CA2074116C - Allyl isothiocyanate sprays - Google Patents

Allyl isothiocyanate sprays

Info

Publication number
CA2074116C
CA2074116C CA002074116A CA2074116A CA2074116C CA 2074116 C CA2074116 C CA 2074116C CA 002074116 A CA002074116 A CA 002074116A CA 2074116 A CA2074116 A CA 2074116A CA 2074116 C CA2074116 C CA 2074116C
Authority
CA
Canada
Prior art keywords
allyl isothiocyanate
carbon dioxide
allyl
spray
dioxide gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CA002074116A
Other languages
French (fr)
Other versions
CA2074116A1 (en
Inventor
Yasushi Sekiyama
Yuichi Mizukami
Tessei Yamamoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Foods Corp
Original Assignee
Green Cross Corp Japan
Nippon Sanso Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Green Cross Corp Japan, Nippon Sanso Corp filed Critical Green Cross Corp Japan
Publication of CA2074116A1 publication Critical patent/CA2074116A1/en
Application granted granted Critical
Publication of CA2074116C publication Critical patent/CA2074116C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/46Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=C=S groups

Abstract

An allyl isothiocyanate spray prepared by dissolving 0.1 to 10 % by weight of an allyl isothiocyanate in liquefied carbon dioxide gas and charging the resulting solution into a pressure vessel under a pressurization so that the liquefied carbon dioxide gas can maintain liquid phase.
The spray can practically be employed with safety for bacteriostatic or germicidal treatment or for quality preservation.

Description

- 2~7~1~ 6 ALLYL ISOTHIOCYANATE SPRAYS

l~ACRGROUND OF THE lNVl~ lON AND STATEMENT OF RELaTE:D AR~

This invention relates to allyl isothiocyanate sprays.

Allyl isothiocyanate is also referred to as allyl mustard oil and generally obtained by extraction from a raw material such as mustard and Japanese horseradish (Wasabia japonica Matusum) by steam distillation or by subjecting sodium thiocyanate and allyl chloride to distillation The thus obtained allyl mustard oil is primarily utilized as a flavoring agent for foods or as a raw material of ph~ -ceutical preparations.

The present inventors, having noted the properties of allyl mustard oil and use thereof for bacteriostatic or germicidal treatment or quality preservation, made extensive studies.

They found that satisfactory effect can be exhibited if allyl mustard oil is used even in a very small amount for the purpose of bacteriostatic or germicidal treatment, etc.
:: :
However, allyl mustard oil is an oily liquid which develops peculiar irritating odor and has a comparatively low flash point, so that it involves a number of problems so as to be utilized widely. For example, when allyl mustard oil is used for bacteriostatic or germicidal treatment, it must be vaporized, requiring a vaporizing apparatus for that purpose. Besides, the vaporizing apparatus must indispensably be equipped with a safety device since a low-flash poin-t oil is vaporized, so that the vaporizing apparatus will inevitably be enlarged and expensive.
Accordingly, the vaporizing apparatus cannot conveniently ~7~

be utilized for other purposes than treating a great amount of materials to be treated.

Spraying can be given as an expedient means of vaporizing allyl mustard oil. However, since ordinary spraying methods employ LPG (liquefied petroleum gas) or Freon gas as an atomizing medium, they involve problems in the properties of such gas and in safety. When allyl mustard oil is sprayed using such gaseous medium, the aerosol thus formed comes to have a comparatively great partic}e size as big as that of mist to stain clothes or fabrics and besides it cannot be sprayed uni~ormly over a wide area.
Accordingly, LPG and Freon cannot be employed for spraying allyl mustard oil due to many inconveniences descxibed above.

There is proposed another technique of spraying a solution of a principal spray agent dissolved in liquefied carbon dioxide gas. This technique can give a very fine aerosol, but solubility of allyl mustard oil in liquefied carbon dioxide gas is not known and further this method involves too many technical problems which must be solved, such as strong irritating odor, correlation between the gaseous composition and the practical bacteriostatic or gsrmicidal effect of the aerosol, etc., to be proposed as a practical method.

OBJECT AND SUMMARY OE THE lNY~ ON

This invention is directed to provide an allyl isothiocyanate spray having overcome the above problems which is suita~ly used for bacteriostatic or ge.rmicidal treatment. More particularly, this invention i; directed to provide a spray, prepared by dissolving allyl isothiocyanate in a high-pressure liquefied carbon dioxide gas which is liquid and charging the resulting solution in 2 ~ 7 ~

liquid form in ~ pressure vessel, for example a cylinder or a storage tank, etc.

A first aspect of this invention relates to an allyl isothiocyanate spray, comprising a solution of 0.1 to 10 ~
by weight of an allyl isothiocyanate dissolved in liquefied carbon dioxide gas, charged in a pressure vessel with a pressurization so that the liquefied gas can maintain liquid phase.

A second aspect of this invention relates to an allyl isothiocyanate spray comprising a solution of allyl isothiocyanate dissolved in a liquefied carbon dioxide gas, which is prepared by charging 0.1 to 10 ~ by weight of allyl isothiocyanate and then 99.9 to 90 % by weight of liquefied carbon dioxide gas to a pressure vessel so as to mix these two components and provide a solution.

A third aspect of this invention relates to an allyl isothiocyanate spray in which said pressure vessel is equipped with an atomizing means and the liquefied carbon dioxide gas serves as a propellant.

A fourth aspect of this invention relates to any of the above allyl isothiocyanate sprays, in which the allyl isothiocyanate is an extract from Japanese horseradish or mustard or a prepurified product thereof.

In the spray according to this invention, the principal spray agent allyl isothiocyanate is dissolved homogeneously in liquefied carbon dioxide gas. Meanwhile, since the liquefied carbon dioxide gas is charged with pressurization into a pressure vessel, the spray, when jetted, is allowed to expand quickly by the release from the high-pressure liquefied carbon dioxide gas, so that the allyl isothiocyanate contained in the spray forms a very fine 2 ~ 7 ~
aerosol. The thus finely divided allyl i~othiocyanate stays floating in air over a wide area for an extended time. Accordingly, for example, if a material to be treated is contained in a closed vessel, a gaseous atmosphere of homogeneous composition can be produced to allow the material to be treated to be in contact uniformly with the allyl isothiocyanate and achieve bacteriostatic or germicidal treatment sufficiently.

According to the allyl isothiocyanate spray of this invention, no equipment for vaporizing allyl isothiocyanate is necessary. When the present allyl isothiocyanate spray is used in an actual application, it can be utilized conveniently for various purposes only by carrying the pressure vessel to the desired spots. Besides, safety of the spray can be secured, since the combustible allyl isothiocyanate is jetted together with inert carbon dioxide gas.

According to the present spray, a gaseous composition containing 0.1 to 10 ~ by weight of allyl isothiocyanate can sufficiently exhibit bacteriostatic or germicidal effect with no secondary affect such as of scent or irritating odor. An allyl isothiocyanate content of less than 0.1 % by weight will sometimes bring about insufficient bacteriostatic or germicidal effect; whereas that of more than 10 % by weight is liable to cause secondary affect such as of strong irritating odor and the like.

Now that it was identified according to this invention that even a very small amount of allyl isothiocyanate can exhibit bacteriostatic or germicidal effect, a minimum necessary amount of allyl isothiocyanate may be dissolved in liquefied carbon dioxide gas to obviate such strong irritating odor in practical uses. If even such reduced 2 ~ 7 ~

level of irritating odor is still ~elt offensive, a deodorizer may as necessary be used at the same time or separately.

As allyl isothiocyanate, use may be made of any natural or synthetic allyl isothiocyanate. Allyl isothiocyanate is not restricted solely to a single solid preparation consisting of 100% of allyl isothiocyanate, and a mixture oil containing allyl isothiocyanate, an extract of mustard or Japanese horseradish (usually contains above 90% of allyl isothiocyanate), or a crude product may be used.

BRIEF DESCRIPTION OF THE DRAWING

Fig. 1 is a graph showing a relationship between the temperature and pressure generally necessary for liquefied carbon dioxide gas to retain liquid phase.

D~ATT~n DESCRIPTION OF PREFERRED EMBODIMENTS

Next, a preparation process and a preparation example of the spray according to this invention as well as Test Examples when the sprays thus prepared were used for bacteriostatic or germicidal treatment will be described below. It should be appreciated, however, that the present invention is not limited only to them.

A process for preparing the allyl isothiocyanate spray will be described below.

To a 3 Q volume pressure vessel is charged 0.1 to 10 % by weight of allyl mustard oil based on the liquefied carbon dioxide gas to be charged later. The amount of the allyl mustard oil can easily be calculated from the weight of the entire composition after liquefied carbon dioxide gas is charged with pressure to the vessel.

2~7~.16 Subsequently, liquefied carbon dioxide gas is charged to the pressure vessel having already charged therein an allyl mustard oil in such an amount that the content of the allyl mustard oil may be 0.1 to lO ~ by weight. The relationship between the temperature and the pressure generally required for the liquefied carbon dioxide gas so as to maintain liquid phase is as shown in Fig. 1. Namely, in order that liquefied carbon dioxide gas can maintain liquid phase, a pressure of about 20 kgf/cm2 or more at a temperature of -20 C, about 35 kgf/cmZ or more at a temperature of 0 C, about 52 kgf/cm2 or more at a temperature of 15~C or about 73 kgf/cm2 or more at a temperature of 30 C is required.
When liquefied carbon dioxide gas is charged into a pressure vessel with a pressure not lower than the prescribed level at the corresponding temperature, a temperature change will occur upon completion of charging, causing a pressure change conforming to the curve shown in Fig. 1, and thus the liquefied carbon dioxide gas can maintain the liquid phase.

Since liquefied carbon dioxide gas is usually stored in a heat-insulated container under a pressure of about 20 kgf/cm2 at a temperature of about -20~C, a predetermined amount of liquefied carbon dioxide gas is charged therefrom maint~;n;ng this temperature into the pressure vessel preli~in~rily charg~d with an allyl mustard in such an amount that the content of allyl mustard oil may be O.I to 10 % by weight. If the resulting pressure vessel is left to stand at room temperature, for example at 20~C, the pressure will be elevated to about 60 kgf/cm2; whereas if the pressure vessel is left to stand at about 28~C, the pressure will be elevated to about 70 kgf/cm2, providing a plenum fill state in the pressure vessel with the liquefied carbon dioxide gas while maint~in;ng liquid phase.

Meanwhile, when a liquefied carbon dioxide gas stored in a 2~7~

heat-insulated container under a pressure of about 20 kgf/cm2 at a temperature of -20~C is fed, for example, at a temperature of about 28~C to a pressure vessel preli i n~rily charged with a predetermined amount of allyl mustard oil by means of a cryogenic gas pump, the liquefied carbon dioxide gas may be charged to a pressure o~ about 70 kgf/cm2 where it can retain liquid phase at about 28 C.

An allyl isothiocyanate spray comprising 0.1 to 10 % by weight of an allyl mustard oil and 99.9 to 90 % by weight of liquefied carbon dioxide gas can thus be obtained.

Preparation example of allyl isothiocYanate spray According to the process as described above, the present inventors prepared allyl mustard oil sprays .by dissolving 1 % by weight of an allyl mustard oil in liquefied carbon dioxide gas under a pressure of 70 kgf/cm2 at a temperature of about 28~C and by dissolving 3 % by weight of an allyl mustard oil likewise in liquefied carbon dioxide ~as under a pressure of 70 kgf/cm2 at a temperature of about 28 C, respectively.

Next, Test Examples using these sprays will be described.

Test ExamPle 1 About 1 kg of chopped vegetables was almost equally divided into nine portions and packed in nine polyethylene film bags tthickness: 20 ~m). Three of them were treated ext~rn~lly with the spray containing 1 % by weight of allyl mustard oil for about one second through the spraying means provided for the pressure vessel, and another three bags were treated with the same spray for about 10 seconds. The rest were untreated as controls.

2 ~ 7 ~

These samples were incubated at room temperature for 24 hours to compare change in the freshness of the treated and untreated chopped vegetables. The results of observation are as shown in Table 1.
Table 1 Spraying Results of observation time Browning Odor development Untreated 3/3 3/3 1 sec 1/3 0/3 10 sec 0/3 0/3 As shown in Table 1, positive quality preservation effect was exhibited by treatment with the above sprays.

Test Example 2 Twenty~one packs of raw seaweed (Undaria Pinnatifida) were divided into seven groups each group consisting of three packs. One group was untreated as a control group, and the rest of the groups were treated with the sprays containing 1 % by weight and 3 % by weight of allyl mustard oil under the conditions as shown in Table 2, respectively. These spraying treatments were carried out against the contents taken out of the packages and then packed in the same packages. The thus treated samples were incubated at a temperature of 10~C and at a humidity of 90 % for two weeks at the longest to test the following items.

1) Fungus ~esistance: after 1, 7 and 14 days 2) Residual smell of Japanese horseradish:
; -~iately after treatment and after 1 day 3) General viable ceLl count: after 1 and 4 days The test results are as shown in Table 3.

2~7~

Table 2 Ally mustard oil concentration 1 % by weight 3 % by weight Condition No. 1 2 3 4 5 6 Spraying time 10 20 30 10 20 30 (sec) Table 3 Test result Appearance* Residual horseradish General viable cell Treating odor count conditi~n After After After Immed.After 1 After 1 day After 4 l day 7 days14 days after day days Control - - + - - 1.0 x 106/g 1.9 x 108/g Treated - - + + - 6.4 x 103/g 1.1 x 107/g group 1 Treated - - + + - 8.4 x 102/g 8.5 x 106/g group 2 Treated - - - + - 8.5 x 102/g 2.9 x 106/g ,_ group 3 Treated - - - + - 8.8 x 103/g 1.8 x 107/g group 4 Treated - - - + - 1.5 x 103/g s.3 x 105/g group 5 Treated - - _ + _ 9.6 x 102/g 7.4 x 104/g group 6 * Appearance was evaluated according to.the following criteria:
+: Molding occurred substantially over the entire surface.
+: Molding occurred at some parts.
-: No change ; ~,, - 2~7~

As apparent from Table 3, in the treated groups using the above two types of sprays, not only molding was prevented but also the general viable cell count was controlled to about l/102 to 103 compared with the control groups, showing a positive bacteriostatic effect. On the other hand, although the odor of Japanese horser.adish was identified in~ediately after treatment proportional to the intensity of treatment, the odor was ~ i tni nished to a undetectable degree after 1 day. This suggests that the original taste or flavor of the food may not substantially be affected.

Claims (4)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. An allyl isothiocyanate spray comprising 0.1% to about 10% by weight of an allyl isothiocyanate dissolved in liquid carbon dioxide to form a solution in which the solution is under sufficient pressure to be in the liquid phase.
2. An allyl isothiocyanate spray comprising 0.1% to 10% by weight of allyl isothiocyanate dissolved in about 99.9% to 90% by weight of liquid carbon dioxide in a pressure vessel so as to mix these two components and provide an aerosol solution.
3. An allyl isothiocyanate spray according to claim 2, wherein said pressure vessel is equipped with an atomizing means and the liquid carbon dioxide charge serves as a propellant to form the aerosol spray.
4. An allyl isothiocyanate spray according to claim 1, 2 or 3, wherein the allyl isothiocyanate is an extract from Japanese horseradish or mustard, or a purified product thereof.
CA002074116A 1991-07-18 1992-07-17 Allyl isothiocyanate sprays Expired - Fee Related CA2074116C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP178370-1991 1991-07-18
JP17837091A JP3076822B2 (en) 1991-07-18 1991-07-18 Allyl isothiocyanate spray

Publications (2)

Publication Number Publication Date
CA2074116A1 CA2074116A1 (en) 1993-01-19
CA2074116C true CA2074116C (en) 1998-04-21

Family

ID=16047310

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002074116A Expired - Fee Related CA2074116C (en) 1991-07-18 1992-07-17 Allyl isothiocyanate sprays

Country Status (3)

Country Link
US (1) US5334373A (en)
JP (1) JP3076822B2 (en)
CA (1) CA2074116C (en)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL147222A0 (en) * 1999-06-25 2002-08-14 Abiogen Pharma Spa Preparation and metering of components with co2
US6361812B1 (en) * 1999-11-18 2002-03-26 The Procter & Gamble Co. Products comprising an isothiocyanate preservative system and methods of their use
US7497623B2 (en) 2002-02-27 2009-03-03 Pactiv Corporation Packages with active agents
DE10314878A1 (en) * 2003-04-01 2004-10-28 Zimmer Ag Method and device for producing post-stretched cellulose filaments
US8475862B2 (en) 2003-10-01 2013-07-02 The Procter & Gamble Company Isothiocyanate preservatives and methods of their use
US7658961B2 (en) * 2003-10-01 2010-02-09 The Procter & Gamble Company Isothiocyanate preservatives and methods of their use
US20050123528A1 (en) * 2003-12-08 2005-06-09 Gorton Stephen J. Application of a non-toxic organic enzyme formulation and process for reducing fungi-caused decay on fruits and vegetables
US20050196492A1 (en) * 2004-03-04 2005-09-08 Muller Wayne S. Food preservative method and system using vanillin and constituent having isothiocynate compound
US20070110780A1 (en) * 2005-11-14 2007-05-17 Nzymsys, Ip Inc. Building material surface treatment biocide, and method for treatment of building material surfaces
US20070280919A1 (en) * 2006-05-30 2007-12-06 Gorton Stephen J Produce-treatment composition and method for treatment of fresh produce
US8697150B2 (en) 2010-03-31 2014-04-15 The Procter & Gamble Company Process of extracting isothiocyanates
US20110244078A1 (en) 2010-03-31 2011-10-06 Athula Ekanayake Mustard Compositions
CN102984937B (en) * 2010-05-23 2015-08-19 高砂香料工业株式会社 Bactericidal composition
WO2012074922A1 (en) * 2010-11-29 2012-06-07 Security Equipment Corporation Defense spray using isothiocyanate as an ingredient
US20130280388A1 (en) 2012-04-24 2013-10-24 Athula Ekanayake Solid Food Products and Methods of Their Preservation
JP5841962B2 (en) * 2013-04-11 2016-01-13 アース環境サービス株式会社 Insecticide / sterilizing spray and method for producing the same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755064A (en) * 1967-08-11 1973-08-28 Ncr Water insoluble polymeric web structures and filaments containing encapsulated components
AU636342B2 (en) * 1989-04-07 1993-04-29 Welfide Corporation Generator of isothiocyanic ester vapor, method of sterilizing with isothiocyanic ester vapor, and apparatus therefor

Also Published As

Publication number Publication date
JP3076822B2 (en) 2000-08-14
JPH0523155A (en) 1993-02-02
US5334373A (en) 1994-08-02
CA2074116A1 (en) 1993-01-19

Similar Documents

Publication Publication Date Title
CA2074116C (en) Allyl isothiocyanate sprays
US5597599A (en) Method for processing a perishable product
SE438425B (en) FRESH PRESERVANT AGENTS FOR VEGETABLES AND FRUITS, CONSISTING OF A PARTICULAR COMPOSITION CONTAINING AT LEAST TWO ADSORBENTS
US6265006B1 (en) Method and apparatus for applying volatile substances to materials
Cagnon et al. Fresh food packaging design: A requirement driven approach applied to strawberries and agro-based materials
DE2436099C3 (en) Process for the post-ripening of fruits
Wang et al. Comparison of practical methods for postharvest preservation of loquat fruit
Segall et al. Design and analysis of a modified-atmosphere package for minimally processed romaine lettuce
CN102726514A (en) Novel method for inhibition of peel browning of Huangguan pears
CN108432868A (en) A kind of wood receives the synthesis air regulating fresh-keeping method of lattice grape
CN104855506A (en) Freshness retaining process for storage and transportation of mangos
Xu et al. Preparation and Measurement of Controlled‐Release SO2 Fungicide Active Packaging at Room Temperature
Warsiki et al. The Effects of the Use of Corrugated Cardboards Covered with Ethylene Absorbers on Mango Fruit Quality after Short-Term Storage (L.)
Lee et al. Modified atmosphere packaging for green chili peppers
CN104757101B (en) A kind of inner wrapping air regulating fresh-keeping method of caraway
CA1105317A (en) Process for extending the life of cut vegetables
KR100348473B1 (en) Power wave water and a method for preparing thereof, and a method for maintaining freshness of vegatables using the same
CN109548863A (en) The new application that thioacetic acid esters compound is used to that fruits and vegetables tissue to be inhibited to change colour
JPS5655147A (en) Keeping of freshness of vegetable and fruit
Hewett Bitter pit reduction in ‘Cox's Orange Pippin’apples by controlled and modified atmosphere storage
Teoriman et al. Effect of ozone solution immersion treatment on the quality of fresh red chilies during modified cold-storage.
JP2003284487A (en) Freshness retaining package for vegetable and fruit
JPH0848371A (en) Package of fresh plant
Hong et al. Quality of'Fuji'Apple Packed with Functional MA Film to the Films Thickness
CA2030548C (en) Isothiocyanate vapor-generating agent, germ-destroying treatment method using isothiocyanate vapors and apparatus therefor

Legal Events

Date Code Title Description
EEER Examination request
MKLA Lapsed
MKLA Lapsed

Effective date: 20070717