Abstract:
This invention relates to the use of mixtures of terpene alcohols and terpene hydrocarbons, such as pine oil, in combination with surface active agents of the anionic and nonionic type containing dispersing and stabilizing agents, for controlling the population of certain colonial insects, especially fire ants.

Description:
BACKGROUND OF THE INVENTION 
     There is a scurge of insects invading the United States and many other parts of the world in increasing numbers, ever since government restrictions have been placed on the use of chemicals that have been employed in controlling them. The government restrictions have been imposed in the effort to protect the environment from real or imaginary toxic effects of the chemicals employed. Amoung the chemicals banned or restricted in use by governments are DDT, Chlorodane, Lindane, Aldrin, Heptechlor, Dieldrin and Mirex. Mirex was employed as an effective insecticide against fire ants, however since its use has been banned in the United States, the fire ant population has been increasing so rapidly that major destruction of crops such as soybeans, potatoes, and other vegetables, has been occurring in the sun belt region of the United States where the fire ant is taking over. In addition fire ants have been known to kill young birds and even small rodents and they will feed on anything or anybody that collaspses from their multiple stings. They are a menace to people in homes, schools, work places, and even in medical facilities, to domestic animals, and especially in agriculture. Fire ants destroy lawns and forage tunnels in the ground and infest any buildings above them. One species, Solenopsis invicta is reported to nest in super colonies called insect megalopolises, containing 10 to 20 million ants. 
     PRIOR ART 
     The order Hymenoptera, family Formicidae includes numerous species of ants. The order Isooptera, family Termitidae includes various species of termites. Representative species of ants and termites are given in Columns 3 and 4 in U.S. Pat. No. 4,421,759 issued to R. J. Boisvenue on Dec. 20, 1983 and assigned to Eli Lilly &amp; Company. This patent discloses and claims the use of fluoro-benzimidazoles and fluoro-benzimidazolines for controlling ants and termites, especially fire ants. 
     Another patent directed to the control of fire ants is U.S. Pat. No. 4,353,907 issued to J. B. Lovell on Oct. 12, 1982 and assigned to American Cyanamid Company. This patent discloses and claims the use of fluoro-aminido hydrazones and their bait formulations with edible oils, such as soybean oil, cottenseed oil, coconut oil, corn oil, olive oil, peanut oil, palm oil, tall oil, and their mixtures, for controlling fire ants. 
     Still another patent directed to the control of fire ants is U.S. Pat. No. 3,220,921 issued to Greenbaum and Weil on Nov. 30, 1965 and assigned to the Hooker Chemical Corporation. This patent disclosed and claims the dimer of hexachlorocycyopentadiene, also known as Mirex, with baits such as peanut butter. Mirex was found to be one of the most effective fire ant killers and was employed in solid baits such as peanut butter and ground up corn cobs because of its pronounced toxicity when ingested in the insects digestive tract, as distinguished from its contact insecticidal activity which is not so great. Although Mirex is an effective agent for killing fire ants it can not be employed in those juristrictions where it has been banned because it is toxic to the environment. 
     Pine oil is a naturally occuring material, which is obtained by the distillation of the cones, needles, stumps, etc. of various species of pines, which are coniferous trees. They consist principally of isomeric tertiary and cyclic terpene hydrocarbons and alcohols, with variable quantities of terpene ethers, ketones, phenols, phenolic ethers amoung other constituents, including alpha pinene. 
     Various patents have been issued on the use of materials originating from pine trees. For example, U.S. Pat. No. 141,512 issued to J. B. Lunbeck back in Aug. 5, 1873 discloses a composition produced by boiling one gallon of pine tar; one quart of soft soap; one-half pint of tobacco juice and one-half gallon of alkali for use in destroying insects, worms and grubs and protecting fruit and other trees. Another patent issued to G. C. Richards on Apr. 13, 1926 discloses and claims an insecticide paint made from pine tar, a thinner, sulfur and carbolic acid. Still another patent 2,258,390 issued to W. D. Martin issued on Oct. 7, 1942 discloses the use of pine rosin in special formulations including kerosene for use as a larvacide. 
     OBJECTS OF THE INVENTION 
     It is an object of this invention to provide a composition and method which is economical, easy and safe to use, and which is effective in killing and controlling fire ants, and which is assimilable in the environment without any deleterious effects. 
     It is a further object of this invention to employ materials that have been present in the environment for long periods of time without any adverse effects whereby their saftey and acceptability to man and his environment is already established, thereby reducing or eliminating the need for long and expensive testing and documentation inorder to obtain government approval to employ the compositions and methods in commerce. These and other objects of the invention will become apparent by the disclosures made herein. 
     BRIEF DESCRIPTION OF THE INVENTION 
     These and other objects are accomplished by applicant&#39;s unexpected findings and invention that mixtures of terpene alcohols and terpene hydrocarbons such as pine oil in combination with surfactants kill fire ants when the mixture is contacted with mounds of fire ants, as more fully described and claimed hereinafter. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     In order that this invention may be more readily understood it will be described with respect to certain preferred embodiments, however it is to be understood that these embodiments are not to be construed as limiting the invention except as defined in the appended claims. 
     The preferred compositions of this invention are prepared by making a mixture of approximately one part of pine oil which is a mixture containing terpene alcohols and terpene hydrocarbons including alpha terpineol and alpha pinene with a quanity of a surfactant sufficient to form an emulsion, which is usually an amount equal to the pine oil employed. This composition is then diluted for use in the field by using at least about one ounce of it per gallon of water, and preferably about five to six ounces of said emulsion per gallon of water. More particularly, optium results in killing fire ants are obtained by employing an emulsion made from commercially available pine oil materials, such as Unipine 85 manufactured by Union Camp Corporation with commercially available dish washing detergents, such as Dawn manufactured by Proctor &amp; Gamble Corporation. The diluted composition is thoroughly mixed then applied to the locus of the fire ant mounds by pouring, injecting into or spraying the mounds. 
     Table 1 gives the results obtained in testing over 60 fire ant mounds. Ten of the mounds were used as controls, five of which had nothing done to them and five of which had plain water, in like amounts to the compositions of this invention being tested, poured over them. In Table 1 the &#34;Date&#34; is given in months/day; the &#34;Location&#34; were all in the southern part of Texas; the &#34;Condition&#34; is the weather condition at the time of the test; &#34;Time&#34; is given in 24 hour clock terms; the &#34;Temp&#34; is in Fahrenheit; &#34;Product&#34; is the material actually employed in the test; complete descriptions of the Products tested are given in the notes following the Table; &#34;Mound Size&#34; is measured in inches and the &#34;Results&#34; are given in percentage of kill of the fire ants, with the time required to get the percentage kill. 
     Table 2 gives the details on the commercial products available for controlling and killing fire ants. 
     Table 3 gives the composition ranges for individual components found in United States Domestic pine oils, which may be employed in accordance with this invention. 
     
                                           TABLE 1__________________________________________________________________________TEST MONITORING LOGDate    Location      Condition            Time               Temp.                   Product                         Mound Size                                Results__________________________________________________________________________Part 19/16    Woodbranch      Hot/  14:30               90  Raid  12 × 5                                75% kill 30 minutes    Field  Clear                     95% kill 1 hour9/16    Woodbranch      Hot/  14:30               90  Prod Five                         10 × 4                                75% kill 20 minutes    Field  Clear                     95% kill 1 hour10/26    Residential      Cloudy            15:30               71  Prod Five                         12 × 4                                60% kill 20 minutes    Lawn                             100% kill 22 hours                                increased solution to 3/4 C.10/26    Residential      Cloudy            15:30               71  Enforcer                         multiple                                negligible 20 minutes    Lawn                             negligible 22 hours10/26    Residential      Cloudy            15:30               71  Raid  9 × 4                                75% kill 20 minutes    Lawn                             90% kill 22 hours10/26    Residential      Cloudy            15:30               71  Prod Five                         10 × 3                                75% kill 20 minutes    Lawn                             95% kill 21/2 hours                                100% kill 22 hours10/26    Residential      Cloudy            15:30               71  Enforcer                         2&#39; × 5&#34;                                No impact 2 hours    Lawn                             Mound abandoned 3 days10/28    Residential      Cool/ 10:30               65  Raid  9 × 3                                90% kill 30 minutes    Lawn   Rainy10/28    Residential      Cool/ 10:30               65  Prod Five                         9 × 3                                100% kill 30 minutes    Lawn   Rainy10/28    Residential      Cool/ 10:30               65  Amdro 10 × 4                                No impact 2 hours    Lawn   Rainy                     Mound abandoned 2 days10/28    Residential      Cool/ 10:30.sup.-               65  Rid-A-Bug                         12 × 4                                75% kill 2 hours    Lawn   RainyPart 24/24    Woodbranch      P Cldy            11:50               78  P5/UD 18 × 5                                80% kill 20 minutes    Field                            100% kill 35 minutes4/24    Woodbranch      P Cldy            11:55               78  P5/UP 12 × 6                                100% kill 20 minutes    Field4/24    Woodbranch      P Cldy            12:00               78  P5/AT 14 × 5                                10% kill 20 minutes    Field                            20% kill 40 minutes4/24    Woodbranch      P Cldy            12:08               78  Raid  10 × 7                                15% kill 20 minutes    Field                            60% kill 40 minutes4/24    Woodbranch      P Cldy            12:15               78  P5/UP 10 × 9                                100% kill 15 minutes4/26    Residential      Clear 17:15               72  P5/UP 12 × 12                                100% kill 15 minutes    B. Hill                          kills grass4/26    Residential      Clear 17:15               72  P5/UP 10 × 10                                100% kill 18 minutes    B. Hill                          kills grass4/26    Residential      Clear 9:15               72  P5/UP 20 × 2                                100% kill 10 minutes    M. Craven                        browns grass4/26    Residential      Clear 9:25               72  P5/UP 8 × 8 × 8                                100% kill 15 minutes    M. Craven4/26    Residential      Clear 17:30               74  P5/At 15 × 9                                25% kill 20 minutes    M. Craven                        30% kill 40 minutes4/26    Residential      Clear 16:15               73  P5/UP 16 × 20                                90% kill 10 minutes    D. Hennley                       kills grass4/26    Residential      Clear 16:20               73  P5/UD 15 × 16                                80% kill 20 minutes    D. HennleyPart 310/4    Residential      Cloudy            14:40               70  P5/PB/UP                         12 ×  6                                20% slow kill on surface    W. Sublette                      2 day duration10/4    Residential      Cloudy            14:50               70  Peanut                         10 × 6                                Negligible kill    W. Sublette         Butter only10/4    Residential      Cloudy            15:05               70  Surfactant                         14 × 4                                None    W. Sublette         &amp; Water10/5    Residential      Cloudy/            14:30               71  P5/PB/UP                         14 × 5                                25% slow kill on surface    D. Hennley      Rain10/5    Residential      Cloudy/            14:40               71  Peanut                         10 × 3                                Negligible kill    D. Hennley      Rain         Butter only10/5    Residential      Cloudy/            14:45               71  Surfactant                         12 × 3                                None, browns grass    D. Hennley      Rain         only10/5    April Vig      Cloudy/            15:05               71  Water only                         9 × 2                                None    cul-de-sac      Rain10/5    April Vig      Cloudy/            15:10               71  UP &amp; Water                         11 × 3                                80% kill in 20 minutes    cul-de-sac      Rain                      spotty kill pattern                                due to poor suspension__________________________________________________________________________NOTES  Product 5 as indicated on Part 1 of Table I was the initial mixture  used to test the hypothesis and  consisted of 1/3 cup Real-Pine (a commercially available disinfectant  with a composition of 30% pine  oil) and 1/3 cup surfactant (Dawn Dishwashing Detergent) mixed in 1  gallon of water. The solution  was mixed and poured on the villages as a mound drench. Ingredients are  as follows:Real-Pine:   Pine Oil          30%   Soap              11%   Isopropanol       9%   Inert Ingredients 50%Dawn:   Water             50%   Magnesium Alkyl Sulfate                     15%   Magnesium Alkyl Ethoxylate Sulfate                     15%   Amoniam Alkyl Ethoxylate Sulfate                     7%   Ethenyl           7%   Amin Oxide        2%   Amonium Chloride  2%   Amonium Zyline Sulfinate                     2%   Trace of Minor Ingredients  Raid as indicated on Part 1 of Table 1 is a commercially available  consumer product which is a  concentrated mound drench solution that must be added to water.  Ingredients by label are:Active Ing:      Chlorpyrifos [0,0-Diethyl-0-(3,5,6-trichlor-2-pyridyl)phosphoro      thioate                         2.00%Inert Ingredients:                         98.00%  Enforcer is a commercially available consumer product in an aerosol  form utilizing a injection  tube to penetrate the mound. Its ingredients by label are:Active Ing:      Tetramethrin [1-Cyclohexene-1. 2-Dicarboximido) methyl 2.      2-Di-                           0.200%      methyl-3-(2-methylpenyl) Cylopropanecarboxlate]      Cyano (3-Phenoxyphenyl) Methyl 4 chloro-alpha-(1-methylethyl)                                      0.400%      Benzeneacetate      Petroleum Distillate            2.278%Inert Ingredients:      97.122%  Andro is a commercially available consumer product which is a solid  bait. It is sprinkled  on the mound in significant proportion to cover the mound area.  Ingredients by label are:Active Ing:      Tetahydro-5,5-dimethyl-2 (1 .sub.--H)-phrinidinone      (3-4[trifluoro-                 0.88%      methyl)phenyl]-1-(2-[4-(trifluoromethyl) phenyl]-ethenyl)-2-pro      penylideneInert Ingredients:      99.12%  Rid-A-Bug is also a commercial mound drench solution Its ingredients by  label are:Active Ing:      Chlorpyrifos [(0.0-diethyl 0-(3,5,6-trichloro-2-pyridyl)      phosphorthioate                 0.50%      3,7-Dimethyl-6-octen-1-ol       0.011%      3,7-Dimethyl-6-octedien-1-ol    0.002%      3,7-Dimethyl-6-octanol          0.002%      Xylene lange aromatic solvent   0.28%Inert Ingredients:                         99.205%  All commercial products were applied by following label directions at  the same time applications  of my product were made to other mounds in the exact same conditions.  -7. After further testing components in Real-Pine, it was determined  that pine oil was the active ingredient.  Further experiments were carried out with chemically produced versions  of natural pine oil.  The &#34;product&#34; codes shown on Part 2 substitute the 1/3  cup Real-Pine  for 1/3 cup measures of three other  substances, P5/UD indicates Unitene DTR was substituted for Real-Pine.  P5/UP is the designation  for Unipine 85 substituted for Real-Pine, while P5/AT indicates ALpha  Terpineol was the substitute.  In all cases the substitute was exactly 1/3 cup of the chemical to 1/3  cup N--Butyl  Acetate. While the substitutes showed varying degrees of results, the  inclusion of N--Butyl Acetate  neither enhanced or negated the kill ratio and was only for masking  agent purposes.  The results utilizing UD, UP, and AT individually indicated those to be  the active ingredient when  mixed in water and applied to the mounds. Using surfactant alone, water  alone, or the two in  combination showed no effective kill.  The results clearly indicate that UD, UP, and AT individually combined  with a surfactant and added  to water offer superior performance over and above the commercial  products tested. The UP  solution is far and away the most effective of all combinations and  clearly out performs by leagues  other off-the-shelf products.10.  The composition of the products, or abreviations for products, embraced  within this invention, that  are given in Table 1 are as follows:  Product 5 (P5) - 1/3 cup of Real-Pine; 1/3 cup of Dawn mixed in one  gallon of water. (See page 4 of  Table 1 for composition of Peal-Pine and Dawn).  Unipine 85 (UP) - A pine oil manufactured by Union Camp Corporation -  87.8% terpene alcohols;  11.9% terpene hydrocarbons; 0.3% moisture. This combination meets U.S.  Government specification  LLL-P-400A Type 1.  Unitene DTR(UD) - 5% terpene alcohols; 55% monocyclic hydrocarbons; 25%  pine oils;  9% camphene; 6% alpha pinene; and 0.01% moisture.  Pine Oil - crude and refined. (See Table 3 for composition ranges of  domestic oine oil).  Alpha Terpinol (AT).  Alpha Pinene (AP).  The test results indicated on Table 1 Part 3 were to test various  ingredients separately from each other  as well as an additional compound utilizing a mixture of ordinary  peanut butter and Unipine 85 as  indicated by the &#34;product&#34; code P5/PB/UP. In summary, the use of water  as the only treatment,  and the use of water and surfactant in combination all had negligible  results and simply caused the  mound to wash away and the ants built another village. However, with  the combination once again  proved to be very lethel.  Utilizing a similar technique, peanut butter by itself was applied to  mounds with no effect. However,  the addition of enough Unipine 85 to form a fairly liquid paste again  caused a substantial kill.  However, like Amdro, the solid bait must be ingested and it is very  difficult to determine the  effectiveness other than observing the dead ants on the mound surface.  It should be noted that the label on Amdro indicates this is a food  chain killer wherein soldier ants  carry the bait into the mound (inferring to the queen). It also  indicates that it should take from one  to four weeks to kill an appreciable number of soldiers and the queen.  Further, the label indicates a  visible reduction in mound activity should be observed in two to eight  weeks. Accordingly, the mix-  ture of peanut butter and Unipine 85 does kill in a faster time frame,  at least on the surface, whereas  Amdro will not kill as fast or as effectively as products of this  invention. Further, when it rains,  or the bait is moisturized, Amdro looses its effectiveness entirely. 
    
     
                       TABLE 2______________________________________COMMERCIAL PRODUCTS WITH HIGHESTCONSUMER ACCEPTABILITY PROFILE______________________________________Product: Raid Fire Ant KillerManufacturer: Johnson &amp; JohnsonActive Ing:Chlorpyrifos [0,0-Diethyl-0-(3,5,6-trichlor-2-                       2.00%pyridyl)phosphorothioateInert Ingredients:          98.00%EPA Reg No.                 4822-264EPA Est No. 4822-WI-1Form: LiquidProduct: Enforcer Fire Ant KillerManufacturer: C &amp; J ChemicalActive Ing:Tetramethrin [1-Cyclohexene-1. 2-Dicarboximido)                       0.200%methyl 2. 2-Dimethyl-3-(2-methylpropenyl)Cylopropanecarboxlate]Cyano (3-Phenoxyphenyl) Methyl 4 chloro-                       0.400%alpha-(1-methylethyl) BenezeneacetatePetroleum Distillate        2.278%Inert Ingredients:          97.122%EPA Reg No. 40849-13EPA Est No. 10807-GA-1 49830-GA-1Form: AerosolProduct: Rid-A-BugManufacturer:Kenco Chemical &amp; Manufacturing CompanyActive Ing:Chlorpyrifos [(0.0-diethyl 0-(3,5,6-trichloro                       0.50%2-pyridyl) phosphorothioate3,7-Dimethyl-6-octen-1-ol   0.011%3,7-Dimethyl-2-6-octedien-1-ol                       0.002%3,7-Dimethyl-6-octanol      0.002%Xylene lange aromatic solvent                       0.28%Inert Ingredients:          99.205%EPA Reg No. 8845-34EPA Est No. 8845-FL-1Form: LiquidProduct: Amdro Fire Ant InsecticideManufacturer: American Cyanamid CompanyActive Ing:Tetahydro-5,5-dimethyl-2 (1 .sub.--H)--phrinidinone                       0.88%(3-4[trifluoromethyl)phenyl]-1-(2-[4-(trifluoromethyl) phenyl]-ethenyl)-2-propenylideneInert Ingredients:          99.12%EPA Reg No. 241-160EPA Est No. 33596-IL-01Form: Granule______________________________________ 
    
     
                       TABLE 3______________________________________COMPOSITION RANGES FOR INDIVIDUALCOMPONENTS FOUND IN DOMESTIC PINE OILS             RANGE FOR ALL             GRADES OF PINE OIL             % Min.   % Max.______________________________________BI &amp; TRICYCLIC TERPENEHYDROCARBONSTricyclene          ND         0.1Alpha-Pinene        ND         2.0Camphene            ND         1.0Beta-Pinene         ND         0.3MONOCYClIC TERPENEHYDROCARBONScis- -p-Menthane    ND         Ttrans- -p-Menthane  ND         1:13- -p-Menthene      ND         0.31- -p-Menthene(Carvomenthene)               ND         1.28-Menthene          ND         0.14(8)- -p-Menthene   ND         Talpha-Phellandrene  ND         0.6beta-Phellandrene   ND         0.4alpha-Terpinene     T          2.3gamma-Terpinene     ND         3.1Dipentene ( -d,1-Limonene)               0.1        10.0 -p-Cymene          0.1        4.5Terpinolene         0.8        14.62,4(8)- -p-Menthadiene               ND         1.7alpha- -p-Dimethyl-styrene               ND         0.5TERPENE ALCOHOLSDihydroterpineol    ND         6.1Terpinene-1-ol (3- -p-Menthen-1-ol)               T          13.1alpha-Fenchol       1.5        11.3Terpinene-4-ol (1- -p-Menthen-4-ol)               1.1        11.3beta-Terpineol (cis &amp; trans)               0.5        9.2Terpineol (alpha &amp; gamma)               34.9       76.7Isoborneol          0.1        4.3l-Borneol           ND         14.68-Cymenol           ND         0.9pino-Carveol        ND         0.41,8-Terpin (Terpin hydrate)               ND         0.7MISCELLANEOUS TERPENES(Ethers &amp; Ketones)1,4-Cineole         ND         5.21,8-Cineole         ND         4.2Fenchone            ND         2.0Camphor             0.4        8.3Estragole (Methyl Chavicol)               ND         2.4cis-Anethole        ND         6.2trans-Anethole      ND         2.5Pinol               ND         0.1UNKNOWNS            &lt;0.1       0.4______________________________________ ND -- Not Detected T -- Trace 
    
     Amoung the active ingredients for killing or controlling fire ants that may be employed in accordance with my invention are specific components of pine oil. For example, I have found that alpha pinene may be used instead of the pine oil, also, the specific fractions of pine oil resulting from its distillation are effective fire ant killers including crude pine oil and refined pine oil. Alternatively synthetic pine oil may be substituted in whole or in part for the natural material. The foregoing materials may be substituted for or used as a partial replacements for each other, in the same manner as above described. 
     Various alcohols may be employed such as methyl alcohol to facilitate the formation of the emulsions in the preferred embobiment of my invention. The lower aliphatic alcohols such as ethyl, propyl, butyl and similar alcohols may be used in whole or in part with the preferred methly alcohol of this invention. 
     The surfactants that may be used are those which cause the emulsification of the pine oil mixture of this invention. For example ordinary soap may be used or even the household detergents used for laundry or dishes may be used. The preferred surfactants to employ in accordance with my invention are products having a composition or function similar to Dawn. The amount of surfactant used to make the emulsions of the pine oil water mixture is only that amount necessary to make the emulsions. For example, when using concentrations of pine oil at the lower end of the preferred range in one gallon of water smaller amounts of liquid surfactant may be employed than when using concentrations of pine oil at the higher end of the preferred range. 
     The concentrations of ingredients employed to make up the compositions of this invention may be varied widely. For example, I have found that although one part of pine oil to one part of surfactant is preferred that more or less of each may be employed and all that is required is an amount which is effective in emulsifying the mixture. Mixtures of only half the amount of pine oil to surfactant and mixtures of twice the amount of pine oil to alcohol are usefull. The amount of pine oil/surfactant emulsion employed in making the diluted composition for use in the field is preferably at least one ounce of said mixture to one gallon of water; the optimum being about two to three ounces of each to one gallon of water. Although concentrations as high as one to one to eight of active ingredient to surfactant to water may be employed in accordance with this invention, these higher concentrations are not necessary for effective kill, except under extreme conditions requiring faster kill. When using these high concentrations the surrounding environment may be deleteriously effected, for example, by browning of nearby vegetation. However, more may be used with the concommittent result that there is faster and more effective kill of the fire ants. By doubling the strength of active ingredient in accordance with this invention one may double the kill in half the time, and so on, however the effects on the environment and economical reasons are best served by using an effective amount which in accordance with this invention is between about 1 to 1 to 128 to between about 1 to 1 to 8 of pine oil/surfactant/water, respectively. 
     It is to be understood that various modifications within the spirit and scope of my invention are possible, some of which have been referred to above, and although I have given detailed description of my invention by illustrating specific embodiments, I do not intend to be limited thereto, except as defined by the following claims.