AU603376B2 - Substantive insect repellent/toxicant composition - Google Patents

Description

A ACHED MAIL 5845/2 c'NACCacEPTED AND AMENDMENTS A LL ED jXL r i :r 3376 S F Ref: 36380 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: Class Int Class Complete Specification Lodged: Accepted: Published: This document contains the amendments made under Section 49 and is correct for printing.

Priority: trC Ct Related Art: Name and Address of Applicant: Address for Service: Minnesota Mining and Manufacturing Company 3M Centre Saint Paul Minnesota 55144 UNITED STATES OF AMERICA Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia SComplete Specification for the invention entitled: C Substantive Insect Repellent/Toxicant Composition The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/3 Declred at Minnesota, this 18th dacy of August 1987

U.S.A.

Donald..Miller..Sell Chief. .Patent..Counsel SFl'4 To: The Commissioner of Putents Signature ol Declarant(s) 11/81 I 1 41918 AUS 8A SUBSTANTIVE INSECT REPELLENT/TOXICANT COMPOSITION BACKGROUND OF THE INVENTION 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 repellent/toxicant, applied to an animal's body hair, is I rendered effective for an extended period of time by means Jof a polymeric binder.

Insect repellents/toxicants for use on domestic animals are well known in the art. Examples of commercially I available products are Super Swat available from Farnam j '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 speed of this decomposition (or environmental degradation) is dependent upon the environment in which the pyrethrins are placed but typically takes place in from c|C, 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 23.38); and by the use of various other carriers. The use of certain carriers often results in a cosmetically unacceptable product. Appearance is an important consideration when the compositions are used on "show" animals.

I

I,

-2- SUMMARY OF THE INVENTION 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 15 present invention are liquid formulations comprising an oil f 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 bi i synergists, antioxidants, germicides, and ultraviolet light absorbers.

The insect repellent/toxicant compositions of the present invention are substantive to animal hide and hair I and are resistant to removal by water rinsing 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 acrylate polymers into oil-in-water emulsion formulations will result in an improved moisturizing

S

c 30 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 effective level. However, what was more surprising was the fact that in spite of the known instability of the pyrethroids the composition had effective life times far exceeding the compositions without the acrylate polymers. Although the exact mechanism is not fully understood it is believed that the oil soluble, water lrr .<y N~rp^^ j insoluble acrylate polymer may serve to keep the pyrethrins in intimate contact with the antioxidant and ultraviolet absorbers 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 is 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, which patent is incorporated herein by reference,- and include homopolymers, copolymers, F 15 terpolymers, etc., derived from the same or different ester monomers of the formula:

R

3

R

2 1 I CH C

CO

2

R

Formula I where R' is alkyl containing 1 to 18 carbon atoms in straight or branched chain configuration, R 2 is hydrogen, methyl or -CH 2

CO

2 H, and R 3 is -CO 2 H or -CO 2 R, provided that when R 3 is -CO 2 H or -COR 1

R

2 is hydrogen. The polymer may optionally contain up to about 50 mole percent of the same or different acid monomers of the formula: C C V cC c cc R4 I I CH C

CO

C02H Formula II where R 4 is hydrogen or -CO 2 H, and R 5 is hydrogen, methyl or -CH 2

CO

2 H, provided that when R 4 is -CO 2 H, R 5 is hydrogen.

The acrylate polymers can be prepared from the corresponding alkyl esters of acrylic, methacrylic, ,i -4itaconic 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 18 carbon atoms. Currently the most preferred esters are isooctylacrylate and stearyl methacrylate. Esters wherein the alkyl group contains less than four carbon atoms may be included in small amounts, less than 10 mole percent. However in order to achieve the requisite solubility parameter, the polymers should generally not contain a significant amount.

of lower alkvl ester monomers.

acrylate polymers may optionally contain up to 30 mole percent of the unesterified c, O-olefinically I 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 mole percent of the acid monomers and from 100 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 olefinically unsaturated monomers is well documented 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 S c 30 by free radical-generating catalysts such as peroxides, azo catalysts and the like. To be most effective, the reactor j 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 final polymer solution preferably contains 30 to 60 percent solids.

The molecular weight of the polymers used in the LIA compositions may vary over a broad range. The molecular n~br I 5 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 Sformulate easily into cosmetically-acceptable compositions. Generally, polymers having a Brookfield viscosity between 50 and 100,000 cps, and preferably between 500 and 15,000 cps, when measured at 16.6 percent nonvolatiles will be 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) in poorly hydrogen bonding solvents. The method for determining solubility parameter ranges of polymers and an extensive list of solvents (classified I 4 as either poorly hydrogen bonding, moderately hydrogen bonding, or strongly hydrogen bonding) are described in Polymer Handbook published in 1975 by John Wiley Sons, New York (edited by Bandrup 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 preferably comprise from about 0.1 to percent, and most 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 as flies, gnats, mosquitoes, fleas, etc. They generally are not harmful to plants, domestic animals and Suitable pyrethroids for use in the compositions of the present invention include both the naturally occurring pyrethrum esters derived from the dried flower heads of Chrysanthemum cinnerariaefolium and Chrysanthemum coccineum and the synthetically prepared esters of chrysanthemic acid.

RLF/1153h 6 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 allethrlms, 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 of 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 Minneapolis, MN is suitable for use in the present invention. The pyrethroids preferably comprise from Sabout 0.05 to 5.0 percent, and most preferably from about 0.1 to S percent, by weight of the composition.

Suitable insecticidal synergists for inclusion in the compositions generally have little or no insect repellent or toxicant activity by *I t 1 themselves but significantly increase the performance of the pyrethroids when combined therewith. A variety of synergists are useful in compositions of the present invention. 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 Spreferred biological synergists are the piperonyl alkyl ethers such as [3,4-(methylenedioxy)-6-propylbenzyl] butyl diethyleneglycol ether (also known as piperonyl butoxide), commercially available under the trade designation "Butacide" from Niagara Chemical Division of FMC Corp. and N-(2-ethylhexyl)-bicyclo[2.2.11-5-heptene-2,3-dicarboximide commercially available under the trade designation "MGK-264" from the McLaughlin Gormley I King Co. of Minneapolis, MN. The synergists preferably comprise up to percent, and, when a natural pyrethrin is employed, preferably from about to 10.0 percent, by weight of the /i -7composition.

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 present invention. Representative examples include alkylated phenols such as 2,6-di-t-butyl cresol, 2,2'-methylenebis(6-t-butyl-4-methyl phenol), 2,2'-thio bis(6-t-butyl-4-methyl phenol), pentaerythritol tetrakis (3-(3,5-di-t-butyl-4-hydroxyphenyl)Ipropionate, octadecyl 3-(3 ',5'-di-t-butyl-4'-hydroxyphenyl)propionate commercially available under the trade designation of Sr 15 "Irganox 1076" available from Ciba Geigy Corp., etc; thioesters such as dilauryl thiodipropionate, dimyristyl thiodipropionate; and phosphites such as tris (nonylphenyl phosphite). The antioxidantsycomprise 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 range of about 270-350 panometers and convert it to a harmless form. They have a high absorption coefficient in the near ultraviolet portion of'the spectrum a log molar extinction coefficient of from about 2 to but only minimal absorption in the visible portion of the spectrum. Among the compounds which are useful as ultraviolet light absorbers are substituted benzophenones C C 30 such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, etc; the benzotriazoles such as 2-(2-hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-diallyl-2'-hydroxyphenyl)benzotriazole, etc; salicylates such as 2-ethyl-n-hexylsalicylate, phenyl salicylate, etc; cinnamates such as 2-ethoxyethyl-p-methoxycinnamate, etc.; and aminobenzoates such as 2-ethylhexyl-p-dimethylaminobenzoate. The 7 g,'L7A

A

ultraviolet light absorbers *i-\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-in-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 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 invention.

i 15 The emulsifier may-4.e\present in about 0.1 to 5.0 percent by weight of the composition.

J ,r 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 solvent.

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 screen top together.with 15-20 house.flies. The percentage of flies knocked down after 15, 30 and 60 minutes of exposure -to the

I

hide is then recorded.

Insect repellency is determined by means of a i Sbioassay test. In performing the bioassay, sections of Sc 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 formulations.

After exposure the hides are attached to the interior surface of the backside of a cage containing several hundred houseflies. Each cage will accomodate x<0 7-

'N

-i 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 treated 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-Meter 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 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.

7

II

a ;7,

I

B: .S

I

i i" I c 10 i 6 4.

t

CI

L€

C

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

lngredient W/W in Formulation *Polymer (45% polymer in 1:2 ethyl acetate heptane) Pyrethrins 1.1 (56% extract in kerosene) Piperonyl Butoxide 1.2 MGK 264 (N-octyl bicycloheptene dicarboximide) Igepal CO 630 (nonoxynol-9) Irganox 1076 (octadecyl 0.02 15 t-butyl-4'-hydroxyphenyl]propionate) Uvinul M-40 0.2 (2-hydroxy-4-methoxybenzophenone) Water 92.28 100.0 20 MGK 264 is a biological synergist available from McLaughlin Gormley King Co. of Minneapolis, MN.

Igepal CO 630 is an emrlsifier available from GAF Irganox 1076 is an antioxidant available Ciba Geigy 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.

a) 10:70:20 b) 30:50:20 c) 50:30:20 d) 20:70:10 e) 40:50:10 f) 60:30:10 The specified polymers have the following solubility parameters and Brookfield viscosities at 16.67% solids: Polymer Solubility Parameter Brookfield Viscosity a 9.35 7560 b 9.45 990 c 9.58 200 d 9.28 421 e 9.36 235 f 9.47 106 t -11- Sections of bovine hide were sprayed with the formulations then allowed to dry for two hours before being rinsed for one minute with warm (35 to 451C.) water. The hides 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 with the same formulation minus the polymer.

Example 2 Formulations Using Different Levels of Polymer ee,¢ i r S I Eight different formulations containing different levels of polymer were prepared and tested.

ingredient Poymer mole ratio of 50:3020 of iso-octyl acrylate:stearyl 20 methacrylate: acrylic acid; 45% polymer in 2:1 n-heptane:ethylacetate) Pyrethrins (56% extract in kerosene) Piperonyl Butoxide MGK 264 W/W in Formulation 0.0a, i.Ib 2.2 3 3 d 4.4, 0.0 1.1i g 1.7 h C C C C C 4: 4C 1.1 1.2 1. 0 Igepal CO 630 Irganox 1076 Uvinul M-40 0.02, 0.5 0.2, 0 Water 94.48a, 9338, 92.28r, 91.18 d 90.08 93.70 f 92.609, 9 2 0 0 h 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 using the bioassay described previously. The hides sprayed where R is alkyl containing 1 to 18 carbon atoms, R 2 is -12with test formulations showed greater repellency than did hides sprayed only with water. The hides sprayed with formulations containing polymer showed greater repellency than the hides sprayed with formulations that did not contain polymer. Bovine 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 rinsing.

Example 3 Formulations Using Different Levels of Antioxidant A series of formulations using different amounts of antioxidant were prepared and tested.

_r :a Ij i I:e I::oi i

.:B

r I;

-O

ii Ingredient %W/ 50:30:20 mole ratio of iso-octyl acrylate:stearyl methacrylate: acrylic acid 45% polymer in 2:1 n-heptane:ethyl acetate Pyrethrins 56% extract in kerosene W in Formulation 2.2 b 1.1 1.1 Piperonyl Butoxide MGK 264 Igepal CO 630 Uvinul M-40 Irganox 1076 Water Bovine hides were sprayed allowed to dry for about an hour a: 0.0, 1.0, b: 0.0, 0.02, c: 0.25, 0.5, a: 92.3, 91.3, 90.3 b: 92.3, 92.28, 90.3 c: 92.85, 92.6, 92.1 100.0 with formulation, then placed in a a "i .t i w" -13- Weather-O-Meter for about three hours. About sixteen hours later the hides were tested for insect repellency using the bic ssay 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 for 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 Usinq Different ro C t C Cl

'CC

Liquid Carriers A series of formulations carriers was prepared and tested.

using different liquid Ingredient 50:30:20 mole ratio of iso-octyl acrylate:stearyl methacrylate: acrylic acid 45% polymer in 2:1 n-heptane:ethyl acetate W/W in Formulation 2.2 Pyrethrins (56% extract in kerosene) Piperonyl Butoxide MGK 264 Igepal Irganox 1076 Uvinul M-40 0.02 92.48' 100.0 Liquid Carrier -14- Six different liquid carriers were used: water, isopropyl alcohol, 5.0% isopropyl alcohol in water, isopropyl alcohol in water, 5.0% ethanol in water, and ethanol in water. Bovine hides were sprayed with the test formulations, allowed to dry for about an hour and a half, and then placeu Ln 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 S 5 the other formulations.

Example Formulations Using Different Ultraviolet Light Absorbers Ingredient W/W in Formulations 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 Igepal CO 630 SIrganox 1076 0.02 UV absorber Liquid carrier 91.48 100.0 Mine 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 1 CL;:lf on- (2,2'-dihydroxy-4-methoxybenzophenone: available from American Cyanamide) were prepared using isopropyl alcohol as the liquid carrier. Formulations containing Uvinul 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 Co, 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 i carrier. Bovine 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 para-aminobenzoic acid, Specra-Sorb-UV-24, Giv-Tan F and 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.

U|TeiorpiachlbsdUiu -0fruainws--, pjbte hntewtrbse omlto.Uiu -0 i T--ra r.

f -16- Example 6 Formulations Using Different Levels of Ultraviolet Light Absorber Ingredient W/W in Formulation 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 Igepal CO 630 Irganox 1076 0.25a, 0 02 b c Uvinul M-40 a: 0.0, 0.25, 0.5, 0.75 b: 0.0, 0.2, c: 0.0, Water a: 92.25, 92.0, 91.75, 91.5 b: 92.48, 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.

Bovine 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 absorber.

Claims (6)

1. An insect repellent/toxicant composition substantive to animal hide and hair comprising: an amount effective to repel insects of a pyrethroid insecticide; at least 0.1 percent by weight of a water insoluble oil soluble 1I/2 acrylate polymer having a solubility parameter of 6 to 10 (cal./cc.) 1 in poorly hydrogen bonding solvents and a Brookfield viscosity between 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 monomers of the formula: R 3 R 2 CH C CO2R 1 where R 1 is alkyl containing 1 to 18 carbon atoms, R 2 is hydrogen, methyl or -CH2C0 2 H, and R 3 is hydrogen, -CO 2 H or -C0 2 R 1 provided that when R 3 is -CO 2 H or -C0 2 R 1 R 2 is hydrogen; and optionally contains up to 30 mole percent of the same or different acid monomers of the formula: R 4 R I I CH C CO2H c where R 4 is hydrogen or -CO 2 H and R 5 is hyrdogen, methyl or S -CH 2 CO 2 H, provided that when R 4 is -CO 2 H, R 5 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. I :*3 S a+ Ci A> .Aea.is C. '11 n a4~l- .t ct~t r C, 'Ac RLF/1153h

18- S4. 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, mole percent stearyl methacrylate and 20 mole percent of acrylic acid. S7. 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 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 further ir ,a(ect\ cs\\A comprising 1a bio!gica1l\synergist, an antioxidant and an ultraviolet light absorber. 0SIV I_ 19 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. 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 2 to 5 with respect to radiation having wavelengths in the range of 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: from 0.25 to 1.0 percent by weight of a 50:30:20 mole ratio of iso-octyl acrylate:stearyl methacrylate: acrylic acid terpolymer; from 0.1 to 1.0 percent of natural pyrethrins; from 0.2 to 10.0 percent of 3,4-methylenedioxy-6-propylbenzyl butyldiethylene glycol ether; from 0 to 3.3 percent of N-(2-ethylhexyl)-bicyclo[2.2.1]-5- heptene-2,3-dicarboximide; from 0.02 to 1.0 percent of octadecyl 3-(3',5'-di-t-butyl-4'- hydroxyphenyl)propionate; from 0.1 to 1.0 percent of 2-hydroxy-4-methoxybenzophenone; from 82 to 99 percent of a liquid carrier.

19. The composition of claim 18 wherein the liquid carrier is water further comprising from 0.1 to 5.0 percent of nonoxynol-9. 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. DATED this TWENTIETH day of AUGUST 1990 Minnesota Mining and Manufacturing Company Patent Attorneys for the Applicant SPRUSON FERGUSON