the armpit bad smell of perspiration, the smelly one class body odor such as grade of pin, or decomposed by bacterium by anti-hidroschesis or sebum this class stink is no longer taken place.Because this propellant has the usefulness of killing fungi, so it can be used for handling by fungus-caused skin disease, as eczema or ringworm.

Use term " goods " among the present invention, refer to the various article of the puzzlement that is subjected to the harmful microorganism undue growth, as food and so on.

The various ester classes that belong to aliphatic (acid) ester and aromatic compound of isothiocyanic acid are arranged, all can be used as isothiocyanates, preferably use allyl group isosulfocyanate (CH ₂=CHCH ₂NCS) and alkyl isothiocyanates (RNCS, R: alkyl (alkyl)).In the present invention can be with mustard oil as isothiocyanates.

Below the present invention is described in detail.

(1) with fluid is the preparation of the ISOTC solution of solvent

According to the present invention, the solution that can give out ISOTC steam prepares by ISOTC is dissolved in the fluid.Under 30 ℃ of conditions of temperature, its steam pressure (saturated vapour pressure) is 2.66622 * 10 ⁵Pascal's [2mmHg (mercury column)] or lower, preferably 1.33311 * 10 ⁵Pascal's [1mmHg (mercury column)] or lower fluid can be used as the solvent of this solution.Because of the ISOTC solution in the fluid that is dissolved in low like this steam pressure, can suppress the evaporation of ISOTC preferably, and the steam that comes out from this solution contains the steam of fluid hardly, and therefore, the steam that comes out is ISOTC steam basically.Goods contact with this steam, can not produce owing to goods contact the trouble of bringing with fluid steam.Have its boiling point and be at least 180 ℃ of fluid that are preferably 200 ℃ or 230 ℃, generally can fine solvent as ISOTC.For example following grease can be used as the fluid solvent of above-mentioned solution.Fat and oil, as olive oil, sesame oil, safflower oil, sunflower oil, cotton seed oil, peanut oil, corn oil, rape seed oil, soya-bean oil, castor oil, cocoa butter, palm oil, caryophyllus oil, coconut oil, butter (fat), fish oil, fixed oil, lanolin oil, turtle oil, tsubaki oil, cured as liquid lanolin, carbon compound oil as liquid paraffin, liquid polyisobutene and squalane, higher fatty acids is oily as oleic acid, castor oil acid and lysine, the pure and mild oleyl alcohol of higher alcohol such as octyl group, polyalcohols such as polyethylene glycol, glycol polypropylene and glycerine, and by ester synthetic oil such as linoleic acid acetate (linolacetate) hexyl laurate.It is preferably scentless or almost be scentless to be used for fluid of the present invention.

ISOTC is dissolved in the amount in the fluid, is 0.01～50% by weight, preferably account for ISOTC oil solution weight 0.1～40%.

Even have only very a spot of ISOTC to exist, also can give out the intense stimulus smell, and be difficult to handle, but as utilize with the oil solution form of ISOTC in a manner described, the evaporation of ISOTC can effectively prevent.Thereby can have no being controlled of difficulty to ISOTC.This ISOTC solution also can be used as above-mentioned such ISOTC vapor-generating agent.

After the ISOTC lyolysis is in fluid, can add each auxiliary element as required, promptly be dissolved in this solution.But this class supplementary element surfactant; The material of HMW should be solid-state in normality, high molecular alcohol, high fatty acid, fatty acid ester or fat and oil; Colouring agent; Viscosity-control additive; And antioxidant.In addition, low alcohol, as ethanol, propyl alcohol or low boiling point solvent, as acetone, methyl, ethyl ketone, ether, ethyl acetone or hexane also can be used as auxiliary element, add in the solution in a small amount, with the evaporation capacity of control ISOTC from fluid.

According to the fluid that contains ISOTC of the present invention, can contain seed or the cell of ISOTO by handle,

Or the mode of dissolving in the fluid after it is ground is produced.Dissolving in the amount of the seed or the cell of fluid, is by 1～80% of fluid weight, preferably 10～60%.The fluid of this ISOTC of containing also can have in fluid under seed or the cell situation and uses.

(2) the ISOTC vapor-generating agent of solid state or gel state, and contain the preparation of the product of ISOTC vapor-generating agent.

Can prepare by the mode that porous mass is immersed in the above-mentioned ISOTC oil solution.ISOTC vapor-generating agent (abbreviating ISOTC solution below as), when being soaked into porous mass among the ISOTC, because the high evaporation rate of ISOTC, when porous mass one bubble is gone among the ISOTC, have a large amount of ISOTC steam to generate at once, ISOTC steam makes the working environment variation as a result.In addition, because the evaporability of the ISOTC that porous mass absorbs is still very strong, stably produce ISOTC steam in the time thereby make porous mass be difficult in a long period.According to the present invention, the measure that overcomes this difficulty be ISOTC to be dissolved in the form of above-mentioned fluid, be added to porous mass by immersion and get on.And, ISOTC easily and water react, so can not be stable with its storage.This problem also is to utilize the oil solution that ISOTC is prepared into above-mentioned it to solve.

As adsorbent, the material of filler all can be used as porous mass usually for those.This class examples of substances is: clay or clay class mineral, and as diatomite, loess, potter's clay, talcum, zeolite, U.S.'s atlapulgite, sepiolite, and other materials, as active carbon, silica, silica gel, alum clay, magnesia, siallite, Attagel and synthetic aluminosilicate.Porous mass can adopt different shape, as powdery, and the ball shape, spherical, prism-shaped and garden column.Material as porous mass preferably will be through dehydration or dry the processing, and making wherein, moisture removes fully.

Porous mass and solution are soaked, the method that can mix porous mass with ISOTC solution.With the method for ISOTC spray solution to the porous mass, the porous mass bubble in ISOTC solution method or other with it similarly method implement.Connect the amount of the ISOTC solution of absorption by porous mass by immersion, can be greater than the saturated absorption ability of this porous mass.General this uptake is 1～100% of porous mass deadweight, and the optimal absorption amount is by ISOTC solution and the decision of porous mass kind.

In the present invention, when porous mass with Powdered when being immersed in ISOTC solution, porous mass can be used traditional forming mode, makes it shapes such as flat board, ball, prism, the available flat-plate molded method that is shaped, compression molding method is implemented.When implementing molding procedure, available moulding binding agent.The example of moulding binding agent, organic binder bond, as carboxymethyl cellulose, polyvinyl alcohol, Sodium Alginate, inorganic binder, as bentonite, potter's clay, alum clay hydrogel, silicate gel.Various short fibers also can be used as the moulding binding agent as grey pertinax.In order to control the heat radiation of ISOTC steam, contain on the porous mass of ISOTC this coated measure of resin that can coated one deck can make the ISOTC vapour transmission, can further suppress ISOTC steam and from porous mass, distribute outward.

Another kind of ISOTC vapor-generating agent, the available method that above-mentioned ISOTC solution is encapsulated in the capsule prepares.Encapsulated can realize with known the whole bag of tricks.For example, a kind of method is the solution of ISOTC solution and a kind of macromolecule weight, respectively by the inside and outside nozzle of a biliquid nozzle, sprays in the water sample medium simultaneously, and this is a kind of surface body polymerization.The also available another kind of method of encapsulated realizes.In this method, ISOTC solution or flooded the porous mass of ISOTC solution mixes with a kind of easy molten material.A little kind materials at room temperature are solid-state, and its fusing point is 100 ℃ or lower, is preferably between 40～60 ℃.Make the cooling of mixed mixture and solidify, then it is ground.In this method, fusible material can be above-mentioned high molecular alcohol or their ester, and fat and oil are cured etc.Encapsulated can realize with another kind of method.In this method, ISOTC or flooded the porous mass of ISOTC solution mixes (as epoxy resin ingredient or unsaturated polyether resin Composition) with a kind of thermoplastic resin component of having melted, and this component at room temperature or be liquid under 100 ℃ or lower temperature.Mixed mixture cooling is solidified, then they are ground.ISOTC solution with as cyclodextrin (cyclodextrin), a class inclusion enclave chemical combination such as urea, formation medium reaction also can provide the encapsulated material.

In the present invention, above-mentioned ISOTC solution flooded the porous mass of ISOTC solution, contained the porous mass molded article of ISOTC solution, and the material of ISOTC solution after with encapsulated, and all use used pack material seal packing back.Should one of them part can allow the ISOTC steam see through as packaging material.The example of this based packaging material can be made by polypropylene, polyethylene or these class plastics of ethylene/vinyl resin acetate copolymer, can allow film, thin plate or the container of ISOTC vapour transmission.Can not see through the packaging material that the plastics of ISOTC steam are made, can be by for example using the laser beam method, the measure of making micropore thereon makes it the packaging material of ISOTC vapour transmission.In addition, paper, nonwoven webs, surface-treated paper or nonwoven webs, or with the paper that can form through the plastic sheeting of ISOTC steam, nonwoven webs, or yarn fabric laminated product also can be used as above-mentioned packaging material.

In addition, the ISOTC vapor-generating agent also can be produced by above-mentioned ISOTC solution is mixed this measure of gel-like substance.

Various known gel-like substances all can use, gel-like substance for example: alginic acid, polyvinyl alcohol, dextrin, starch, cellulose, carboxymethyl cellulose (Carboxymethyl), gelatin, deer horn Lay genin, agar.A kind of method of ISOTC solution being mixed gel-like substance is the mixing of ISOTC solution, to permeate in the ready-made gel-like substance; Other method is that ISOTC solution is joined in producing the gel-like substance process, preferably it is joined in the raw material of producing gel-like substance, also available other similar method with it.The content of ISOTC in gel-like substance is generally 0.05～20% of (gel) weight, is preferably 0.5～10%.The content of concrete ISOTC is by the gel-like substance kind decision of using.When adding ISOTC solution in the gel-like substance, ISOTC can make the encapsulation capsule form in advance and use.

According to ISOTC vapor-generating agent of the present invention, normally put into and be encapsulated in a kind of paper bag through waterproof or anti-oil processing, plastics make the bag or container in use.As a kind of plastic film bag or container, it should be able to see through ISOTC steam.

According to the present invention, various goods with sterilization functions can be produced by utilizing above-mentioned ISOTC vapor-generating agent.For example, add as helper component, above-mentioned ISOTC solution, flooded the powdery porous mass of ISOTC solution, or known traditional coated component of the material of ISOTC solution after with encapsulated, as binder component, coating composition, or red ink paste used for seals component all can be used as the goods with sterilization functions.This based article can be in every field, as in food service industry, and the packaging material industry, building material industry, in, as having the coated component of sterilization functions.

According to the present invention, also provide as paper, nonwoven webs, a class thin layer or a thin-film material such as plastic sheeting, but on these materials all coated contain the coated component of above-mentioned ISOTC material.In this class laminar article, can be at two of material or coated on the one side wherein, or each layer asked and carried out coated in stratified material.As a kind of lamelliform material with sterilization functions, it can be used for food service industry, and the packaging material industry is in the every field such as building material industry.

According to the present invention, have sterilization functions sheet material (as hardboard, semihard cardboard, insulation board, board made of particles etc.), the available above-mentioned powdery porous mass that flooded ISOTC solution, with wood chip, fibrous material such as art powder and glue mix, and produce through compression molding method.Grey rubber cardboard with sterilization functions, the also available above-mentioned Powdered porous mass that contains ISOTC mixes with the slurry that burnt gypsum reaches as pulp material, wood pulp material one class, makes through the method that is molded into plate then.Plastic plate with sterilization functions, the also available Powdered porous mass that flooded ISOTC solution, with the resin component that can under environment temperature or cryogenic conditions, harden, mix as epoxy resin ingredient or unsaturated polyester resin component, make with compression molding and method for curing.This based article is used as sterilization in building material industry, i.e. mildew-resistant sheet material (board-like material).

In addition, according to the flushing liquor that the invention provides a kind of ISOTC of containing, promptly be dissolved in its concentration by weight in the ethanol and be 0.01～5% ISOTC solution.At this used alcohol, can be hydrous ethanol, but the content of its water should be 50% or less by weight.Because ethanol itself has strong sterilization functions and mildew-proof function, be good so use this flushing liquor.When ISOTC with a kind of solution form that is difficult to evaporated liquid, be added in the ethanol and disperse after, when being sprayed onto on the object as a kind of flushing liquor, the evaporation of control ISOTC from the deposit solution that deposits ISOTC is possible.After ISOTC was dissolved in the ethanol with a kind of form of oil solution, a kind of had the flushing liquor of good shelf characteric just can obtain.Be critical even hydrous ethanol is also irrelevant.According to flushing liquor of the present invention, can add surfactant, high molecular weight material, the viscosity control medium, antioxidant, and pulverizing is the auxiliary interpolation components such as adsorbent of superfine particle.

Flushing liquor of the present invention is packed in the suitable sprayer unit, during use, makes flushing liquor pass through specific nozzle.The flushing liquor device that the most suitable the present invention uses is a kind of suspended particulates type sprayer unit that uses ejection medium.In general, use the suspended particulates type sprayer unit method of flushing liquor of the present invention to be, flushing liquor is packed into to be had in the airtight container of nozzle, in this container of under certain pressure ejection medium being packed into then.Known liquefied carbon hydrogen compound gas, as propane, normal butane, iso-butane, pentane, isopentane and their mixture all can be used as ejection medium of the present invention.In general, liquefied petroleum gas or liquefied natural gas also are suitable for this use, also can use as fluorine dichloro-methane gas.

Because when ISOTC is dissolved in 30 ℃ of temperature, its steam pressure is equal to or less than the solution that the fluid of 2mmHg (mercury column) forms, and so the performance that has good inhibition ISOTC to distribute is very easy to the disposal of ISOTC solution.In addition and since one for a long time in, ISOTC solution gives out ISOTC steam gradually, the hold facility that the ISOTC steam of ISOTC solution produces ability is good.So ISOTC solution itself just can be used as the ISOTC vapor-generating agent, and can be used as bactericide in industry-by-industry, mould inhibitor removes the agent of (smelly) flavor, antistaling agent etc.In addition, ISOTC solution also can use as the special material with sterilization functions in industry-by-industry.

In above-mentioned porous mass of crossing with the ISOTC solution impregnation and seal capsule that ISOTC solution is housed, its ISOTC vapor evolution ability has been subjected to strong inhibition, so can be them as the solid producer that distributes ISOTC, be used for as food service industry, the packaging material industry, every field such as building material industry.

The above-mentioned coated component that contains ISOTC solution is used the porous mass of ISOTC solution immersion, or is packaged with the microcapsules encapsulating material of ISOTC solution, and the functional material that can be used as sterilization functions is applied to every field.The coating that contains this component gives out ISOTC steam gradually and reaches the sterilization functions of expectation.

The lamelliform material of above-mentioned this coated of use component can give out ISOTC steam gradually, so it can be at food, packaging material, printing material is in such industry-by-industry such as construction material, as the lamelliform functional material with sterilization, mildew-resistant, fresh-keeping and deodorize performance.

Contain according to the present invention ISOTC solution like gelatinous material, it is in a kind of mode that very suppresses, that little by little does segment length's time gives out ISOTC steam, and this material has the hold facility of good bactericidal action.Thereby it helps using in industries such as food.

Contain the spray wine liquid of ISOTC solution according to the present invention, use it and be sprayed at above the object as liquid droplet.Since be this material, restrain strong ISOTC smell beastly because ISOTC sprays with the low concentration solution state, so that surrounding environment is not had special bad influence.Because ISOTC contacts with object with liquid form, its role is more faster with the vapor form role than ISOTC.This flushing liquor is widely used in the detrimental microorganisms growth or bad smell brings in the different field at problem place, and for example, the performances such as sterilization, mildew-resistant and deodorizing by it are applied in the food service industry.Because ISOTC can show a kind of antibacterial action to the hair tinea, flushing liquor of the present invention can be used to treat skin disease (for example treating eczema).

(3) Biocidal treatment method and use equipment thereof

According to the present invention, a kind of Biocidal treatment method of goods comprises making goods contact this step with ISOTC steam.The gaseous state ISOTC steam that contacts with goods, its concentration by volume is at least 5/1000000ths, but should be lower than the saturated concentration of ISOTC steam.Its concentration is generally 20/1000000ths～5000, is preferably 50/1000000ths～1000, and this should select according to different treatment articles.According to the concentration of ISOTC gas, be 0.1～60 minute general time of contact, when the ISOTC vapour concentration is 20/1000000ths when above, is preferably 0.5～30 minute time of contact, and processing time length is according to processed goods choose reasonable.

In the present invention, the goods that preparation contacts with ISOTC steam, available polypropylene, polyethylene or ethylene one class plastic package material encapsulate it.Prove through present inventor's check, above-mentioned packaging material have ISOTC steam height hold facility, the goods of packing with this based packaging material, after standing sterilization treatment, no longer to being harmful to the pollution sensibility second time of mushroom, in between this packing articles storage life, can effectively prevent the infection of harmful bacteria.

Be used for the ISOTC vapour concentration that contacts with packaged goods, preferably be higher than the concentration that is used for the ISOTC steam that contacts with unpacked goods, this concentration generally gets 100/1000000ths～5000.

This packaging material that are used for packing articles are a kind of abbreviations that have a wide reach, and it comprises the different shape container, film and layer material.One of various suitable method of packaged article is, goods packed in the bag, and it is encapsulated.Another kind method is, goods are put into the open containers of as dish and so on, and opening part is sealed up with film subsequently.Another kind method is, goods are packed in the box, gets up with film wrapped subsequently.Also have a kind of method to be, the goods of liquid state are put into plastic containers, with lid it is covered then.

Use term " packings of goods " in the present invention, refer to the goods that comprise in the packing, under packed state, can prevent the pollution that it is subjected to harmful mushroom, and not only be meant goods are sealed in the packing, make it isolated with ambient air.

The packaging material that are used for packing articles have at least a part can make the ISOTC vapour transmission.For example this based packaging material is a polyethylene, polypropylene, ethylene, or container, layer material and film that the plastics of ISOTC vapour transmission are made such as ethylene/propene copolymer.Can not make the material of ISOTC vapour transmission,,, then also can be used as the packaging material that make the ISOTC vapour transmission as being processed into micropore thereon with the laser beam method as nylon, aluminium foil, the packaging material made.In addition, paper, nonwoven webs, or with the plastics that can see through ISOTC steam, surface-treated paper or nonwoven webs material, or paper, the laminated product of nonwoven webs and cloth also can be used as packaging material.

According to the present invention, when carrying out sterilization treatment, packing or unpacked goods will contact with the gas that contains ISOTC steam, this contact the whole bag of tricks of realization is arranged: a kind of method is that package is put into the air-tightness chamber, and ISOTC steam or liquid feed this chamber with Sprayable; Another kind method is that package is put into the airtight container that has fed ISOTC steam in advance, after a scheduled time, this package is taken out.A kind of straightforward procedure is that goods are packed in the big polybag, then ISOTC is sprayed in this bag with liquid form, or the ISOTC vapor-generating agent is fed in this bag.

Distributing of ISOTC steam, available above-mentioned solution, or the various solid material that contains ISOTC solution, or ISOTC itself realizes.Concerning ISOTC solution or contain the ISOTC solution solids material, ISOTC steam wherein, can be certain control the size slowly comes out.

When the goods of having packed, when contacting with ISOTC steam with above-mentioned method, ISOTC steam enters in the packing, and after waiting to finish sterilization treatment, the ISOTC vapor permeable packaging material of feeding are dispersed into outside the package gradually.Concerning the sterilization viewpoint, the concentration of the ISOTC steam in package is preferably high, and ISOTC steam was remained in the package in a long period.In general, the ISOTC vapour concentration preferably is 10/1000000ths, and keeps in package 10 minutes, or the longer time.Because the ISOTC vapor evolution is outside package, so as time passes, the ISOTC vapour concentration in package reduces gradually.ISOTC concentration decline degree can be controlled by in advance adsorbent being put into package.After adsorbent is put into package, during goods contact with ISOTC steam and handle in packing, adsorbents adsorb ISOTC steam.After finishing dealing with, adsorbent still can give out ISOTC steam, thereby makes in the package ISOTC vapour concentration retention time controlled.Because ISOTC steam too is incorporated in the goods, can make the quality of goods be subjected to bad, so not wishing ISOTC steam stays in the package for a long time, best suitable selection packaging material kind, determine to put into sorbent quantity, make that the ISOTC vapour concentration reduced to 10/1000000ths or lower in the package in 48 hours.

Unpacked goods can carry out sterilization treatment earlier, and then encapsulate with packaging material, make it to avoid harmful mushroom and pollute.Be in fear of after sterilization treatment, occur owing to ISOTC steam excessively penetrates into when making psychological that the quality of goods degenerates in the goods, the way that conforms with hope is, in advance together with goods and adsorbent package, too much ISOTC steam can be absorbed for adsorbent, above-mentioned various porous mass all can be used as such adsorbent and uses.

ISOTC steam in the package of the goods of process sterilization treatment, As time goes on can be dispersed into gradually outside the package, and when package turnover and sealing, ISOTC steam almost drains, so the people of the product of unpacking can not smell the niff of ISOTC.

According to the present invention, harmful mushroom can contain ISOTC steam by introducing and makes it to eliminate in the seal cavity.Therefore, this airtight space and the goods that are placed in this space can make it aseptic.At this use " seal cavity " term, refer to a kind of space that air wherein can not freely be linked up with outside air.The space of various buildings, as the warehouse of factory, the room of hospital, the cabin of freighter, the space by cover or film (plate) separate reaches various containers, all can be the example of seal cavity.

The present invention proposes a kind of being used for goods is carried out sterilization treatment method, it is characterized in that this method may further comprise the steps: with the form of ISOTC steam or liquid droplet, import the sterilization treatment chamber, make and form the air that contains ISOTC steam in this process chamber, goods are put into this process chamber, goods are contacted with the gas that contains ISOTC and carry out sterilization treatment, after sterilization treatment work is finished, from process chamber, discharge the air that contains the ISOTC steam, and from the air of discharging, remove ISOTC steam.

In the present invention, a kind of equipment that is used for goods are carried out sterilization treatment also is provided, it is characterized in that this equipment has an air inlet pipe that ISOTC is imported process chamber, and blast pipe that the air that contains ISOTC steam is discharged from process chamber, the container of the ISOTC that links to each other with air inlet pipe and hold, one links to each other with blast pipe, is used to get rid of the device of ISOTC steam.

This sterilizing methods and equipment thereof are described in detail as follows:

In above-mentioned method and apparatus, use sterilization treatment chamber (present disclosure abbreviates process chamber later on as), as a sterilization treatment chamber, the pending goods of its handlebar are contained in inner space wherein, this space is bubble-tight, so that its gas inside can not be overflowed.This process chamber has one ISOTC imported air inlet pipe inlet in the chamber with steam or liquid droplet mode, and the air that handle contains ISOTC steam is discharged outdoor exhaust outlet.

The structure of process chamber, can according to the goods in the process chamber handle be continuously or the mode of in batches intermittently carrying out reasonably selected.Carrying out continuously in the mode, process chamber have import partly and outlet partly, this two partly all is designed to air tight structure, preventing that working gas is overflowed in the process chamber, this designing two portions becomes to have only goods to enter or when taking out, process chamber just can be opened.The import and export of air tight structure can known manner design.For example, this two part of process chamber can be closed with the dividing plate that artificial rubber or plastic sheet material are made, and a kind of air tight structure is provided.To the goods sterilization treatment is interrupted mode when carrying out, and is provided with a door that allows the air proof that goods put into and take out on process chamber.

Deposit the container of ISOTC with the solid form of vapor form, liquid form or dipping, link to each other with the air inlet pipe of process chamber, be preferably in agitator or heater are housed in this container, so that according to the needs of sterilization treatment, ISOTC is sent into process chamber with steam or liquid droplet form from this container.

A kind of goods Biocidal treatment method divides several steps: (A) goods are sent into process chamber, (B) with steam or droplet form ISOTC is imported process chamber, make and form the air that contains ISOTC steam in this chamber.At process chamber, when carrying out work in a continuous manner,, be after (A) step (B) step of ISOTC importing process chamber.When carrying out work in interrupted mode, (B) step is before goods are put into process chamber (A) step.

ISOTC enters the mouth by air inlet pipe with steam or droplet form, enters process chamber from reservoir.When importing with vapor form, ISOTC elder generation carburation by evaporation forms the gas that contains ISOTC.When importing with the droplet form, ISOTC sprays into process chamber with a kind of gas from mixed jet.Air, nitrogen, carbon dioxide packing all can be used as this gas.

Evaporation ISOTC, the method that makes it to become the gas that contains ISOTC steam is: liquid ISOTC or the heating of ISOTC solution, make it to form the steam that mixes basically with gas.In one approach, ISOTC steam is produced by the ISOTC vapor-generating agent, and makes it to mix basically with gas.Other method is, makes gas by containing the liquid of ISOTC, makes this gas have ISOTC steam.The concentration of the ISOTC of gaseous state is 5/1000000ths or higher.The upper limit of ISOTC vapour concentration is equivalent to the saturated vapour pressure of ISOTC steam in this gas.Common ISOTC vapour concentration is 10/1000000ths～5000.Use injector, gas is mixed with ISOTC or its solution, when suction, can obtain containing the gas of ISOTC steam and ISOTC solution droplet.Such gas is imported process chamber, also is a kind of effective ways.

Make goods carry out sterilization treatment method, also have the step (C) that goods are contacted with the gas that contains ISOTC steam.In this step, goods kind different change of the temperature during processing because of handling.In general, treatment temperature is 0～100 ℃, gets 20～60 ℃ usually.When handling fresh food, can adopt environment temperature, or 0～15 ℃ low temperature.The not special regulation of the pressure of process chamber.Decompression or pressurized measure all can adopt, and in general, processing is depressed at decompression state or normal atmosphere and carried out.When in the system that works continuously, carrying out sterilization treatment, in order to prevent that the gas in the process chamber is overflowed when opening or closing the import and export of process chamber.Be preferably under the high negative pressure of-5～-50 millimeters of water and handle.During to its another part, the gas part of preferably rotating fan or need being fed siphons away a part of original gas earlier, and the gas in the process chamber can evenly be mixed from a part gas bleeding of process chamber.

The sterilization treatment method also comprises one after to goods sterilization treatment end-of-job, with the gas in the process chamber, discharges outdoor step (D), and the ISOTC that contains that discharges in the outdoor gas is removed step (E).With a suction pump gas in the process chamber is discharged, will remove the then available cooler of ISOTC steam in the gas of discharging, the absorption tower, or similar device is implemented.As long as cooler can preferably can be cooled to any cooling structure about 0 ℃ with the gas cooled of discharging to the temperature that is lower than process chamber.The gassy adsorbent, as active carbon, sepiolite, silica, alumina.The combination utilization on cooler and absorption tower can effectively be removed ISOTC steam from the gas of discharging.Brief Description Of Drawings.

Shown in Figure 1, how to finish view to the goods sterilization treatment.

Fig. 2 is the equipment flowsheet that goods is carried out sterilization treatment,

Fig. 3 carries out the key diagram of sterilization treatment in confined space.

Realize best mode of the present invention.

Referring to Fig. 1.Blower fan 1 and 4, ISOTC steam generating chamber 2, sterilization treatment chamber 3, ISOTC absorption plant 5.There is the structure that can deposit ISOTC therein in ISOTC steam generating chamber 2, and in this case, ISOTC can solution or the form of gel.In addition, ISOTC also can be deposited in a kind of porous mass by dipping, and the state of ISOTC is not specially limited, as long as can produce ISOTC steam.

In the ISOTC vapor absorption device 5 adsorbent is arranged, it can remove active carbon, sepiolite containing ISOTC steam in the gas in the feeder by suction-operated, diatomite, alumina, silica, silica gel, silica-alumina, magnesia, or zeolite all can be used as adsorbent in general.All any adsorbents that can adsorb ISOTC steam all can use.

The sterilization treatment of goods, come into effect by starting fan 1, blower fan 1 makes gas enter steam generating chamber 2 by pipe 6, and make by pipe 10 gases that contain ISOTC steam are sent into the process chamber 3 that goods are housed from generation chamber 2, usually with the carrier of air as ISOTC steam, nitrogen and carbon dioxide also can be used as carrier.The portion gas that ISOTC steam generating chamber 2 ejects, through pipe 11, valve 12 is to pipe 9 reciprocation cycle, with the concentration of control by the ISOTC steam in the gas of pipe 10.

ISOTC steam mixes with gas in the process chamber 3 and when reaching predetermined concentration, just stall of blower fan 1, and valve 13 cuts out, make process chamber 3 maintain sealing state.This sealing state is kept a predetermined period of time, so that by absorbing ISOTC goods are handled.Be preferably in and adorn a fan in the process chamber 3, stir indoor gas, to promote ISOTC steam in indoor disperse.ISOTC steam in process chamber, concentration by volume is 5/1000000ths～5000, is preferably 10/1000000ths～2000, through the processing of certain hour, can make goods obtain satisfactory bactericidal effect.The goods kind of the time of handling because of handling, and the concentration of ISOTC steam is different and different in the process chamber, it is fixed to go with same rule.But in general, the processing time is 1～60 minute, preferably 5～20 minutes.

After finishing sterilization treatment, valve 15 is opened, starting fan 4, through absorption plant 5, pipe 22 enters atmosphere gas in the process chamber, during exhaust, negative pressure appearance occurs for preventing inner treatment chamber, can be communicated with an open to atmosphere valve with process chamber.In absorption plant 5,, can remove the ISOTC steam that contains in the gas owing to wherein adsorbent is housed.In absorption plant 5, adsorbent just can sop up the ISOTC steam in the gas with after gas contacts a period of time.Can be by the gas that part is discharged from absorption plant 5, through pipe 18,19, valve 20, pipe 17 circulates, and controls the length of time of contact.In process chamber 3 and the absorption plant 5, can adorn heater and cooling device, to reach to temperature controlling.When the adsorbent in absorption plant 5 is saturated, can feed absorption plant 5 to thermal medium, the adsorbent reduction is upgraded resemble steam.

When gas in the process chamber mixes, can directly spray into process chamber at ISOTC of the present invention, and replace the ISOTC steam that feeds the evaporation of above-mentioned ISOTC steam generating chamber with ISOTC liquid or its solution.ISOTC is separated from gas, and the also material that reacts of available energy and ISOTC carries out as the chemical reaction of solid amine, and replaces the use of adsorbent.

The chamber of any air tight structure all can be used as the sterilization treatment chamber.The gas that contains ISOTC steam not only can feed in the process chamber 3 as described above discontinuously, and feeds serially, but should discharge by pipe 14 simultaneously.Under continuous feeding situation, a part of gas through pipe 14 is discharged can pass through a flow control valve, makes it recirculation and returns process chamber 3.

Sterilization treatment in process chamber 3, both available continuation mode carries out, and also available discontinuous manner is carried out, and when adopting continuation mode, goods enter process chamber 3 with constant speed.

Among Fig. 2, sterilization treatment chamber 1, ISOTC steam generating chamber 2, blower fan 3, gas distributor 4, ISOTC absorption plant 5.

Sterilization treatment chamber 1 and ISOTC steam generating chamber 2 are communicated with internally by the pipe 6 that a switch valve 7 is housed betwixt.And sterilization treatment chamber 1 and blower fan 3 are communicated with internally by the pipe 11 that a switch valve 12 is housed therebetween.Blower fan 3 and gas distributor 4 are communicated with internally by the pipe 14 that a switch valve 15 is housed therebetween.

Gas distributor 4 can be the large diameter pipe minor structure of a closed at both ends, is connected with escape pipe with an air inlet pipe.

Gas distributor 4 and ISOTC absorption plant 5 are communicated with internally by the pipe 16 that a switch valve 17 is housed therebetween.And gas distributor 4 and ISOTC steam generating chamber 2 are communicated with by the pipe 18 that a switch valve 19 is housed therebetween.Gas distributor and sterilization treatment chamber 1 are communicated with by the pipe 21 that a switch valve 21 is housed therebetween.In addition, the both sides up and down of blower fan 3 are communicated with by the pipe 24 that a flow control valve 25 is housed on it, and 3 pairs of gas transporting velocities of blower fan are controlled.

Each switch valve is electronic control, can be controlled on control flow.

Above-mentioned sterilizing installation, it is as described below that goods are carried out the sterilization treatment situation: at first the door 10 of process chamber 1 is opened, put into pending goods, close to the doorstep 10, starting fan 3, at this moment valve 9,17, and 21 still are in and close, and open valve 7,12,15,19.After blower fan 3 startings, make gas flow in the process chamber 1, then make gas through blower fan 3, gas distributor 4, the route ring that ISOTC steam generating chamber 2 and process chamber 4 are formed follows mobile.The result of gas reciprocation cycle enters in the circulating current ISOTC steam that evaporates in the ISOTC steam generating chamber 2, enters process chamber 1 at last, so make the ISOTC vapour concentration in this chamber more and more high.When the ISOTC vapour concentration reaches a predetermined value, open valve 21, to shut valve 7,19, thereby make the gas of the ISOTC steam that contains predetermined concentration, reciprocation cycle between each chamber need not to cut off the passage towards ISOTC steam generating chamber 2.To the ISOTC concentration monitor in the recyclegas, by being contained in concentration determination meter control on process chamber 1 or the pipe 11.For example gas chromatograph separator or conductance instrument all can be made this concentration determination meter and use.

Behind a predetermined period of time, open valve 17, shut off valve 19,21, opening and close with timer of valve controlled automatically.Then purge gas is fed process chamber 1 through pipe 8, though air also can be made purge gas usefulness, the air or the nitrogen that use sterilization treatment to cross are better.Purge gas is discharged from process chamber 1 through pipe 11 after feeding process chamber 1, and again through blower fan 3, gas distributor 4 feeds ISOTC absorption plant 5.Therefrom remove the gas of ISOTC, enter atmosphere through pipe 30 as the gas of having used.When being reduced to predetermined value with the ISOTC vapour concentration in the gas of crossing, just close blower fan 3, open door 10, the goods of having handled well are taken out.Arrive this, sterilization treatment process constipation bundle.By repeating above-mentioned operating process, another sterilization treatment process can begin again to carry out.

Though Fig. 2 represents a sterilization treatment device that is interrupted working method, by using a kind of structure that can send and take out goods continuously to, the sterilization treatment device that also can make continuously-running duty uses.The basic operation of continuously-running duty, with the basic operation of above-mentioned interruption working method be similar.But, necessarily, continuously feed the sterilization treatment chamber the gas of the ISOTC steam that contains predetermined concentration.For this reason, on the connection pipe 20 between gas distributor 4 and the process chamber 1, the switch valve 21 (seeing shown in Figure 2) that can control gas flow is housed, make a part that feeds the gas in the gas distributor 4, enter process chamber 1 by pipe 20, control the ratio of the gas flow of the pipe 20,18 of flowing through with this.

From above-mentioned sterilization treatment as can be known, various goods, as food, available a kind of safe and effective mode is carried out sterilization.When handling food, after processing finished, the gas that contains ISOTC steam in the process chamber was together sent into the ISOTC absorption plant with purge gas, by suction-operated ISOTC was removed there, then, these gases was entered atmosphere.So in the entire process process, the intense stimulus smell of ISOTC can not be distributed, and can avoid the pollution of working environment.

Fig. 3, ISOTC steam raising plant 1, seal cavity 2, ISOTC vapor absorption device 3, blower fan 4,5.

ISOTC steam raising plant 1 is equipped with the heating and cooling device, and design has the container that wherein can hold ISOTC.At the ISOTC of device in 1, can liquid, solution or gel form deposit, ISOTC also can be placed in the device 1 by the form that dipping infiltrates in a kind of porous mass.

ISOTC vapor absorption device 3 wherein is placed with adsorbent, by suction-operated, removes sending into the ISOTC steam that contains in the gas, as long as can absorb ISOTC steam, any adsorbent all can use.

When seal cavity 2 is made sterilization treatment, start blower fan 4, make air pass through ISOTC steam generating chamber 1, make the gas that contains ISOTC steam, enter seal cavity 2 through pipe 8 through pipe 6, when the ISOTC vapour concentration in the space 2 reaches predetermined value, shut valve 7, open valve 10, gas is circulated in space 2, therefore, in seal cavity 2, realized sterilization treatment.

Processing stops blower fan 4 after finishing, and shuts valve 10, opens valve 15,12, starting fan 13, and (school person: should be 5) makes purge gas enter seal cavity 2 through pipe 14 thus, thereby makes the gas that contains ISOTC steam, and 2 enter ISOTC absorption plant 3 from the space.In absorption plant 3, through suction-operated the ISOTC steam that contains in the gas is removed, last, the gas that does not contain ISOTC steam enters atmosphere through pipe 16.With similarly mode seal cavity 2 is carried out disinfection, the ISOTC steam of using in the disinfecting process is discharged from seal cavity 2.Like this, the smell excitatory that not do not cause in the seal cavity 2 by ISOTC steam.

Though air also can be used as above-mentioned purge gas,, the air or the nitrogen that use sterilization to handle are better.

In the present invention, the size of seal cavity preferably at least should be the ISOTC steam raising plant 1 of a part, blower fan 4 and 5, and ISOTC vapor absorption devices etc. install in seal cavity 2, but when this seal cavity was very little, they have to be contained in its outside.

The concentration of the ISOTC steam in seal cavity 2 is 5/1000000ths～2000, is preferably 10/1000000ths～500.The time that ISOTC steam is kept in seal cavity is 1 minute to 12 hours.When adopting above-mentioned standard to carry out sterilization treatment.Harmful microorganism in seal cavity almost can all be eliminated.

According to said method, the air of seal cavity, the surface of machinery and equipment, all sterilization effectively.In addition, because ISOTC corroding metal not, so do not exist to the metal erosion worry.And even there is the ISOTC steam of denier not to be eliminated, it is also harmless to human body.

Below by example explanation the present invention, but this never is only limited to the present invention in these examples.Hereinafter, except as otherwise noted, part and % all refer to weight to be benchmark.

Example 1:

Allyl group isosulfocyanate is dissolved in the edible oil of using as fluid (as soya-bean oil), to make ISOTC solution.

The degree of the emission capabilities time to time change by measuring allyl group isosulfocyanate, this solution is tested, in the test, 5 gram ISOTC solution are placed on that (diameter is 75mm, highly be 20mm) in the pallet (Schale), at ambient temperature, the odour intensity that pallet gives out, with the following parameters is according to judging that judged result is listed in the table 1.

A: probably differentiate penetrating odor with eyes,

B: mustard gas smells with one's nose

C: can smell a spot of mustard gas

D: can't smell smell

For further comparison, 0.05 gram allyl group isosulfocyanate is placed in the pallet of above-mentioned size, and similarly tests.In 30 minutes, penetrating odor can make that eye is fine roughly feels the distributing of allyl group isosulfocyanate, but after one hour, just can not check out the existence of smell.

Table 1

The concentration % of allyl group isosulfocyanate	Elapsed time (my god)
		30 (minute) 15 10 15 20
	0.5		B C C C C D
1		B B C C C C
	5		A A B B B C
10		A A B B B B
	20		A A A B B B
30		A A A A B B

Example 2 contains ISOTC solution with what allyl group isosulfocyanate was dissolved in the corn oil the various concentration of preparation.Each solution (about 9 grams) is placed on diameter 85mm (floor space 56.7cm ²), in the pallet of high 15mm, then it is put into the constant temperature of one (volume is 88 liters), in the airtight container, and the evaporation capacity of wherein allyl group isosulfocyanate detected.Testing result is listed in table 2.Listed evaporation capacity is to be divided into 100 parts with the solution weight in pallet at the beginning to make radix in the table 2, measures to have evaporated what parts in per 100 parts.

Table 2

ISOTC concentration	Evaporation capacity (umber by weight)
		Elapsed time (hour) 123456
	100 50 23 20 5 0.5		13.3 22.9 33.7 47.0 56.2 66.2 9.0 18.5 27.0 33.9 37.1 39.9 7.8 15.2 20.7 24.9 27.2 29.8 5.9 10.5 14.6 17.5 19.3 19.7 1.3 2.2 2.9 3.4 3.9 4.2 0.14 0.2 0.26 0.3 0.33 0.36

Example 3

With allyl group isosulfocyanate, be dissolved in the corn oil preparation concentration and be 50% ISOTC solution.Be about 3.5mm, 100 parts of the calcined diatomite particles of the about 1mm of diameter are produced the ISOTC vapor-generating agent with 40 parts of above-mentioned solution impregnation.Check the evaporation capacity of ISOTC in example 2 same modes; Time dependent situation, and will the results are shown in the table 3, the evaporation capacity of the allyl group isosulfocyanate of drawing up in table 3 is so that the total solution weight branch work in pallet is that what part allyl group isosulfocyanate solution are each hundred parts of weight of cardinal measurement evaporate for 100 parts in the zero hour actually.

Table 3

Elapsed time	1 2 3 4 5 6
		(by weight) Zheng Fa umber	4.4 10.1 12.9 14.3 14.6 14.9

Example 4:

Allyl group isosulfocyanate is dissolved in the corn oil, and the concentration that preparation is counted by volume is 50%, 20%, 10% and 5% solution.Mould to be tested is placed in the confined space under the room temperature condition, and makes mold exposure in the steam that comes out from above-mentioned solution.Cultivated 3 days down at 28 ℃ then, check fungus growth situation after 3 days, assay is listed in table 4.

The mould that is used for this check is three kinds according to the special regulation of the Z 2911-1981 of Japanese Industrial Standards (sterile test method): rope Penicillium notatum (IFO 6345 green mold bacterium, as the A bacterium in the table 4), chaetomium globosum (Kunze ex Fries) IFO 6347 (belongs to hair shell family, as the B bacterium in the table 4), bud branch plate spore bacterium (Fresenius de vries) IFO 6348 (FERMS-8; IAM F517, it is mould to belong to Kurokawa, as the C bacterium of table 4).

Finding above-mentioned three kinds of bacterium, is being to expose 15 minutes in the steam that is evaporated in the ISOTC solution of 50% concentration by volume, and expose 120 minutes in the steam that is evaporated in the ISOTC solution of 5% concentration by volume after, is all killed.

Table 4

Mushroom	ISOTC is concentration (%) in solution	The cell number that retains after the sterilization treatment (%)
			Open-assembly time (minute) 0248 15 30 60 120
		A		50 20 10 5	100 0 100 87.2 62.4 0 100 85.4 66.7 30.2 0 100 86.4 71.8 19.4 5.8 0
B	50 20 10 5		100 42.6 0 100 85.7 30.4 24.5 1.0 0 100 60.6 32.3 18.2 5.1 0 100 62.7 36.6 16.9 10.2 0
		C		50 20 10 5	100 33.3 24.2 19.7 0 100 95.9 64.9 35.1 18.9 0 100 71.7 64.6 46.0 28.3 15.0 0 100 74.8 57.0 53.3 37.4 17.8 9.3 0

Example 5:

In two (about 3 liters) containers, respectively put a fish of drying up (Jurel fish), put 10 ml concns therein in container and be 1% allyl group isosulfocyanate solution with the soya-bean oil preparation, these container cover loam cakes, deposit at ambient temperature then, take out that fish frequently from container and check its smell, the result, fish with allyl group isosulfocyanate solution is put together after six days, still keeps fish peculiar smell when drying up, in contrast, that that deposit fish separately, finding has bad smell, stale.

Example 6:

Replace the fish dry up with rice cake, do experiment by example 5 the same manners, the result is, the rice cake of depositing separately is just mouldy after 3 days, and the rice cake of depositing with allyl group isosulfocyanate solution, even not mouldy after one month yet.

Example 7:

Mustard seed seed (30 parts by weight) and edible oil (soya-bean oil, 70 parts by weight) are mixed, and this mixing is easy to implement, does not cause the surrounding environment pollution again, because the mustard seed seed does not almost have the penetrating odor of isothiocyanates.

Above-mentioned solution is checked the time dependent situation of evaporation degree of allyl group isosulfocyanate with test, in this test, putting into diameter with 20 gram allyl group isosulfocyanate solution is 70mm, height is in the pallet of 15mm, at ambient temperature, from then on odoriferous intensity in the container serves as that foundation is tested with following parameter, and the results are shown in Table 5:

A: roughly can judge penetrating odor with eye is fine,

B: the mustard oil smell that smells with one's nose,

C: can only smell the mustard oil smell of minute quantity,

D: can't smell smell.

Table 5

Elapsed time	30 minutes 1 day 5 days 10 days 15 days 20 days
		Odour intensity	D C C C C C

In order to compare, get the pallet that 0.05 gram allyl group isosulfocyanate is put into same size, carry out same test, available eye is fine in 30 minutes roughly determines its penetrating odor, but after one hour, any smell also can not surveyed.

Example 8

Allyl group isosulfocyanate is dissolved in the edible oil (soya-bean oil, commercially available), and preparation concentration is 1～10% solution.Per 10 parts of ISOTC solution are mixed separately, and disperse is made the gel-like material that contains allyl group isosulfocyanate therefrom in 100 parts of pelvetia silquosa gels made from 95% water and 5% pelvetia silquosa.

Then to every part of this gel rubber material, method with the time dependent situation of the degree of distributing of allyl group isosulfocyanate is tested, in this test, be placed on a high 20mm with this gel-like material of 5 grams, in the pallet of diameter 75mm, at ambient temperature, the odour intensity that gives out in the container from then on, differentiate according to following parameter, the result is in table 6.

A: differentiate penetrating odor with the big activation of eyes,

B: the mustard gas smell that smells with one's nose,

C: can only smell the minute quantity smell,

D: can not smell smell.

For relatively, 0.05 restrain allyl group isosulfocyanate be placed on top same pallet in, do same test, in 30 minutes, roughly can differentiate penetrating odor, but after one hour, smell can not surveyed just with eyes.

Table 6

Specimen coding	Allyl group isosulfocyanate concentration (%) in the solution	Elapsed time (my god) 60 235 10 14 20 (minute)
			1 2 3 4 5	1 2 3 5 1	B B C C D D D B B B C C C D A B B B B C C A B B B B B B A B B B B B B

Example 9:

Gel-like material (10 gram) with No. 4 samples of example 8 is put into a beaker, then this beaker and a cake made of glutinous rice, sold in sliced pieces (available on the market) are put into a long 150mm, in the air-tightness plastic container of the wide 200mm of high 150mm (available on the market), the covered container lid also seals it, deposits at ambient temperature.

For relatively,, repeat rice cake is tested with above-mentioned same method except without the gel-like material.

Above-mentioned rice cake is carried out corrosion-resistanting test, the result is: the rice cake that does not use gel-like material of the present invention, just mouldy after three days, on the contrary, use gel-like material of the present invention after, after 30 days, rice cake does not still have mouldy, this situation shows, gel-like material of the present invention has good mildew-resistant, sterilization, fresh-keeping performance.

Example 10:

Replace rice cake with bread, repeat example 9 tests, the result is, after on-test played three days, the bread of container of finding not put into gel-like material of the present invention was mouldy.On the contrary, put into the bread of the container of gel-like material of the present invention, even it is not spent 30 days, still mouldy.

Example 11:

(1) preparation of sample

Bread is cut into 1 cm thick thin slice, is divided into three groups by A, B, C:

The A group: it is in the 100 μ m polythene film bags that three bread are respectively charged into thickness, then the hot sticky method of each bag usefulness is sealed up.

The B group: it is in the 100 μ m polythene film bags that three bread are respectively charged into thickness, every bag of Polythene Bag (thickness is 30 μ m) of packing into simultaneously the ISOTC solution of being made up of 20 milliliters of soya-bean oil and 10% allyl group isosulfocyanate wherein being housed is sealed up each bag with hot sticky method then.

The C group: it is in the 100 μ m polythene film bags that three bread are respectively charged into thickness, every bag vacuumizes then, seal up with hot sticky method at last, these sacks of sealing are put in the airtight container that volume is about 2 liters, this container fills 5 milliliters allyl group isosulfocyanate, be placed in 25 ℃ the environment, make to be full of pi-allyl steam in it, the time that these pockets that bread is housed are placed in this airtight container is 1 hour.

(2) result of the test

A to C organizes, and three bags every group totally 9 bags of bread are at room temperature deposited, and see whether bread is mouldy in each pocket, result of the test such as table 7:

Table 7

Sample	Elapsed time (my god) 137 10 20 30
		A group B group C group	- ++ +++ +++ +++ +++ - - - - - - - - - - - -

Description of symbols:

-: do not have mouldy

+: have 1～2 place mouldy ++: have 3～4 places mouldy +++: have 5～more many places mouldy, or the mould spot diameter of garden shape expand to 1 centimetre at least.

Example 12

Is a concentration that 0.5% allyl group isosulfocyanate is dissolved in 99% the alcohol, produces spray solution.Getting flushing liquor 300 gram is in 500 milliliters the aerosol container with 80 gram sprinkling media (liquefied butane) volume of packing into, thereby constitutes a flusher.When flushing liquor sprays from flusher, make the droplet that is atomized into uniform smoke-like.In spraying operation, answer addition of constraints, pollute surrounding environment so that prevent the penetrating odor of allyl group isosulfocyanate effectively.

Use this flusher flushing liquor to be sprayed onto in the airtight container that rice cake is housed, covered container lid then, it is deposited one month after, do not find Signs of Mould.For relatively, the rice cake that does not spray this solution is tested equally, the result is, after three days, the rice cake surface from mildewing.

Example 13:

Be the concentration by weight that is 100 parts by weight 1% allyl group isosulfocyanate solution and be that 100 parts soya-bean oil mixes by weight, make a kind of flushing liquor.With this spray solution with spray medium, pack in the sprinkler with example 12 the same manners, thereby constitute a flusher.When flushing liquor sprays, form a kind of vaporific droplet from flusher.When carrying out spraying operation, it should be noted that the penetrating odor of the allyl group isosulfocyanate of this flushing liquor compared with the situation in the example 12, prevents manyly easily.

Example 14

Commercially available small-sized, the Minton dryer that is interrupted work in a kind of market, it has a hothouse, is provided with vacuum interface on chamber interior walls, air intlet and bubble-tight door.Vavuum pump links to each other with vacuum interface by the adsorbing medium of active carbon is housed, and the gas outlet pipe of ISOTC holder is connected to the air intlet place through a switch triple valve.Be placed with in the holder with the impregnated sepiolite powder of allyl isothiocyanate salt (ISOTC vapor-generating agent), on the sidewall of holder a blast pipe arranged.The syndeton of aforesaid way just constitutes a sterilization treatment device of the present invention.

Open the door of bactericidal unit, the polythene film bag that sealing is equipped with the cake made of glutinous rice, sold in sliced pieces puts in, and closes to the doorstep then, opens triple valve, ISOTC steam in the ISOTC holder is entered in the hothouse of this device, after 24 hours, open vavuum pump, close triple valve, therefore cut off the path that leads to the ISOTC storage chamber, connect the air intake path simultaneously, thereby discharge the gas of the work of hothouse through the absorption tower, just the ISOTC steam that contains in this gas is removed.

After closing vavuum pump, open the door of hothouse, the indoor bag that rice cake is housed is taken out.The packaged rice cake of so handling can be deposited in atmospheric environment.

For relatively, use above-mentioned the same manner, a rice cake is packed in the polythene film bag, sterilize but do not carry out sterilization treatment, just be placed in the atmospheric environment and deposit.

That piece rice cake of comparative test, deposit after three days just mouldy, on the contrary, the rice cake through crossing with sterilization treatment of the present invention, even deposit one month, not mouldy yet.

Claims (5)

1. one kind is carried out sterilization treatment method to goods, it is characterized in that, these goods are contacted with the steam that solution produced that the isothiocyanates that by concentration is 0.01-50% by weight is dissolved in the fluid, and described fluid is 2.666222 * 10 30 ℃ vapour pressure ⁵Pascal or be lower than 2.66622 * 10 ⁵Pascal, or contact with the steam that solution of isothiocynate vapor-generating agent produced that contains described isothiocyanic acid ester solution.

2. one kind is carried out sterilization treatment method to goods, it is characterized in that, these goods are contacted with the gas that contains isothiocyanates steam with a kind of gas that is selected from air, nitrogen and carbon dioxide, described isothiocyanates steam is to be produced by the liquid of isothiocyanates or the solution that contains isothiocyanates, and described goods are to use the packaging material of isothiocyanates vapor permeable packaged in advance.

3. one kind is carried out sterilization treatment method to goods, it is characterized in that described method comprises the following steps:

With the form feeding sterilization treatment chamber of isothiocyanates, in described sterilization treatment chamber, to form a kind of aerosol that contains isothiocyanates steam with steam or liquid particulate; Wherein said isothiocyanates with vapor form is formed by following method: (a) solution with liquid isothiocyanates or isothiocyanates heats with this isothiocyanates of vaporizing, again with the isothiocyanates of vaporize and a kind of mixed gases that is selected from air, nitrogen and carbon dioxide, perhaps (b) a kind of gas that will be selected from air, nitrogen and carbon dioxide is by containing the liquid of isothiocyanates gas, and wherein said liquid microparticle is to form by the solution spray with this isothiocyanates; These goods are put into described sterilization treatment chamber; These goods are contacted with the aerosol gas that contains isothiocyanates steam in described sterilization treatment chamber, carry out sterilization treatment; After sterilization treatment, with this aerosol gas by emitting in the described sterilization treatment chamber; With by cooling off this aerosol gas and/or this aerosol gas being contacted with a kind of adsorbent by removing isothiocyanates steam in the gas of emitting.

4. according to a kind of method of claim 3, wherein these goods are to use the packaging material of isothiocyanates vapor permeable packaged in advance.

5. method in confined space sterilization, wherein,

The gas that will contain isothiocyanates feeds this confined space, make this confined space carry out sterilization treatment, the said gas that contains isothiocyanates produces by following steps: (a) solution with isothiocyanates liquid or isothiocyanates heats with this isothiocyanates that gasifies, again with the isothiocyanates of gasification and from air, a kind of mixed gases of selecting in nitrogen and the carbon dioxide, perhaps (b) will be selected from air, a kind of gas of nitrogen and carbon dioxide is by containing the liquid of this isothiocyanates, then the gas in this confined space is removed device by cooling and/or by contacting with gas absorbent through isothiocyanates steam, remove isothiocyanates from this confined space.

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