CA1286985C

CA1286985C - Substantive insect repellent/toxicant composition

Info

Publication number: CA1286985C
Application number: CA000546130A
Authority: CA
Inventors: John W. Matteson; Neil A. Randen
Original assignee: Minnesota Mining and Manufacturing Co
Current assignee: 3M Co
Priority date: 1986-10-10
Filing date: 1987-09-04
Publication date: 1991-07-30
Anticipated expiration: 2008-07-30
Also published as: AU7814287A; NZ221641A; AU603376B2

Abstract

ABSTRACT OF THE DISCLOSURE

Insect repellent/toxicant compositions for use on domestic animals comprising an effective amount of a pyrethroid, an oil soluble, water insoluble acrylate polymer and a liquid carrier are disclosed. The compositions are effective for an extended period of time.

Description

~8~'t3~5 41918 CAN lA

SU~ST~NTIVE_IN5ECT REPELLEWT/TOXICANT COMPOSITION
BACRGROUND OF THE INVENl ION

The present invention relates to insect repellent/toxicant compositions for use on domestic animals.
More particularly, the invention relates to insect repellent/toxicant compositions wherein a pyrethroid 10 repellent/toxicant, applied to an animal's body hair, is rendered effective for an exten~ed perio~ of time by means of a polymeric binder.
Insect repellents/toxicants for use on domestic animals are well known in the art. Examples of commercially 15 available products are Super Swat* available from Farnam Companies, Inc. of Omaha, Nebraska; Absorbine Super Shield*
II available from W.F. Young, Inc. of Springfield, MA; and Poridon* available from Fearing Manufacturing Co., Inc. of South St. Paul, MN.
Many of the prior art compositions are not water resistant and are easily removed by rain or perspiration.
Many of the compositions employ natural pyrethrins which are readily decomposed into inactive products in the presence of oxygen and ultraviolet light. The 25 speed of this decomposition (or environmental degradation) is dependent upon the environment in which the pyrethrins are placed but typically takes place in from several minutes to several hours. Attempts have been made to overcome these problems by encapsulation of the pyrethrins (United States Patent 4,056,610); by incorporating a film-forming agent (European Patent Application 84 11 2338 published June 5, 1986), and by the use of various other carriers. The use o certain carriers often results in a cosmetically unacceptable product. Appearance is an important consideration when the compositions are used on "show" animals.

~Trade-mark 12~ 385 SUMMAR~ NVENTION
The present invention relates to insect repellent/toxicant compositions for use on domestic animals which are effective for an extended period of time. The compositions comprise one or more pyrethroid insect repellents/toxicants, an oil soluble, water insoluble acrylate polymer and a liquid carrier. When natural pyrethrins are employed, the compositions may further comprise biological synergists, antioxidants and ultraviolet light absorbers. -DETAILED_DESCRIPTION OF THE INVENTION
The insect repellent/toxicant compositions of the present invention are liquid formulations comprising an oil-soluble, water insoluble acrylate polymer, one or more pyrethroids and a liquid carrier. When the insect repellent/toxicant is a natural pyrethrin, the compositions may further comprise biological synergists, antioxidantsr germicides, and ultraviolet light absorbers.
According to one aspect of the present invention there is provided an insect repellent~toxicant composition substantive to animal hide and hair comprising:
an effective amount of a pyrethroid insecticide;
at least 0.1 percent by weight of a water insoluble acrylate polymer having a solubility parameter of 6 to 10 (cal./cc.)l/2 in poorly hydrogen bonding solvents and a Brookfield viscosity between about 50 and 100,000 cps. when measured at 16.6 percent nonvolatiles; and a liquid carrier.

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s 2a 60557-330 According to a further aspect of the present invention ~here is provided a composition substantive to animal hide and hair comprising:
a. from about 0.25 to 1.0 percent by weight of a 50:30,20 mole ratio of iso-octyl acrylate:stearyl methacrylate:acrylic acid terpolymer;
b. from ahout 0.1 to 1.0 percent of natural p~rekhrins;
c. from about 0.2 to 10.0 percent of 3,4-methylenedloxy-6-propylb~nzyl butylcliethylene glycol ether;
d. ~rom about 0 to 3.3 percent of N-(2-ethylhexyl)-bicyclo[2.2.1]-5-heptene-2,3-dicarboximide;
e. from about 0.02 to 1.0 percent of octadecyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate;
f. ~rom about 0.1 to 1.0 percent of 2-hydroxy-4-methoxybenzophenone;
g. from about 82 to 99 percent of a liquid carrier.
The ins~ct repellent/toxicant compositions of the present invention are substantive to animal hide and hair and are resistant to removal by water rinsing (e.g., by rain or perspiration). Further even those compositions containing natural pyrethrins remain effective for an extended period of time. U.S.
Patent 4,552,755 teaches that the incorporation of specific oil-soluble, water insoluble acryla~e polymers into oil-in-water emulsion formulations will result in an improved moisturizing composition by maintaining the emolient oils on the skin s surface longer. Therefore, it was surprising to find that pyrethroids incorporated into such polymers are still available at an :., - . -. : :

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2b 60557-3302 effective level. However, what was more surprlsiny was the fact that in spite of the known instability of the pyre~hroids the composition had effectlve life times far exceediny the composition~ without the acrylate polymers. Althouyh the exact mechanism is not fully under.s~ood it is believed that the oil soluble, water , .... . . . : ~
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. .,. ~;.' ' insoluble acrylate polymer may serve to keep the pyrethrins in intimate contact with the antio~idant and ultraviolet sabsorbers and thereby their decomposition is inhibited.
Further the compositions of the present invention are cosmetically acceptable. The amount of oil soluble, water insoluble acrylate polymer is controlled such that the composition is substantive to the hide and hair but i6 not so sticky that it will attract dust and other extraneous material.
The acrylate polymers which are useful in the present invention are those which have been described in U.S.
Patent 4,552,755, and include homopolymers, copolymers, terpolymers, etc., derived from the same or different ester monomers of the formula:

CH = C Formula I
C2 Rl wherein R1 is alkyl containing 1 to 18 carbon atoms in straight or branched chain configuration, R2 is hydrogen, methyl or -CH2CO2H, and R is -CO2H or -CO2R , provided that when R3 is -CO2H or -CO2R1, R2 is hydrogen.
25 The polymer may optionally contain up to about 50 mole percent of the same of different acid monomers of the formula:
Rq Rs CH = C Formula II

where R4 is hydrogen of -CO2H, and Rs is hydrogen, methyl or -CH2CO2H, provided that when R4 is -CO2H, R5 is hydrogen.
The acrylate polymers can be prepared from the 35 corresponding alkyl esters of acrylic, methacrylic, `i~,j~

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. -',~ ' . ' , ' ' ' ' itaconic or maleic acid, wherein the ester alkyl groups may contain 1 to 18 carbon atoms and are exemplified by methyl, ethyl, butyl, methylisoamyl, n-hexyl, 2-ethylhexyl, isooctyl, isodecyl, lauryl, octadecyl, stearyl groups and the like. The preferred esters are the acrylates and methacrylates with alkyl groups containing 6 to 1~ carbon atoms. Currently the most preferred esters are isooctyl acrylate and stearyl methacrylate. Esters wherein the alkyl 10 group contains less than four carbon atoms may be included in small amounts, e.g., less than 10 mole percent. ~lowever in order to achieve the requisite solubility parameter, the polymers should generally not contain a significant amount of lower alkyl ester monomers.
The acrylate polymers may optionally contain up to 30 mole percent of the unesterified a, ~-olefinically unsaturated carboxylic acids of Formula II such as acrylic acid, methacrylic acid, maleic acid or itaconic acid.
Currently acrylic acid is preferred.
The preferred polymers are derived from 0 to 25 mole percent of the acid monomers and from lO0 to 75 mole percent of alkyl ester monomers having 6 to 18 carbon atoms in the ester alkyl group.
The preparation of the polymers from the ;~5 olefinically unsaturated monomers is well documente~ in the literature and can be carried out by standard bulk, solution or emulsion techniques. Generally, the latter two ~; are preferred with solution polymerization being most preferred. The polymerization of the monomers is catalyzed 30 by free radical-generating catalysts such as peroxides, azo catalysts and the like. To be most effective, the reactor for such polymerizations should be purged with an inert gas in order to remove traces of oxygen. The solution polymerizations are run in a compatable solvent and the 35 final polymer solution preferably contains 30 to 60 percent solids.
The molecular weight of the polymers used in the compositions may vary over a broad range. The molecular ~ .
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weight must be suitably large to provide the requisite substantivity effect. The upper limit is determined by formulation requirements. As the molecular weight increases, the polymers tend to become too viscous to formulate easily into cosmstically-acceptable compositions.
Generally, polymers having a srookfield viscosity between 50 and 100,000 cps, and preferably between 500 and 15,000 cps, when measured at 16.~ percent nonvolatiles will be 10 useful in the compositions of the invention.
The acrylate polymers useful in the compositions are insoluble in water and must have a solubility parameter between about 6-10 (cal/cc)~/2 in poorly hydrogen bonding solvents. The method for determining solubility parameter ranges of polymers and an extensive list of solvents (classified as either poorly hydrogen bonding, moderately hydrogen bonding, or strongly hydrogen bonding) are described in Polymer Handbook (edited by ~andrup and .
Immergut), pages IV, 344-358. Acrylate polymers having the requisite solubility parameters are also oil soluble and compatible with the pyrethroids.
The acrylate polymers may comprise from about 0.1 to 4.0 percent, and preferably from about 0.25 to 1.0 percent, by weight of the composition.
Pyrethroids, including both the naturally occurring compounds and their synthetically prepared analogs, are a well known class of insect repellents/toxicants. They have broad spectrum activity, that is, they are effective against a variety of pests such 30 as flies, gnats, mosquitoes, fleas, etc. They generally are not harmful to plants, domestic animals and humans and are consequently environmer.tally safe.
Suitable pyrethroids for use in the compositions of the present invention include both the naturally 35 occurring pyrethrum esters derived from the dried flower heads of Chrysanthemum cinnerariaefolium and Chrysanthemum coccineum and the synthetically prepared esters of chrysanthemic acid.

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Naturally occurring pyrethrum esters comprise the group including pyrethrin I, pyrethrin II, cinerin I, cinerin II,and jasmolin II. Synthetically prepared esters comprise the group including allethrims, barthin, dimethrin, resmethrin, tetramethrin, permethrin and cypermethrin. The pyrethroids used in the compositions may comprise any of the naturally occurring pyrethroids, any of the synthetically prepared pyrethroids, or combinations of two or more of either or both types. A solution o~ a combination of naturally occurring pyrethroids in deodorized kerosene which is commercially available under the trade designation "Pyrethrum Pyrocide~ 175" from McLaughlin Gormley King Co. of ~inneapolis, MN is suitable for use i51 the present invention. The pyrethroids may comprise from about 0.05 to 5.0 percent, and preerably from about 0.1 to 1.0 percent, by weight of the composition.
Suitable biological synergists for inclusion in the compositions generally have little or no insect repellent or toxicant activity by themselves but significantly increase the performance of the pyrethroids when combined therewithO A variety of ~ynergists are useful in compositions of the present invention.
25 Representative examples of these synergists are given on pages 196-197 of Pyrethrum the Natural_Insecticide, edited by John E. Casida, Academic Press, New York, 1973. Among the preferred biological synergists are the piperonyl alkyl ethers such as [3,4-(methylenedioxy)-6-propylbenzyl] butyl 30 diethyleneglycol ether (also known as piperonyl butoxide), commercia~ly available under the trade designation "sutacide" from Niagara Chemical Division of FMC Corp. and N-(2-ethylhexyl)-bicyclo~2.2.1]-S-heptene-2,3-dicarboximide commercially available under the trade designation MGK-264 from the McLaughlin Gormley Xing Co. of Minneapolis, MN. The synergists may comprise up to 30 percent, and, when a natural pyrethrin is employed, preferably from about 0.5 to 10.0 percent, by weight of the ~c~ e~ k . ~ . .. .. . ` .. , . . . .. `
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composition.
Antioxidants may also be included in the composition to minimize the degradative effects of oxygen by inhibiting the formation of hyperoxide groups and their subsequent decomposition into alkoxy and hydroxy radicals in the compositions. A variety of antioxidants are useful in compositions of the preslent invention. Representative examples include alkylated phenols such as 2,~-di-t-butyl c~esol, 2,2'-methylenebis(6-t-butyl-4-methyl phenol), 2,2'-thio bis(6-t-butyl-4-met:}lyl phenol), pentaerythritol tetrakis 13-(3,5-di-t-buty:L-4-hydroxyphenyl)]propionate, octadecyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate commercially available under the trade designation of "Irganox~1076" available from Ciba Geigy Corp., etc;
thioesters such as dilauryl thiodipropionate, dimyristyl thiodipropionate; and phosphites such as tris (nonylphenyl phosphite). The antioxidants comprise up to 5 percent, and, when a natural pyrethrin is employed, preferably from about 0.02 to 1.0 percent, by weight of the compostion.
Ultraviolet light absorbers may also be included in the compositions. Suitable compounds absorb ultraviolet radiation in the ~ange of about 270 350 nanometers and convert it to a harmless form. They have a high absorption 25 coefPicient in the near ultraviolet portion of the spectrum ~e.g. a log molar extinction coefficient of from about 2 to 5) b~t only minimal absorption in the visible portion of the spectrum. Among the compounds which are useful as ultraviolet light absorbers are substituted benzophenones 30 such as 2,4-dihydroxybenzophenone, 2-hydroxy~4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, etc; the benzotriazoles such as 2-(2-hydroxy-5'-methylphenyl)bPnzotriazole, 2-(3',5'-diallyl-2'-hydroxyphenyllbenzotriazole, etc;
35 salicylates such as 2-ethyl-n-hexylsalicylate, 5-butyl phenyl salicylate, etc; cinnamates such as 2-ethoxyethyl-p-methoxycinnamate, etc.; and aminobenzoates such as 2-ethylhexyl-p-dimethylaminobenzoate. The ~ Jr-c~c~ q~k . . .. .. . . - .

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ultraviolet light absocbers may comprise up to 5 percent, and, when a natural pyrethrin is employed, preferably from about 0.1 to 1.0 percent, by weight of the composition.
When the liquid carrier is water, the compositions of the invention are formulated as oil-ir.-water emulsions in the conventional manner. All lipophilic ingredients are combined in the oil phase; the resulting mixture is stirred, and may be optionally warmed to about 50 C., until all the ingredients are in solution.
The oil phase is then added to the aqueous phase with moderate stirring.
Any conventional oil-in-water emulsifying agent may be used in the compositions of the present inventlon.
lS The emulsifier may be present in about 0.1 to 5.0 percent by weight of the composition.
When the liquid carrier is a solvent such as isopropyl alcohol, the formulations may be prepared by combining all ingredients and then diluting with the slvent.
Insect toxicity is determined by means of a bioassay. In performing the bioassay, a section of bovine hide is sprayed with a known amount of formulation and then placed in a glass container fitted with a fine mesh scrsen 25 top together with 15-20 houseflies. The percentage of flies knocked down after 15, 30 and 60 minutes of exposure to the hide is then recorded.
Insect repellency is determined by means of a bioassay test. In performing the bioassay, sections of 30 bovine hide are sprayed with known amounts of formulations.
The hides are then subjected to either simulated sunlight or to simulated rainfall. This exposure reduces the toxicant effect and prevents fly mortality from interfering with testing the repellency produced by different 35 formulations.
After exposure the hides are attached to the interior surface of the backside of a cage containing seYeral hundred houseflies. Each cage will accomodate :, , . , , - : . . -.~ .
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, ' ' twelve sections of hide thus allowing for three replicates of three different formulations plus controls. Improvements in repellency can be detected by comparing the number of flies on the hides treated with the test formulations to the number of flies on the control hides.
outdoor conditions are simulated by placing the t~eated hides in a Weather-O-Meter for three to four hours and exposing them to high levels of ultraviolet light and high humidity. The Atlas Weather-O-Mete ~ available from Atlas Electric Devices Company, Chicago, Illinois is suitable for use in this assay. The hides are subsequently evaluated for residual repellency.
Rainfall or sweating is simulated by holding treated hides under a spray of warm (35 to 45 C.) water for varying lengths of time, usually 30 to 60 seconds. After the residual water is allowed to evaporate, the hides are tested for residual repellency.
The following examples are presented to further illustrate, but not limit, the present invention. All formulae are given in parts and percentages by weight unless otherwise noted.

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Example 1 Formulations Using Different Polymers Formulations were prepared using six different polymers. All other ingredients were held constant.

Ingredient _ W/W in Formulation 1 *Polymer (45% polymer in 2.0 1:2 ethyl acetate : heptane) Pyrethrins 1.1 (56% extract in kerosene) Piperonyl 9utoxide 1.2 MGK 264 (N-octyl bicycloheptene 2.0 dicarboximide) Igepal CO 630 (nonoxynol-9)1.0 Irganox 1076 (octadecyl 3-l3',5'-di- 0.02 20 t-butyl-4'-hydroxyphenyl3propionate) Uvinul M-40~ n . 2 (2-hydroxy-4-methoxybenzophenone) Water 92.28 100 . O
- MGK 264 is a biological synergist available from McLaughlin Gormley King Co. of Minneapolis,MN.
Igepal CO 630 is an emulsifier available from GAF
Irganox 1076 is an antioxidant available Ciba Geigy 30 Uvinul M-40 is an ultraviolet light absorber available from BASF-Wyandotte *The six polymers used are listed below. The ratios are given in moles of iso-octyl acrylate : stearyl methacrylate : acrylic acid.
35 a)10:70:20 b) 30:50:20 c) 50:30:20 d) 20:70:10 e) 40:50:10 f) 60:30:10 C~ e~ clrk - : :
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'' ' : ' Sections of bovine hide were sprayed with the formulations then allowed to dry for two hours before being rinsed for one minute with warm ( ~5 to 45C. ) water. The hide~ were allowed to dry for about sixteen hours and then were tested for insect repellency using the bioassay previously described. All hides treated with test formulations showed significantly greater insect repellency for a minimum of 21 hours commencing with the rinsing than did hides treated 10 with the same formulation minus the polymer.

Example 2 Formulations Usinq Different Levels of Polymer . . . ~

Eight different formulations containing different levels of polymer were prepared and tested.

In redient % W/W in Formulation Po ~ymer tmole ratio of 50:30:20 -~~~-of iso-octyl acrylate:stearyl 0.0 , 1.1 20 methacrylate: acrylic acid; 2.2', 3.3d 45% polymer in 2:1 4.4-, 0. of n-heptane:ethylacetate) 1.19, 1. 7h Pyrethrins ~56~ extract in kerosene) 1.1 Piperonyl Butoxide 1.2 MGK 264 2.0 Igepal CO 630 1.0 Irganox 1076 0.02, 0.5f-h 30 Uvinul M-40 0.2, o. 5f-h Water 94.48a, 93.38b, 92 28C 91 18d 90.08 , 93.70 , 92.609, 92.00 100 . O
Bovine hides were sprayed with the test formulations, allowed to dry for about two hours, rinsed with warm water for one minute and then allowed to dry for about sixteen hours. The hides were then tested for insect repellency usin~ the bioassay described previously. The hide6 sprayed , ': :, ; : ' , , . .

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with test formulations showed greater repellency than did hides sprayed only with water. The hides sprayed with formulations containing polymer ~howed greater repellency than the hides sprayed with formulations that did not contain polymer. ~ovine hides that had been treated with formulations f, g and h were placed in a Weather-O-Meter for three hours and then tested for insect repellency. The results were the same as those subjected to the water 10 rinsing.
Example 3 Formulations Usin~ Different Levels of Antloxidant A series o formulations using different amounts of antioxidant were prepared and tested.

Ingredient ~W/W in Formulation 50:30:20 mole ratio of iso-octyl 2.2a,b, l lc 20 acrylate:stearyl methacrylate:
acrylic acid 45~ polymer in 2:1 n-heptane:ethyl acetate Pyrethrins 1.1 56% extract in kerosene 25 Piperonyl Buto~ide 1.2 MGR 264 2.0 Igepal CO 630 1.0 Uvinul M-40 0.2~,b, 0.5c 30 Irganox 1076 a: 0.0, l.0, 2.0 b: 0.0, 0.02, 2.0 c: 0.25, 0.5, 1.0 Water a: 92.3, 91.3, 90.3 b: 92.3, 92.28, 90.3 c: 92.85, 92.6, 92.1 100.0 Bovine hides were sprayed with formulation, allowed to dry for about an hour then placed in a - , ~ , .
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Weather-O-Meter for about three hours. About sixteen hours later the hides were tested for insect repellency using the bioassay described previously. The hides treated with test formulations showed greater repellency than hides sprayed with water. The hides treated with formulations containing 0.25% to 2.0% Irganox showed greater insect repellency ~or a minimum of 24 hours commencing with the Weather-O-Meter exposure than did the hides treated with formulations containing 0.02% or 0.0% Irganox.

Example 4 Formulations Usin~ Different Li~uid Carriers A series of formulations using different liquid carriers was prepared and tested.

Ingredient % W/W in Formulation 50:30:20 mole ratio of iso-octyl 2.2 20 acrylate:stearyl methacrylate:
acrylic acid 45% polymer in 2:1 n-heptane:ethyl acetate Pyrethrins 1.1 25 (56% extract in kerosene) Piperonyl sutoxide 1.2 MGK 264 - 2.0 Igepal 1.0 Irganox 1076 0.02 35 Uvinul M-40 1.0 Liquid Carrier 92.48 100.0 - : -~ . -. , . : -.

Six different liquid carriers were used: water, i~opropyl alcohol, 5.0% isopropyl alcohol in water, 2.5%
isopropyl alcohol in water, 5.0% ethanol in water, and 7.5~
ethanol in water. sOvine hides were sprayed with the test form~31ations, allowed to dry for about an hour and a half, and then placed in a Weather-O-Meter for about three hours.
About eighteen hours later they were tested for insect repellency. The hides treated with the formulation using isopropanol as the liquid carrier showed greater repellency for a minimum of 48 hours commencing with the Weather-O-Meter exposure than did the hides treated with the other formulations.

Exampl e S
F mulations Usin4 Different Ultraviolet Light Absorbers Ingredient ~ W/W in Formulations 20 50 30 20 mole ratio of iso-octyl 2.2 acrylate:stearyl methacrylate:
acrylic acid 45% polymer in 2:1 n-heptane:ethyl acetate Pyrethrins 1.1 ~56~ extract in kerosene) Piperonyl Butoxide 1.2 MGK 264 2.0 Igepal CO 630 1.0 Irganox 1076 0.02 UV absorber 1.0 Liquid carrier 91.48 ~ 100.O
Nine formulations were prepared using different - ultraviolent light absorbers with either water or isopropyl alcohol as the liquid carrier. Formulations containing Uvinul M-40, para-aminobenzoic acid, and Spectra-Sorb-UV-24 -~@ r~ e~ c~

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~15-~2,2'-dihydroxy-4-methoxybenzophenone: available from American Cyanamide) were prepared using isopropyl alcohol as the liquid carrier. Formulations containing Uvinul M-40, Giv-Tan F~(2-ethoxyethyl-p-methoxycinnamate available from Givaudan Corp., Clifton, NJ), Parsol MCX
(octylmethoxycinnamate, availabLe from Givaudan Corp.), Escalol ~ 507 (2-ethylhexyl-p-dimethylaminobenzoate;
available from Van Dyk & Cot Inc., Belleville, NJ), Sunarome WMO~ (2-ethyl-n-hexylsalicylate; available from Felton International, Inc., Brooklyn, NY), and glyceryl p-aminobenzoate were prepared using water as the liquid carrier. sovine hides were sprayed with the test formulations, allowed to dry for about one hour and then placed in a Weather-O-Meter for three hours. About sixteen hours later the hides were tested for insect repellency.
The isopropyl alcohol based Uvinul M-40 formulation was better than the water based formulation. Uvinul M-40, para-aminobenzoic acid, Specra-Sorb-UV-24, Giv-Tan F and 20 Parsol MCX all resulted in effective formulations. The formulations using Escalol 507 and Sunarome WMO were less effective and the formulation using glyceryl para-aminobenzoate was significantly less effective than the other formulations.

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Example 6 Formulations Usina Different Levels of Ultraviolet Li~ht 5 Absorber Ingredient % W/W in Formulation 50:30:20 mole ratio of iso-octyl 2.2 acrylate:stearyl methacrylate:
acrylic acid 45% polymer in 20l n-heptane:ethyl acetate Pyrethrins l.l (56~ extract in kerosene) Piperonyl Butoxide l.2 MG~ 264 2.0 Igepal CO 630 l.0 Irganox lO76 0.25~, 0.0 2b,C
Uvinul M-40 a: 0.0, 0.25, 0.5, 0.75 b: 0.0, 0.2, 2.0 c: 0.0, 1.0 Water a: 92.25, 92.0, 91.75, 91.5 - b: 92.4~, 92.28, 90.48 c: 92.48, 91.48 ' 100'.0 A series of formulations using different levels of Uvinul M-40, an ultraviolet absorber, were prepared.
sovine hides were sprayed with the test formulations, allowed to dry and then placed in a Weather-O-Meter for about three hours. About sixteen hours later the hides were tested for insect repellency. The hides treated with formulations containing Uvinul M-40 showed greater repellency for a minimum of 40 hours commencing with the Weather-O-Meter exposure than the hides treated with formulations that did not contain the ultraviolet light 35 absorber.

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Claims

1. An insect repellent/toxicant composition substantive to animal hide and hair comprising:
an effective amount of a pyrethroid insecticide;
at least 0.1 percent by weight of a water insoluble acrylate polymer having a solubility parameter of 6 to 10 (cal./cc.)l/2 in poorly hydrogen bonding solvents and a Brookfield viscosity between about 50 and 100,000 cps. when measured at 16.6 percent nonvolatiles; and a liquid carrier.

2. The composition according to Claim 1 wherein said polymer is derived from the polymerization of the same or different ester momomers of the formula:

where R1 is alkyl containing 1 to 18 carbon atoms, R2 is hydrogen, methyl or -CH2CO2H, and R3 is hydrogen, -CO2H
or -CO2R1; provided that when R3 is -CO2H or -CO2Rl, R2 is hydrogen; and optionally contains up to 30 mole percent of the same or different acid monomers of the formula:

where R4 is hydrogen or -CO2H and R5 is hydrogen, methyl or -CH2CO2H, provided that when R4 is -CO2H, R5 is hydrogen.

3. The composition of Claim 2 wherein said polymer contains from 100 to 80 mole percent of said ester monomers and from 0 to 20 mole percent of said acid monomers.

4. The composition of Claim 2 wherein said ester monomers comprise alkyl esters of acrylic and methacrylic acid wherein the alkyl group contains 6 to 18 carbon atoms.

5. The composition of Claim 1 wherein said polymer is a terpolymer of iso-octyl acrylate, stearyl methacrylate, and acrylic acid.

6. The composition of Claim 5 wherein said polymer contains 50 mole percent iso-octyl acrylate, 30 mole percent stearyl methacrylate and 20 mole percent of acrylic acid.

7. The composition of Claim 6 containing 0.25 to 1.0 percent by weight of said polymer.

8. The composition of Claim 1 wherein the liquid carrier is water.

9. The composition of Claim 8 further comprising an emulsifying agent wherein said emulsifying agent is present in an amount between 0.1 and 5.0 percent by weight of said composition.

10. The composition of Claim 1 wherein the liquid carrier is isopropyl alcohol.

11. The composition of Claim 1 wherein said pyrethroid is present in an amount between 0.05 and 5.0 percent by weight of said composition.

12. The composition of Claim 11 wherein said pyrethroid is a naturally occurring pyrethrum ester.

13. The composition of Claim 11 further comprising a biological synergist, an antioxidant and an ultraviolet light absorber.

14. The composition of Claim 13 wherein said synergist is selected from the group consisting of 3,4-methylenedioxy-6-propylbenzyl butyldiethylene glycol ether and N-(2-ethylhexyl)-bicyclo[2.2.1]-5-heptene-2,3-dicarboximide.

15. The composition of Claim 13 wherein said antioxidant comprises octadecyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate.

16. The composition of Claim 13 wherein said ultraviolet light absorber has a log molar extinction coefficient of from about 2 to 5 with respect to radiation having wavelengths in the range of about 270 to 350 nanometers.

17. The composition of Claim 16 wherein said ultraviolet light absorber is a substituted benzophenone.

18. A composition substantive to animal hide and hair comprising:
a. from about 0.25 to 1.0 percent by weight of a 50:30:20 mole ratio of iso-octyl acrylate:stearyl methacrylate: acrylic acid terpolymer;
b. from about 0.1 to 1.0 percent of natural pyrethrins;
c. from about 0.2 to 10.0 percent of 3,4-methylenedioxy-6-propylbenzyl butyldiethylene glycol ether;
d. from about 0 to 3.3 percent of N-(2-ethylhexyl)-bicyclo[2.2.1]-5-heptene-2,3-dicarboximide;
e. from about 0.02 to 1.0 percent of octadecyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate;
f. from about 0.1 to 1.0 percent of 2-hydroxy-4-methoxybenzophenone;
g. from about 82 to 99 percent of a liquid carrier.

19. The composition of Claim 18 wherein the liquid carrier is water further comprising from about 0.1 to 5.0 percent of nonoxynol-9.

20. A method of killing insects on an animal comprising applying a composition of Claim 1 to the animal.

21. A method of repelling insects for an extended period of time from an animal comprising applying a composition of claim 1 to the animal.