Detergent composition liquidates cntenant an insect repellant.

The présonto Pick ion which relates to liquid detergent compositions useful for cleaning hard surfaces and which impart insect repellent properties. More particularly, the present invention relates to liquid detergent compositions for all purpose substance-containing insect repellent, and a method for cleaning surfaces and. items having applied such detergent compositions and for repelling insects.

Many types of insects which meet commonly in houses, such as German cockroaches {Cockroach] the arachnids) or domestic, are classified as pests and much effort have been deployed eradicate or at least repressing their development. Mosquito repellent products are marketed for a long time and various chemical agents that are effective for repelling cockroaches were found. In general, these chemicals and repellents, are used in houses in being applied or sprayed onto the surfaces of walls, floors, cabinets, drawers, packages, containers, carpet, upholstery and floor coverings, and in the places of potential nesting insects, such as the interior walls and Je below floors. However, until now, the substances insect repellents were not usually used in conjunction with hard surface cleaner OD to effectively clean a surface household hard as a kitchen wall, the top of a furnace, the floor of a bathroom, and so forth, while simultaneously applying a substance film insect repellent which is sufficiently adhered to the surface to which the composition is applied for repelling insects.

The incorporated ion of a substance insect repellent to a floor care product is. known in the technology.

The Patent of Ε υ Λ... No. 3,018 217 provides back polish compositions containing soils, dibutyl succinate as an insect repellent. The Patent: back F.!. U A no. 3,034 950 that reports a class of compounds insec: T-I-fuges that may be applied to surfaces in a wax dispersion. The Patent of kk.u. Λ. № 4,455 308 insect repellent formulations containing a liquid vehicle such as aliphatic or aromatic hydrocarbon liquids. An emulsifying agent such as a nonionic surfactant can be added to the hydrocarbon liquid to make the water-dispersible composition 1' waters for its ultimate application. The Patent of E.U.A. no. 4,822 61, 4 provides an insect control ingredient in a hydrocarbon solvent such as isoparaffin hydrocarbons.

The present invention provides an aqueous liquid detergent composition, capable of cleaning a hard surface and repelling insects, comprising (I-) an amount of a compound effect detersive detergent surfactant selected from anionic detergents, non-ionic, cationic and amphoteric surfactants; and (III) an effective amount of insect repellent substance, which is sufficient to repel insects from this hard surface after application of the detergent composition thereto, said liquid detergent composition is substantially free of liquid hydrocarbon.

The present invention is based on the discovery that insect repellent insect repellent properties of a substance are improved in a particular location or area when this area or location, is cleaned with a detergent composition as described herein.

This effect can be attributed to the natural tendency of insects to collect preferentially in areas soiled rather than fortify cleaned surface, as well as the improved adhesion of the substance using on such surfaces washed or cleaned.

The term "insect" is employed herein in its broad sense that encompasses cockroaches such as German cockroach (Insects and qermanica) and the American cockroach (Perioperative pianetaamoricana), as well as mosquitoes, the moths, flies, fleas, ants, the lice and arachnids such as spiders, ticks and mites.

The expression "insect repellent material" is for to encompass a large variety of substances fixings the I nseclnsecl.i properties fuges that are compatible with the type of detergent composition described herein and that exhibit sufficient adhesion to the hard surface on which the the composition is applied to be déterqenteeffective as insect repellents.

Substances include insect repellents useful in the present invention include the compounds following that may be used separately or in association with other substances insect repellents, the designation mentioned in parentheses following some names of compounds being their tradename or common:

The n-alkyl in which the néoaIcanamidesresidue alkyl account 1 to 4 carbon atoms and the grouping 7 to 14 néoaleanoyle account carbon atoms:

The n, n-diethyl-m-toluamide (DEET concentrations);

sulfide OD 2- hydroxyethyl methacrylate and n-octyl

(MGK ARE 874 )¹ ;

N octyocty.l Bi eyeloheptene-to-diearboximide (MGK are 264);

a preferred mixture of the two materials above comprising 66 33% and 264% of MGK are of MGK are 874;

i-hexahydrodbenzofurarine carboxaldehyde (MGK are 11);

isocinchoméronate di-n-propyl (MGK are 326);

2-ethyl -■■1, 3 a-hexane diol (at Rutgers 612);

2- (n- a butyl) - 2 ethyl-1.3 methylpropanediol;

thythy.le dimé phthalate;

the dibuty succinate (Tabutrex);

goal-yl IEA piperonyl; and

pyrét participants were plain

Ii.es MGK are repellents are trade marks of McLaughlin Gormley King's Company analysis, the Minneapolis, MN, bb.u.a.

Although the substances mentioned are more persistent ifugesinsect and are preferred for the purposes of the present invention, other substances insect repellent useful include essential oils such as those of Of Mentha arvensis from (mint), Of Mentha piperita extracts (peppermint), Of Mentha spicata was (spearmint American) and Of Mentha cardîaca (spearmint or scotch), gasoline lemongrass of Indian oriental, lemon oil, gasoline of citronella, the cedarwood oil (Daylilies virgïniana L) and pine oil. The terpenoids are another class of substances having insect repellent properties, the most useful being the (-) -1imonene, the (+) -1imonene, the (-) - carvone comprises, the cineole (cineole), linalool, dextrorotatory camphor, citronellal, the alphaet beta-terpineol, fencholic acid, borneol, 1' isoborneol, bornyl acetate and isobornyl acetate.

Insect repellent substances include non-commercially available which are useful in the present invention, include the following:

The N, N-diethyl-cyclcycl.ohexylacétamide (below)

1 ,2, 3.6-tetrahydro-1 - (2 methyl-1 a-oxopenty1 ) piperidine with n, n-diethyl-3 a-cyclohexylpropionamide (SPC) 2- - ethyl1- (2- methyl -1the oxo - -2- butény1) piperidine with n, n-diethyl-nonanamide, and n, n-diethyl-phenyl acetamide.

With regard to the n-alky 1 a-néoalcanamides mentioned, the alkyl radical is preferably methyl or ethyl, more preferably methyl. The group is preferably the group néoalcanoyle neodecanoyl or néotridécanoyle.

The detergent compositions of the invention contain a proportion to detergent effect of one or more compounds detergent surfactants chosen from anionic detergents, non-ionic, cationic and amphoteric surfactants, established general decorate between about 1 and about 30% by weight, preferably between about 2 and about 20 % in the weight of the composition. The detergent is of preferably a type synthetic organic detergent anionic or non ion, and an association of detergents anionic and non ion is often very preferable. The description a large number of these detergents are in the orfor the title "NDA detergent active surface agent" schwartz, Perry's and Berch, flight. The TT, page 25 - 138, published in 1958 byInterscience Newspaper, Inc. in these compounds are also disclosed in a publication of 1973 entitled " Detergent NDAEmulsifiers " John W McCutcheon. These two fitteding are included below by reference.

The anionic detergents are used normally alkali metal salts, such as sodium or the potassium hydroxide, or salt ^ '^ ^ Pcano' LW-I-infér €ammonium, by such as triethanolamine salts. The anionic detergent can be a sulfate, a sulfonate, phosphate or phosphonate or salt of another suitable acid, but it is in general a sulfate or sulfonate. Anionic detergents include a lipophilic group which counts normally 10 to 18 carbon atoms, preferably in a array of higher alkyl group linear, but can be replaced by other lipophilic groups, comprising of preferably 12 to 16 carbon atoms, such as a the alkylbenzene branched chain. Examples of detergents suitable anionic include sulfonates alcohols such as the higher fatty tridecylbenzene sulfonate of the sodium; of (alkyl 1inéaire) benzene sodium sulfonates, e.g. (1 inéaire dodecyl) benzene-year averageF.onateof the sodium; of oo.léfi fonates RIE etching by-year average; and para F.finesulfonates. The anionic detergents are of preferably oD of sodium salts, but the potassium salts, ammonium and T r ainmon I-um in ethanol are often more advantageous for certain liquid compositions.

The nonionic detergents suitable typically are condensation products of compounds or lipophilic groups and alkylene oxides or lower polyalkoxy moieties. Lipophilic species very preferable are higher fatty alcohols of 10 to 18 carbon atoms, but may also be utilized such as alkylphenols and - butanyl nony1 phenols. The preferred alkylene oxide is ethylene oxide and there are normally 3 to 30 moles of ethylene oxide per mole of lipophilic species. Preferably, this rate of ethoxylation is 3 to 10 moles per mole of higher aliphatic alcohol, more preferably 6 to 7 mole, e.g. 6.5 or 7 mole, per mole of higher aliphatic alcohol (and per mole of nonionic detergent). We can use either ethoxylates to wide distribution that ethoxylates to narrow distribution (EDL and EDI), the difference therebetween residing in 1 ' "spread" of the number of ethoxy groups present, the average of which builds up in the discharge intervals given. For example, the EDI that have on average 5 to 10 moles per mole of the ando nonionic detergent contain at least 70% of their content ando in groups having 4 to 12 groups polyethoxy ando and preferably contain more than 85% of their content ando in that interval. The non-ionic detergents edition have a wider range of moisture contents ethoxy that the EDI, often with a spread of from 1 to 15 groups when the chain of ando ando account on average 5 to 10 groups ando. Examples of nonionic detergents edition include those sold by shell structure of Chemical Company as the trademark Neodol®, including Neodol 25 - 7, Neodol 23 - 6,5 Neodol and 25 - 3. Non-ionic detergents EDI were obtained from Shell Development Company and identify such substances by the designations 23 a-7p and 23 thereof 7z.

Also suitable are cationic surface-active compounds. These include compounds detergent surfactants that contain a hydrophobic organic group that is part of a cation when the compound is dissolved in water, and an anionic group. The false positiveseffecagents cationic are typically amines and of quaternary ammonium compounds.

The quaternary ammonium compounds useful herein are substances known and are of the type high-softening point. There may be mentioned salts of n, n-di(alkyl upper in c₁ ^ - C.₂₄) - N-, n-di (lower alkyl in c ^ ^ - C.) formed with a quaternary ammonium water-solubilizing anion, for example a halide such that the chloride, bromide and iodide, or sulfate, the methylsulphate, and so on, and the heterocyclic amides such 1 that' imidazolinium chloride.

For convenience, ammonium salts quarnary aliphatic may be defined by the structure following:

where R and R₁ each represents an alkyl group of 14 to 24 and preferably 14 to 22 carbon atoms; R2 and Rj each represents a lower alkyl group of 1 to 4 1 to 3 and preferably carbon atoms; X represents a an anion capable of imparting solubility or dispersability in water, including chloride, bromide, iodide, sulfate and methyl sulfate mentioned. Particularly preferred species include aliphatic quaternary salts those that follow:

distearyl

di chloride (if: hydrogenated yew) diméthylammonium chloride di (tallow) dimethylammonium

méthylsu1fate of distéary1dimethylammonium methylsulphate di (hydrogenated tallow) dimethyl ammonium chloride.

The amphoteric detergents are also useful in the invention. This class of detergents is well-known in technology and many detergents that can be used are described by Schartz, Perry's NDA Berch in "NDA detergent active surface agent", flight. The II, Interscience Newspaper, Inc. or, York (1958) at Chapter 4 of this work. Examples of suitable amphoteric detergents comprise:

the beta of iminodipropionates alkyl, RNs (C.2H4-COOM)₂! and the beta amidobetaines alkyl, RNs (hr) C.₂H₄-COOM.

Detergency builders may be present in the liquid detergent composition in an amount of about 1 to 20 % improve detergency synthetic organic detergents. These detergency builders may be organic or inorganic, soluble or insoluble in water. Among these detergency builders include polyphosphates, such as sodium tripolyphosphate; carbonates, for example sodium carbonate; bicarbonates, such as sodium bicarbonate; borates, for example borax; and silicates, e.g. sodium silicate; detergency builders water-insoluble minerals, including zeolites, for example zeolite 4a hydrated; detergency builders and water-soluble organic, therein included citrates, gluconates, nitrilotriacetate and polyacétalcarboxylates.

The detergent compositions may contain various additives such as fluorescent brightening, antistatic agents, antibacterial agents, fungicides, foaming agents, antifoaming agents, flow improvers, suspending agents, antioxidants, anti-gelling agents, agents to facilitate loosening dirt, and enzymes.

The liquid detergent compositions of the invention generally contain about 2 to 20 % detergent compounds of surfactants that are preferably anionic and/or nonionic surfactants, about 1 to 20 % by weight of salts detergency builders for detergents and about 0.2 to 20 %, preferably 0.5 to 10% by weight, insect repellent substance, the rest being mainly composed of water, adjuvants and optionally a wetting or emulsifying agent such as sodium toluene sulfonate, or a solvent suitable for the substance insect repellent such as isopropyl alcohol or acetone. Facilitate the incorporation of a flavor or fragrance in the aqueous liquid detergent composition, it is often advantageous to prepare the liquid detergent composition in the form of microemulsion with water as the phase continuous and oil or hydrocarbon as the dispersed phase.

In field tests, on kitchen floors, counter tops, of droppers and real walls, and kitchen cabinets and in refrigerators, in apartments infested by cockroaches, observed on the surfaces to which or near which the liquid detergent compositions of the invention are applied a decrease in the number of cockroaches much greater than on surfaces controls, and there is less cockroaches on the bottom and the shelves and cabinets and wardrobes when their walls are treated with the detergent compositions of the invention. When the floors, walls, countertops, sinks, cabinets and doors of a house or apartment are treated by the liquid detergent compositions of the invention, the incidence of infestation by cockroaches is reduced compared to dwellings where none insect repellent is not applied.

EXAMPLE 1

A single inventive composition, formulated as described below, is used as a starting material to prepare by diluting the six liquid compositions at various degrees of dilution, the greater containing six different n methy1-to-neodecanamide (MNDA) insect repellent substance.

ΐ ο

(Linear dodecyl) benzene-sulsul.female

4 sodium

, . ( 1 )_ 2 non-ionic detergent

Coconut fatty acid MNDA 2.0 0.5 sodium carbonate anhydrous sodium bicarbonate 1 2

4 Isopropyl alcohol

1 Perfume the remainder water

Condensation product of 1 mole of a mixture of fatty alcohols of 9 to 11 carbon atoms with 6 moles of ethylene oxide.

The percentage of MNDA in each of six detergent compositions examined at each as follows: 0.12, 0.20, 0.22, 0.29, 0.4 and 2.0%.

The repellent effect of each of these six detergent compositions for cleaning hard surfaces was evaluated by the method described below and compared to the repellent effect imparted by comparative three compositions comprising an insect repellent, namely three solutions of acetone containing respectively 0.25, 0.5 and 1.0% by weight of MNDA.

Insects - both German and American are removed from colonies maintained at 27 °c. Workers of carpenter ants are taken from a block of wood containing a colony having a queen and are maintained under the same conditions as cockroaches.

Bioassay - forty-eight hours before the start of the test, 50 is allowed German male become accustomed to the cages test plastic (51 χ 28 the X 20 cm) with food and water available at the center. A thin film of Teflon emulsion (Fluon hoc 1, northern blots Agri, Woonsockett, I.R.) on the sides of the cage accommodates insects on the floor of the stand. Used in testing: either 50 cockroaches german female, either 20 American cockroaches male, either 50 of worker carpenter ants.

The repellent effect of various compositions examined is evaluated over time. The method comprises disposing 5 asphalt tiles 7, 60 x 7, 60 cm in a cubic shelter ("pan") and processing the tiles with the various the compositions examined. The faces are treated turned inwardly. The method is based on the reaction avoidance of light by cockroaches. Two milliliters a composition is examined are applied to the entire interior surface of the cup. Bowls witnesses are treated with acetone or water only. Is leaves the cups during drying 1 hour, then a bowl witness and a cuvette processed are placed upside down in each test cages. Nourishment and water are located centrally in each cage, outside of bowls. The insects that are resting on the walls interior of each cuvette is noted all the middle days of the photophase during 25 days or up that equal numbers are found in the cuvettes treated and untreated. After each count, insects are disturbed and the positions of the pits and treated witness are reversed. Thus, the distribution of cockroach at any given day is considered independent of their distribution on the previous day.

The repellent effect is defined as the percentage of insects that avoid the treated surfaces and is calculated as follows:

100 the X (n-)

Repellent effect, ^ - 100% <"t *^NR c.>

where is the number of insects on the treated surface and n_C. is the number of insects on the surfaces controls treated with acetone. The repellent effect of the compounds is evaluated by the number of days to 90% of repellent effect which is based on

(i to) the number of days of repellent effect overall (100 %) and (ll) a probit analysis at maximum likelihood time/repellent effect ("sluice wear's pilot", sluice with Institute 1985), which is calculated based on a measurement of the number of days to 90% of repellent effect (TRgg~~10% insects on the treated surface, 90% on the display area).

Test results of repellent effect are listed in Figure 1 which is a graph representing the number of days to 90% of repellent effect based on percentage of MNDA in the composition is examined.

As shown in this fig., comparative compositions which do not conform to the invention have been unable to reach 90% of repellent effect at a rate of 0.25% of MNDA insect repellent. In contrast, the compositions of the invention were capable of providing 90% of repellent effect during almost 3 days at a rate of 0.2% MNDA.