Note: Descriptions are shown in the official language in which they were submitted.
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LIQUID HQUSEHOLD CLEANING COMPOSIIION WITH INSE~
R E P ~
BACKGROUND OF THE INVENDQN
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This invention relates to liquid detergent compositions suitable for cleaning
hard surfaces and which impart insect repelling properties. More particularly, this
2 0 invention relates to liquid all purpose detergent compositions containing an insect
repellent material, and to a process for clsaning and repelling insects from surfac~s
and articles to which such detergent compositions are applied.
Many types of insects common in households, such as Gennan (Blaiteh
c~ germanica) or house cockroaches, are classified as pests, and much efforl hag
2 5 been made to eradicate or at least to control them. Mosquito repelbnts have long
been marketed and various chemicals that are effective in repelling roaches havebeen discovered. Typically, these chemicals and repellents are used in the
household by appqing or spraying them to su~faces of walls, floors, cabinets,
drawers, packages, containers, rugs, upholstery and carpeting, and in potential
3 0 nesting places for insects, such as inside walls and between floors. Howeve~,
heretofore insect repellents have not been generally used in conjunc~ion with hard
surface cleaners so as to effectively clean a hard household surface, such as a
kitchen wall, oven top, bathroom floor or the like, while at the same time applying a
~-~ film of insect repellent material which is suHiciently substantive tu the surface to
~;3 3 5 which the composition is applied to repel insects therefrom.
The incorporation of an insect repellent into a polishing product for
household floors is known in the art. U.S. Patent 3,018,217 to Bruce discloses floor
wax coating compositions containing dibutyl succinate as an insect repellent. U.S.
Patent 3,034,950 to Goodhue et al, discloses a class of insect repellent compounds
~ O which may be applied to surfaces dispersed in a wax. In U.S. 4.455.308 to
`!~ Smolanoff, there are described insect repellent formulations containing a liquid
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carrier such as liquid aliphatic or aromatic hydrocarbons. An emulsifying agent
such as a nonionic surfactant may be added to the liquid hydrocarbon to permit the
composition to be dispersed in water for end use application. U.S. Patent
4,822,614 to Rodero, discloses an insect-repellent ingredient in a hydrocarbon-
5 based solvent such as isoparaffinic hydrocarbons.
SUMMARY OF THE INVENTIQN
The prssent invention provides an aqueous liquid detergent composition
10 capable of cleaning a hard surface and repelling insects therefrom comprising (i) a
detersive proportion of a surface active detergent compound selected from the
group consisting of anionic, nonionic, cationic and amphoteric detergent
compounds; (ii) at least about 50%, by weight, water; and (iii) an effective amount
of an insect repellent material which is sufficient to repel insects from such hard
1 5 surface after application of the detergent composition thereto. The liquid detergent
composition is free of an insecticide.
The present invention is predicated on the discovery that the insect repellent
propenies of a repellent material is enhanced with regard to a specific area or
location when such are~ or location is cleaned with a detergent composition as
2 0 herein described. This effect may be attributed to the natural tendency of insects to
preferentially congregate in soiled areas rather than upon a cleaned surface as
well as the increased substantivity of the insect repellent material to such washed
or cleaned surfaces.
The term ~insect~ is used herein in its broad sense and, is intended to
2 5 encompass cockroaches, such as the German (Blattela germanica) and American
(Periplaneta americana) roach, as well as mosquitoes, moths, flies, fleas, ants, lice
and arachnids, such as spiders, ticks and mites.
The term ~insect repellent material~ is intended to encompass a wide varie~y
of materials having insect repellent properties which are compatible with the type of
3 0 detergent composition described herein and which manifest a sufficient
substantivity to the hard surface to which the detergent composition is applied to be
efficacious as a repellent.
Included among the insect repellent materials usaful for the present
invention are the following compounds which may be used individually or in
3 5 combination with other repellent materials, the designation in parenthesis following
certain compound names referring to its commercial or common designation:
N-alkyl neoalkanamides wherein the alkyl is of 1 to 4 carbon atoms, and ths
neoalkanoyl moiety is of 7 to 14 carbon atoms, preferably N-methyl
neodecanamide:
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N,N-diethyl-meta-toluamide (DEET);
2-Hydroxyethyl-n-octyl sulfide (MGK 874);1
N-Octyl bicycloheptene dicarboximide (MGK 264);
A preferred mixture of the above two materials comprising 66% MGK
264 and 33% MGK 874;
Hexahydrodibenzofuran carboxaldehyde (MGK 11);
Di-n-propyl isocinchomerate (MGK 326);
2-Ethyl-1,3-hexanediol (Rutgers 612);
2-(n-butyl)-2-ethyl-1 ,3-propanediol;
1 0 Dimethyl phthalate;
Dibutyl succinate (Tabutrex);
Piperonyl butoxide; and
Pyrethrum
(~) MGK Repellents are trademarks of McLaughlin Gormley King Company;
Minneapolis; Minnesota, USA.
Although the above-mentioned insect repellent materials are longer lasting
and are preferred for purposes of the present invention, other useful repellent
2 0 materials include essential oils such as Mentha arvensis (Commint); Menthapiperita (Peppermint); Mentha spicata (Arnerican Spearmint); Mentha cardica
(Scotch Spearmint); Lemongrass East Indian Oil; Lemon Oil; Citronella;
Cedarwood (Juniperus virginiana L.); and Pine Oil. Terpenoids are another class
of materialshaving insect repellent properties, the most useful being (-)-Limonene;
2 5 (+)-Limonene; (-)-Carvone; Cineole (Eucalyptol); Linalool; Gum Camphor; ~:
'~ Citronellal; Alpha and Bata -Terpineol; Fencholic acid; Borneol iso Borneol, Bornyl ~:
acetate and iso Bomyl acetate.
3 Among the non-commercial repellent materiais useful for ghe invention are
the foliowing:
3 0 . N,N-Diethyl cyclohexylacetamide (DECA)
1 ,2,3,6-Tetrahydro- 1 -(2-methyl-1 -oxopentyl)
3 piperidine
N,N-Diethyl-3-cyclohexyl propionamide (DCP)
2-Ethyl- 1 -(2-methyl- 1 -oxo-2-butenyl)
3 5 piperidine
.I N,N-diethyl nonanamide, and
N,N-Diethyl Phenylacetamide.
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With regard to the aforementioned N-alkyl neoalkanamides, the alkyl group
is preferably methyl or ethyl, and most preferably is methyl. The neoalkanoyl
moiety is preferably neodecanoyl or neotridecanoyl.
S DETAILED DESCRIPTION OF THE INY~NTION
The detergent compositions of the invention contain a detersive proportion
of one or more surface active detergent compounds from among anionic, nonionic,
cationic and amphoteric detergents, which generally will be in the range of from1 0 about 1 to about 30%, by weight, of the composition, preferably from about 2 to
about 20%, by weight. The detergent is preferably a synthetic organic detergent of
the anionic or nonionic type and often a combination of anionic and nonionic
detergents will be most preferred. Descriptions of many such detergents are found
in the text Surface ActEve Agents and C~etergents, Vol, Il, pages 25-138, by
1 5 Schwartz, Perry and Berch, published in 1958 by Interscience Publishers, Inc.
Such compounds are also described in a 1973 publication by John W.
McCutcheon, entitled D~ergents and Emul~ifi~rs. Both such publications are
incorporated herein by reference.
The anionic detergents employed will normally be salts of alkali metals, such
2 0 as sodium or potassium or ammonium or lower alkanolammonium salts, e.g.,
triethanolamine salts. The anionic detergent may be ~ sulfate, sulfonate,
phosphate or phosphonate or salt of other suitable acid but usually will be a sulfate
or sulfonate. The anionic detergents include a lipophilic group, which will normally
have from 10 to 18 carbon atoms, preferably in linear higher alkyl arrangement, but
2 5 other lipophilic groups may be present instead, preferably includin~ 12 to 16
carbon atoms, such as branched chain alkyl benzene. Examples of suitable
anionic detergents include higher fatty alcohol sulfonates, such as sodium
tridecylbenzene sulfonate; sodium linear alkyl benzene sulfonates, e.g., sodium
linear dodecylbenzene sulfonate; olefin sulfonates; and paraffin sulfonates. The3 0 anionic detergents are preferably sodium salts but potassium, ammonium and
triethanolamrnonium salts are often more desirable for some liquid compositions.The suitable nonionic detergents will normally be condensation products of
lipophilic compounds or moieties and lower alkylene oxides or polyalkoxy
moieties. Highly preferable lipophiles are higher fatty alcohols of 10 to 18 carbon
3 5 atoms but alkyl phenols, such as octyl and nonyl phenols, may also be used. The
alkylene oxide of preference is ethylene oxide and normally from 3 to 30 moles of
ethylene oxide will be present per mole of lipophile. Preferably such ethoxylatecontent will be 3 to 10 moles per mole of higher fatty alcohol and more preferably it
will be 6 to 7 moles, e.g., 6.5 or 7 moles per mole of higher fatty alcohol (and per
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mole of nonionic detergent). Both broad ranges ethoxylates and narrow range
ethoxylate (BP~E's and NRE's) may be employed, with the difference between them
being in the ~spread~ of number of ethoxylate groups present, which average within
the ranges given. For example, NRE's which average 5 to 10 EtO groups per mole
5 in the nonionic detergent will have at least 70% of the EtO content in polyethoxy
groups of 4 to 12 moles of EtO and will preferably have over 85% of the EtO content
in such range. BRE nonionic detergents have a broader range of ethoxy contents
than NRE's, often with a spread from 1 to 15 moles of EtO when the EtO chain is in
the 5 to 10 EtO range (average). Examples of the BRE nonionic detergents include10 those sold by Shell Chemical Company under the trademark NeodolR, including
Neodol 25-7, Neodol 23-6.5 and Neodol 25-3. Supplies of NRE nonionic
detergents have been obtained from Shell Development Company, which
identifies such materials as 23-7P and 23-7Z.
Cationic surface active compounds may also be employed. They comprise
15 surface active detergent compounds which contain an organic hydrophobic groupwhich forms part of a cation when the compound is dissolved in water, and an
anionic group. Typical cationic detergents are amine and quaternary ammonium
compounds.
The quaternary ammonium compounds useful herein are known materials
2 0 and are of the high-sof~ening type. Included are the N1 N-di-(higher) C1 4-C24,
N1N-di(lower C1-C4 alkyl quatemary ammonium salts with water solubilizing
anions such as halide, e.g. chloride, bromide and iodide; sulfate, methosulfate and
the like and the heterocyclic amides such as imidazolinium.
For convenience, the aliphatic quaternary ammonium salts may be
2 5 structurally defined as follows:
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R1 +
R-- N --R2 X~
3 0R3
wherein R and R1 represent alkyl of 14 to 24 and preferably 14 to 22 carbon atoms;
3 5 R2 and R3 represent lower alkyl of 1 to 4 and preferably 1 to 3 carbon atoms, X
represents an anion capable of imparting water solubility or dispersibility including
the aforementioned chloride, bromide, iodide, sulfate and methosulfate.
Particularly preferred species of aliphatic quats include:
distearyl dimethylammonium chloride
4 0 di-hydrogenated tallow dimethyl ammonium chloride
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di tallow dimethyl ammonium chloride
distearyl dimethyl ammonium methyl sulfate
di-hydrogenate~ tallow dimethyl ammonium methyl sulfat0.
Anphoteric detergents are also suitable for the invention. This class of
5 detergents is well known in the art and many operable de~ergents are disclosed by
Schwartz, Perry and Berch in Surface Active Agents and Detergents~, Vol. Il,
Interscience Publishers, Inc., New York (1958) in Chapter 4 thereof. i~xamples of
suitable amphoteric detergents include: alkyl betaiminodipropionates,
RN(C2H4COOM)2; and alkyl beta-amino propionates, RN(H)C2H4COOM.
Builders may be present in the liquid detergent composition in an amount of
from about 1 to 20% to improve ~he detergency of the synthetic organic detergents.
Such builders may be inorganic or organic, water soluble or water insoluble.
Included among such builders are polyphosphates, e.g., sodium tripolyphosphate;
carbonates, e.g., sodium carbonate; bicarbonates, e.g., sodium bicarbonate;
15 borates, e.g., borax; and silicates, e.g., sodium silicate; water insoluble inorganic
builders, including zeolites, e.g., hydrated Zeolite 4A; and water soluble organic
builders, including citrates, gluconates, NTA, and polyacetal carboxylates.
Various adjuvants may be present in the detergent compositions such as
fluorescent brighteners, antistatic agents, antibacterial agents, fungicides, foaming
2 0 agents, anti-foams, flow promoters, suspending agents, antioxidants, anti-gelling
agents, soil release promoting agents, and enzymes.
The liquid detergent compositions of the invention will generally comprise
from about 2 to 20% of surface active detergent compounds which are preferably
anionic and/or nonionic, from about 1 to 20%, by weight, of builder salts for such
2 5 detergents and from about 0.2 to 20%, preferably 0.5 to 10%, by weight, of the
insect repellent material, the balance being predominantly water, adjuvants and
optionally an emulsifying agent, or hydrotrope such as sodium toluene sulfonate or
a soivent suitable for the insect repellent material such as isopropyl alcohol or
acetone. To facilitate the incorporation of a fragrance or perfume into the aqueous
3 0 liquid detergent composition, it is often advantageous to forrnulate the liquid
detergent composition in microemulsion form with water as the continuous phase
and oil or hydrocarbon as the dispersed phase.
In practical tests, on actual kitchen floors, counters, drainboards and walls,
and in kitchen cabinets and under refrigerators, in roach-infested apartments,
3 5 significantly fewer roaches will be observed on surfaces to which or near which the
~ invented liquid detergent compositions are applied than on control surfaces, and
;l fewer roaches are found on the bottoms and shelves of cabinets and pantries when
~i walls thereof are treated with the invented detergent compositions. When floors,
-~ walls, counters, sinks, cabinets and doors in a house or apartment are treated with
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the liquid detergent compositions of the invention, the incidence of cockroach
infestation is reduced, compared to control apartrnents where no repellent is
applied.
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EX~MplE
A single composition in accordance with the invention formulated as shown
below was used as the starting material to prepare by dilution six liquid
compositions of varying degrees of dilution containing six correspondingly different
5 levels of N-methyl neodecanamide (MNDA) insect repellent matarial.
LI~VID HARI? SURFACE C~ER ..
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COMIPONEIII PE~ ~G~
Sodium linear dodecylbenzene sulfonate 4
Nonionic detergent(~) 2
MNDA 2.0
l 5 Coconut fatty acid 0.5
Soda ash 2
Sodium bicarbonate
Isopropyl alcohol 4
j Water Balance
2 0 Fragrance
(~)Condensation product of one mole of a mixture of fatty alcohols of 9-11 carbon
atoms with 6 moles of ethylene oxide.
2 5 The percentag~ of MNDA in each of the six tested detergent compositions
varied, respectively, as follows: 0.12, 0.20, 0.22, 0.29, 0.4 and 2.0%
The insect repellency of each of these six hard surface cleaning detergent
compositions was tested by the procedure described below and compared with the
repellency imparted by three repellent~con~aining comparative compositions, i.e.3 0 three solutions of acetone containing 0.2~, 0.5 and 1.0%, by weight, respectively, of
MNDA.
TE~I PRQC~DUF~
Insects -- German and American cockroaches were from established
3 5 colonies maintained at 27C. Carpenter ant workers were collected from a logcontaining a queenright colony and were kept in the same conditions as the
cockroaches.
Bloassay -- Forty-eight hours prior to initiation of an assay, 50 male
German cockroaches were allowed to acclimate to the plastic test cages (~1 x 28 x
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20 cm) with food and water available in the center. A thin film of teflon emulsion
(Fluon AD-1, Northern products, Woonsocket, R.l.) on the sides of the cages
restricted the insects ~o the floor of the cage. The assays used either 50 female
German cockroachas, 2Q males American Cockroaches, or 50 carpenter ant
workers.
The repellency of the various compositions to be tested were evaluated over
time. The procedure consisted of arranging five 3 x 3 inch asphalt tiles into a cubic
shelter (~cup~) and treating the tiles with the various test compositions. The treated
sides faced inward. The method relies on the light avoidance response of the
cockroaches. Two milliliters of a test composition was applied to the entire inside
surface of the cup. Control cups were treated with acetone or water only. The cups
were allowed to dry for 1 hr and then a control and a treated cup were inverted into
each of the test cages. Food and water were provided in the center of each cage,outside of the cups. The number of insects resting on the inner walls of each cup
1 5 were recorded in the middle of the photophase daily for 25 days or until equal
numbsrs were found in treated and untreated cups. After each count the insects
were disturbed and the positions of the treated and control cups were reversed.
Accordingly, the distribution of cockroaches for any given day is considered
independent of the previous days distribution.
2 0 Repellency was defined as the percentage of insects that avoided the
treated surfaces and was calculated as
1 00 x (Nt )
% Repellency = 100 -
(Nt + Nc )
2 5 where Nt is the number of insects on the treated surface and Nc is the number on
the acetone treated control surfaces. The repellency of compounds was evaluated
on the basis of the number of days of 90% repellency which is based on (i) the
number of days of complete (100%) repellency and (ii) a maximum likelihood probit
analysis of time/repellency (SAS User's Guide, SAS Institute 1985) from which a
~,3 0 measure was calculated of the number of days of 90% repellency (RTgo -- 10% of
the insects on the treated surface, 90% on the control surface).
The results of the repellency tests are indicated in Figure 1 which is a graph
showing the number of days with 90% repellency as a function of the percent of
MNDA in the test composition.
3 5 As noted in the Figurs, the comparative compositions not in accordance with
the invention were unable to achieve 90% repellency at a level of MNDA repellentof 0.25%. In contrast thereto, the compositions of the invention were able to
provide almost 3 days of 90% repellency at a 0.2% level of MNDA.
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