(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2012/074922 Al 7 June 2012 (07.06.2012) W P O P C T

(51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every B05B 11/06 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, (21) International Application Number: CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, PCT/US201 1/062236 DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, (22) International Filing Date: HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, KR, 28 November 201 1 (28.1 1.201 1) KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, (25) Filing Language: English OM, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SC, SD, (26) Publication Language: English SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: 61/417,597 29 November 2010 (29. 11.2010) US (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (71) Applicant (for all designated States except US) : SECUR¬ GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, ITY EQUIPMENT CORPORATION [US/US]; 747 Sun UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, Park Drive, Fenton, Missouri 63026 (US). TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, (72) Inventors; and LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, (75) Inventors/Applicants (for US only): NANCE, Robert SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, [US/US]; 13033 Barrett Crossing Court, St. Louis, Mis GW, ML, MR, NE, SN, TD, TG). souri 63026 (US). MILLIGAN, Clive [CA/CA]; 5158 48th Avenue, Suite 328, Delta, British Columbia V4K 5B6 Published: (CA). — with international search report (Art. 21(3)) (74) Agent: ROBBINS, Glenn; Spencer Fane Britt & Browne — before the expiration of the time limit for amending the LLP, 1 North Brentwood Blvd., Suite 1000, St. Louis, claims and to be republished in the event of receipt of Missouri 63 105-3925 (US). amendments (Rule 48.2(h))

© (54) Title: DEFENSE SPRAY USING AS AN INGREDIENT ¾ (57) Abstract: A defense spray having an incapacitating effect of shorter duration is provided. The defense spray composition corn prises isothiocyanate as an active ingredient. The source of the isothiocyanate can include , oil or mustard. Iso - thiocyanate has a high degree of volatility and readily evaporates. By incorporating isothiocyanate as an active ingredient in compos - itions of the inventive defense spray, it produces an incapacitating effect on a subject that is of shorter duration than that associated with traditional defensive sprays, such as and CS . DEFENSE SPRAY USING ISOTHIOCYANATE AS AN INGREDIENT

RELATED APPLICATIONS

[0001] The present patent application claims priority benefit of an earlier-filed U.S. provisional patent application of the same title, Serial No. 61/417,597, filed November 29, 2010. The identified earlier-filed application is hereby incorporated by reference into the present application.

BACKGROUND OF THE INVENTION

[0002] 1. FIELD OF THE INVENTION [0003] The present invention relates to non-lethal defense sprays and crowd control used by law enforcement, corrections institutions, military and security personnel to control resistive and/or violent subjects. [0004] 2. DESCRIPTION OF THE PRIOR ART [0005] There exist many types of non-lethal defense sprays used by law enforcement, corrections institutions, military and security personnel to control resistive and/or violent subjects. Such defense sprays include CS tear gas, CN tear gas and red pepper spray. When using such defense sprays, it is desirable and critical that they have sufficient "stopping power" in order to be effective in establishing control over the subject. To achieve that goal, the defense spray must have an appropriate concentration of an active ingredient having the necessary stopping power. For example, red pepper spray must have an appropriate concentration of capsaicinoids to provide the necessary stopping power. Understandably, the higher the concentration level of the capsaicinoid, the greater the stopping power. [0006] Pepper spray has been used as a less lethal inflammatory agent in law enforcement, security and military operations for several decades. It has a definite role for use by officers in controlling subject behavior. However, quite often, officers are hesitant to use pepper spray and other defensive sprays because of their long-lasting effects. The length of time in which the effects are felt is a significant concern given the likely possibility of contamination of fellow officers. Due to the dynamics of the confrontation, other officers may be accidentally sprayed resulting in them having to fight through the discomfort and distraction of the inflammatory agent. Due to the oily compounds and long lasting effects of most -based (chili peppers) aerosols, some officers may themselves become incapacitated for a considerable amount of time by misdirected spray. If this occurs, the afflicted officers then become a protracted hazard to their own and the other assisting-officers' safety. Some aerosol defense sprays have a very long-lasting effect and can take an extremely long time to de-contaminate (even when using counter-acting decontamination solutions). Aside from the most important aspect (possible officer safety issues) this further results in a loss of productive time and effective resource management (such as immediate re-deployment of officers after the arrest). [0007] Defense sprays may also render the intended subject incapacitated well beyond the time necessary to place the subject under control. With respect to red pepper spray, the higher the concentration level of capsaicinoids, the greater the stopping power. However, higher concentrations of capsaicinoids means a longer decontamination period. Once an offending subject is apprehended, it may be counterproductive for the apprehended subject to continue to suffer effects of the incapacitating spray if those effects render the subject unable to cooperate.

SUMMARY OF THE INVENTION

[0008] The present teachings include compositions for a defense spray having an incapacitating effect of shorter duration. In accordance with the invention, an embodiment of the defense spray composition includes isothiocyanate as an active ingredient. The source of isothiocyanate can include wasabi, horseradish oil, or mustard. Alternatively, the isothiocyanate may be produced synthetically. [0009] Isothiocyanate has a high degree of volatility and readily evaporates. By incorporating isothiocyanate as an active ingredient in compositions of the inventive defense spray, it produces an incapacitating effect on a subject that is of shorter duration than that associated with traditional defensive sprays, such as pepper spray and CS tear gas. Accordingly, the inventive defense spray composition provides a strategically useful tool in the deployment of non-lethal force that enables law enforcement and other like personnel to achieve their control objectives in an effective and efficient manner. Furthermore, the shorter duration of the incapacitating effect minimizes collateral disruptive effects that can otherwise be caused by a longer-lasting defense spray weapon. The inventive defense spray composition permits relatively rapid decontamination so that accidentally-sprayed colleagues may quickly be treated for relief from the debilitating aspects of the spray, and controlled subjects may be quickly treated for relief from incapacitation so that they are physically able to cooperate with the apprehending personnel. [0010] In accordance with an aspect of the invention, the defense spray composition comprises a carrier solvent and an isothiocyanate compound of the formula:

wherein R may be selected from the group consisting of alkyl, alkenyl, allyl, and alkylthioalkyl. The defense spray composition may include propellants generally known to those skilled in the art. [0011] In accordance with another aspect of the invention, a weak acid may be included in the composition to provide stability and to control the volatility of the isothiocyanate ingredient. Additionally, emulsifiers may be added to the composition to enhance the solubility of the ingredients. [0012] In a preferred embodiment, the defense spray composition comprises 0.1% to 20% Horseradish oil, and a solvent system. The solvent system can be comprised of 5% to 10% , 1% to 5% Polysorbate 80, 15% to 25% , 50% to 65% water. The composition may also contain other incapacitants such as CS Tear Gas, CN Tear gas or (red pepper) with the Horseradish oil. The composition can be delivered via an aerosol propellant such as nitrogen, carbon dioxide, compressed air, HFC 134a (1,1,1,2-Tetrafluoroethane) or any other commercially available propellants. A marking dye may also be added to the composition. [0013] Another aspect of the invention is to provide a defense spray composition whereby the duration of the incapacitating effects can be controlled to have a shorter duration than that provided with other defense sprays such as red pepper. By modifying the concentration of the isothiocyanate ingredient, the duration of the incapacitating effects can be controlled. [0014] These and other important features, aspects and advantages of the present teachings will become better understood with reference to the following description, examples and appended claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The defense spray composition of the present invention provides a strategic tool for law enforcement and correctional personnel by enabling the deployment of a non-lethal spray that delivers an incapacitating effect of relatively short duration. This feature promotes the achievement of rapid control of a subject while limiting cross- contamination of fellow personnel. A further advantage of the short duration in the effect of the inventive defense spray composition is to permit rapid decontamination of the affected subject once control is achieved. [0016] The inventive defense spray composition includes an isothiocyanate compound as an active ingredient. The formulation includes a solvent and an isothiocyanate compound of the formula sho n below.

[0017] The substituent R group may be alkyl, alkenyl, allyl, or alkylthioalkyl. In particular, the R group may be allyl. The term "alkenyl," alone or in combination, refers to a substituted or unsubstituted straight-chain or substituted or unsubstituted branched- chain alkenyl group containing from 2 to 10 carbon atoms. Examples of such substituents include, but are not limited to, ethenyl, E- and Z-pentenyl, decenyl and the like. The term "alkyl," as used herein, describes substituents which are preferably lower alkyl containing from one to eight carbon atoms in the principal chain and up to about 20 carbon atoms. The principal chain may be straight, branched or cyclic. Representative examples of alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, hexyl and the like. The term "alkylthio," as used herein, describes an alkyl group, as described herein, appended to the parent molecular moiety through a sulfur atom. Representative examples of alkylthio include, but are not limited to, methylthio, ethylthio, tert-butylthio, and hexylthio. The term "allyl," as used herein, refers to a —

CH2CH=CH2 group. The term "thio," as used herein, refers to a —S— moiety. [0018] The isothiocyanate compounds may be produced synthetically or isolated from sources. belonging to the family have high concentrations of . Horseradish, (Armoracia lapathifolia Gilib., (Family: Cruciferae) Armoracia rusticana, syn. Cochlearia armoracia), wasabi, (Wasabia japonica, Cochlearia wasabi, or Eutrema japonica), and mustard (Brassica rapa, Brassica nigra, Brassica alba, Brassica carinata, Brassica oleracea), all have the particularly strong, pungent flavor indicative of isothiocyanates. is commercially produced via the dry distillation of mustard . A preferred embodiment of the present invention utilizes horseradish oil as the source of isothiocyanate. For example, HORIOOO Oleoresin Horseradish obtained from Synthite Industries LTD is a preferred source of horseradish oil. [0019] The spray composition may contain an isothiocyanate compound present in an amount of about 0.1% to about 20% by weight of the formulation. The formulation may contain additional incapacitating agents known to those skilled in the art. The spray's "stopping power" and recovery time may be adjusted by varying the concentration of the isothiocyanate and other incapacitating agents present. The concentration of the active ingredients should be large enough to consistently produce the desired effect, but not so large as to cause undue injury, or result in an excessive recovery time. The formulation includes a solvent. The solvent system should uniformly dissolve or suspend the active ingredients. Preferred solvent systems are chemically stable, non-toxic, non-flammable, and safe for skin contact. Suitable solvents may include propylene glycol, ethanol, water, polypropylene glycol, polyethylene glycol, hydrogenated castor oil, mineral oil, oil, and mixtures thereof. [0020] To help stabilize the volatility of the isothiocyanate compound, the formulation may further include an emulsifier. For example, Polysorbate 80 is a preferred emulsifying agent. [0021] In a preferred embodiment, the defense spray composition comprises:

0.1% to 20% Horseradish oil

5% to 10% Propylene Glycol

1% to 5% Polysorbate 80

15% to 25% Ethanol

50% to 65% water.

[0022] Another preferred embodiment comprises:

1-20% Horseradish oil

50-90% HFC 134a Propellant

10-20% Propylene Glycol 30-40% Glycol Ether DB

[0023] One preferred spray deployment embodiment comprises dispersing the spray as a fog or in a cone-shaped spray pattern. A preferred embodiment of the defense spray composition incorporating this dispersion feature comprises: 5% Horseradish Oil

35% Glycol Ether DB

10% Propylene Glycol

50% HFC 134a

[0024] Another preferred spray deployment embodiment comprises dispersing the spray under high-pressure propellant for more rapid evaporation after deployment. A preferred embodiment of the defense spray composition incorporating this dispersion feature comprises: 5% Horseradish Oil

5% Glycol Ether DB

90% HFC 134a

[0025] In accordance with yet another aspect, the formulation may further include dyes or other marking agents in the spray composition. Given the relatively short duration of the incapacitating effect of the spray composition, it may be useful that the spray leave a mark on the subject as a means to identify the subject as one having been sprayed. A sprayed subject may need to be later apprehended if he is able to withstand the initial spray and escape, but still pose a risk to others after flight. The marking effected by the spray helps in later identification of a subject. A preferred embodiment of the formulation of the defense spray composition in a 50 gallon batch incorporating this dispersion feature comprises: 10.00% Horseradish oil - 5 gallons

25.00% Ethanol - 12.5 gallons

10.00% Propylene Glycol - 5 gallons

2.00% Polysorbate 80 - 1 gallon

0.50% D&C Green #8 Dye - 0.25 gallons

0.01% FD&C Green #3 Dye - 0.005 gallons 51.49% water - 25.745 gallons

1.00% UV Dye - 0.5 gallons

[0026] The spray composition of the present invention is very effectively employed as a means to temporarily incapacitate a subject for a relatively short period of duration. The subject is sprayed with the isothiocyanate composition in the normal manner as that for pepper spray. However, the volatile nature of the isothiocyanate compound causes the felt effects to diminish sooner than that experienced when sprayed by red pepper (or capsaicin). Because of the volatile nature of the inventive spray, there is less potential for mission-jeopardizing cross-contamination of law enforcement personnel from misdirected spray. Furthermore, the inventive spray permits a more rapid decontamination of the subject so that his cooperation can be more readily obtained after the situation giving rise to the need for the spray deployment has been brought under control. This permits a more efficient apprehension and processing of a subject with minimal disruptive effect on law enforcement personnel. [0027] The detailed description set-forth above is provided to aid those skilled in the art in practicing the present invention. However, the invention described and claimed herein is not to be limited in scope by the specific embodiments herein disclosed because these embodiments are intended as illustration of several aspects of the invention. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the invention in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description which do not depart from the spirit or scope of the present inventive discovery. [0028] Having thus described the preferred embodiments of the invention, what is claimed as new and desired to be protected by Letters Patent includes the following: CLAIMS

1. A spray composition for temporarily incapacitating a subject, the spray composition comprising an isothiocyanate compound of the formula

2. The spray composition according to Claim 1 in which R may be selected from the group consisting of alkyl, alkenyl, allyl, and alkylthioalkyl.

3. The spray composition according to Claim 1 in which the isothiocyanate compound is produced synthetically.

4. The spray composition according to Claim 1 in which the isothiocyanate compound is isolated from a Brassicaceae family plant source.

5. The spray composition according to Claim 4 in which the plant is selected from the group consisting of horseradish, wasabi and mustard.

6. A spray composition for temporarily incapacitating a subject, the spray composition comprising horseradish oil as an ingredient between 0.1% to 20% by weight of the spray composition.

7. The spray composition of Claim 6 in which the spray composition includes propylene glycol, ethanol, an emulsifier and water.

8. The spray composition of Claim 6 in which a propellant is added whereby the spray is adapted for dispersion as a fog spray pattern.

9. The spray composition of Claim 6 in which the spray comprises 5% horseradish oil, 5% glycol ether DB and 90% propellant, the propellant comprising HFC 134a, whereby the spray is adapted for rapid evaporation after deployment.

10. The spray composition according to Claim 6 in which a marker dye is added. 11. A method for temporarily incapacitating a subject where the incapacitating time is of short duration, the method comprising spraying the subject with a spray composition comprising an isothiocyanate compound of the formula

12. The method according to Claim 11 in which the R group in the spray composition may be selected from the group consisting of alkyl, alkenyl, allyl, and alkylthioalkyl.

13. The method according to Claim 11 in which the isothiocyanate is provided by a compound selected from the group consisting of horseradish, wasabi and mustard. INTERNATIONAL SEARCH REPORT international application .

PCT/US201 1/062236

A . CLASSIFICATION O F SUBJECT MATTER IPC(8) - B05B 11/06 (201 2.01 ) USPC - 424/1 0.4 According to International Patent Classification (IPC) o r to both national classification and IPC

B . FIELDS SEARCHED

Minimum documentation searched (classification system followed by classification symbols) IPC(8) - A01N 65/00; A61 9/68, 49/00; B05B 1/06 (2012.01 ) USPC - 424/10.4, 405, 725, 739, 755

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

PatBase, Google Patents, Google Scholar

C . DOCUMENTS CONSIDERED T O B E RELEVANT

Category* Citation o f document, with indication, where appropriate, of the relevant passages Relevant to claim No.

US 2003/0170180 A 1 (BAHARY) 11 September 2003 ( 1 .1 1.2003) entire document 1-13

US 2006/0127996 A 1 (FAHEY) 15 June 2006 (15.06.2006) entire document 1-13

US 5,334,373 A (SEKIYAMA e t al) 02 August 1994 (02.08.1994) entire document 1-13

US 5,248,504 A (FRIEDMAN) 28 September 1993 (28.09.1993) entire document 1-13

Further documents are listed in the continuation o f Box C . | |

* Special categories of cited documents: "T" later document published after the international filing date or priority "A" document defining the general state of the art which is not considered date and not in conflict with the application but cited to understand to be of particular relevance the principle or theory underlying the invention "E" earlier application or patent but published on or after the international "X" document of particular relevance; the claimed invention cannot be filing date considered novel or cannot be considered to involve an inventive "L" document which may throw doubts on priority claim(s) or which is step when the document is taken alone cited to establish the publication date of another citation or other special reason (as specified) "Y" document of particular relevance; the claimed invention cannot be considered to involve an inventive step when the document is "O" document referring to an oral disclosure, use, exhibition or other combined with one or more other such documents, such combination means being obvious to a person skilled in the art "P" document published prior to the international filing date but later than "&" document member of the same patent family the priority date claimed Date o f the actual completion o f the international search Date o f mailing of the international search report 19 March 2012 MAR 2012

Name and mailing address o f the ISA/US Authorized officer: Mail Stop PCT, Attn: ISA/US, Commissioner for Patents Blaine R . Copenheaver P.O. Box 1450, Alexandria, 22313-1450 PCT Helpdesk: 571-272-4300 Facsimile No. 571-273-3201 PCT DSP: 571-272-7774