FR2777014A1 - Detergent compositions containing a mixture of insect repellants, useful as fly repellant for domestic and other surfaces - Google Patents

Abstract

Liquid detergent compositions for application to solid surfaces containing at least 2.5% of a first insect repellant (I) which is a mixture of N,N-diethyl-m-toluamide (DEET), 2-ethyl hexane-1,3-diol (EHD), and dimethyl phthalate (PDM), and at least 0.5% of a second insect repellant (II) which is one or more of the following: isobornyl acetate, D-limonene, lilial, terpineol, and terpenyl acetate. (II) preferably comprises a mixture of all five of the named compounds. The compositions preferably further contain 0.5 - 5% butyl diglycol. The other components in these compositions are conventional. The surfactants may be anionic, cationic, non-ionic, zwitterionic or amphoteric and usually comprise 1 - 20% of the composition. The compositions may further contain sequestering agents (such as polyphosphates, polycarboxylates etc.), solvents such as alcohols, esters, glycols, ketones, terpenes, (halogenated) hydrocarbons, glycol ethers, and long chain diols, buffers, such as carbonates or metasilicates, enzymes, suspending agents, preservatives and perfumes. Independent claims are also included for a process of conferring insect repellant properties on to solid surfaces by applying a composition as described at 1 - 10mg/cm<2> and allowing this to dry without rinsing.

Description

The present invention relates to a liquid detergent composition for cleaning solid surfaces, this composition further having insect repellent properties. The present invention also relates to a process for imparting insect repellent properties to solid surfaces as well as the use in a liquid detergent composition of a combination of insect repellent agents.

For the purposes of the present invention, the term “insect repellent” means any substance capable of repelling or warding off insects.

Many insects that are common in homes, such as cockroaches, ants and flies, are considered to be harmful. We therefore seek to destroy them or at least to control them. Insect repellents for mosquitoes have long been known, and several compounds have moreover been discovered which have insect repellent properties for other insects.

It is known to incorporate an insect repellent compound in a liquid detergent composition. We can cite in this regard the request
EP-0 619 363 describing various possible insect repellent compounds and in particular N-methylneodecanamide (MNDA).

It is also known to use a mixture of N-diethyl-mtoluamide (DEET), 2-ethylhexanediol-1,3 (EHD) and dimethyl phthalate (PDM), as an insect repellent against a number of insects. (flies, mosquitoes, ticks, lice, horseflies, etc.). It is generally suggested to use this mixture at concentrations between 10 and 50% by weight.

It has now been found, quite surprisingly and unexpectedly, that the combination of the above-mentioned mixture with certain other compounds of weakly insect-repellent character, obtained from raw materials for perfumery, makes it possible to obtain liquid detergent compositions exhibiting excellent insect-repellent properties while using only very low proportions of insect repellent compounds compared to the respective necessary proportions of the compounds taken in isolation.

A subject of the present invention is thus a liquid detergent composition for solid surfaces, further exhibiting insect repellent properties, characterized in that it contains a combination of less than 2.5% by weight, relative to the total weight of the composition. , a first insect repellant in the form of a mixture of N, N-diethyl-m-toluamide (DEET), 2-ethylhexanediol-1,3 (EHD) and dimethyl phthalate (PDM), and less than 0.5% by weight, relative to the total weight of the composition, of a second insect repellent agent in the form of one or more compounds selected from the group consisting of isobornyl acetate, D-limonene , lilial, terpineol and terpenyl acetate.

The mixture of DEET, EHD and PDM constituting the first insect repellent agent can be produced by a person skilled in the art using his general knowledge, in particular as regards the determination of the respective proportions of the three components DEET, EHD and PDM of the mixture, by tests. routine, depending on the case. In particular, one can advantageously use the mixture as marketed under the name “UNIREP U-18” by the company.
INDUCHEM (Dübendorf, Switzerland).

The second insect repellant is preferably a mixture of isobornyl acetate, D-limonene, lilial, terpineol and terpenyl acetate. As for the first insect repellent agent, the second insect repellent agent can be produced by a person skilled in the art using his general knowledge, in particular as regards the determination of the respective proportions of the various components, by routine tests, as the case considered.

Advantageously, the composition according to the invention also contains butyldiglycol, as solvent, in a proportion of between approximately 0.5 and approximately 5% by weight, relative to the total weight of the composition.

The cleaning composition for solid surfaces according to the present invention can contain the usual ingredients for this type of composition, such as, in particular, surfactants chosen from anionic, nonionic, cationic, zwitterionic or amphoteric surfactants, solvents, or even reinforcers. of detergency.

Several anionic, nonionic, cationic, zwitterionic and amphoteric surfactants can be used in the composition according to the present invention. A typical listing of surfactants is described in US Pat. No. 3,663,961 which is incorporated herein by reference. These surfactants can be used alone or in combination with one another in contents of between approximately 1% and approximately 20% by weight, relative to the total weight of the composition.

Suitable anionic surfactants are soluble salts of alkylbenzenesulphonates, alkyl sulphates, alkyl polyethoxyether sulphates, paraffin sulphonates, alpha-olefin sulphonates, alpha-sulphocarboxylates and their esters, alkyl glycerilether sulphonates, sultates and sulphonates of fatty acid monoglycerides, alkyl phenol polyethoxyether sulfates, 2 -acytoxy-alkane-1 -sulfonates and beta-alkyloxy alkane sulfonates.

Suitable nonionic surfactants are alkoxylated nonionic surfactants and those which have a half-polar character. Alkoxylated surfactants can be defined as being produced by condensation of alkylene oxide groups (hydrophilic in nature) with hydrophobic organic compounds.

Examples of suitable nonionic surfactants are the condensation products of polyethylene oxide with alkyl phenols, the condensation products of polyethylene oxide with primary or secondary aliphatic alcohols, the products obtained by condensation of polyethylene oxide. ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with either propylene glycol or ethylene diamine.

Examples of half-polar surfactants are water-soluble amine or phosphine oxides.

As suitable amphoteric surfactants are the water soluble derivatives of straight or branched chain secondary or tertiary amines with aliphatic substituents which contain solubilizing groups selected from carboxy, sulfonate, sulfate, phosphate or phosphonate groups.

Suitable zwitterionic surfactants are the water soluble derivatives of aliphatic ammonium, phosphonium or sulfonium compounds, in which the aliphatic substituents may be straight chain or branched and contain anionic solubilizing groups.

The composition according to the invention may also contain sequestering agents chosen from salts - soluble in water - of polyphosphates, polycarboxylates, aminopolycarboxylates, polyphosphonates and aminopolyphosphonates.

Among the polyphosphates are pyrophosphates, tripolyphosphates and higher polyphosphates such as methaphosphates and hexametaphosphates.

Among the carboxylate type sequestrants, there are monomeric polycarboxylates such as citric, lactic, acotinic, tartaric, citraconic, succinic, adipic and maleic acids and their salts. There are also carboxylic oligomers or polymers such as homo- and copolymers of polycarboxylic manomers such as maleic, acrylic, metacrylic, citraconic, acotinic, fumaric, mesaconic, alpha-hydroxy-acrylic acids and their salts.

Among the sequestering agents of the aminopolycarboxylic type, there are ethylenediamine tetraacetates, diethylene diamine pentaacetates, nitrilotriacetate, methyl glycine diacetate, isoserine diacetates and their salts.

Among the polyphosphonates and aminopolyphosphonates, we find hydroethyl diphosphonic acids, nitrilo tri (methylene posphonic), ethylenediamine tetra (methylenephosphonics), diethylene-diamine penta (methylenephosphonics) and their salts.

Other common components of compositions for cleaning solid surfaces are organic solvents which can be miscible with water to form immiscible water-solvent solutions. They must be emulsified (or microemulsified) using surfactants.

Among the water-miscible solvents are short chain aliphatic or aromatic alcohols, esters of short chain fatty acids with alcohols, glycols and ketones.

Among the water-immiscible solvents, there are terpenes, hydrocarbons, halogenated hydrocarbons, glycol ethers, long-chain diols.

The composition according to the invention may also contain other ingredients such as buffering agents such as alkaline or ammonium carbonates, bicarbonates, metasilicates and orthophosphates, enzymes, soil suspending agents, preservatives or agents. aromatic.

The present invention also relates to a process for imparting insect repellent properties to solid surfaces at the same time as they are cleaned, comprising the steps of applying by rubbing on the solid surfaces an amount between 1 mg / cm2 and 10 mg. / cm2 of a detergent composition, further exhibiting insect repellent properties, then allowing the rubbed surfaces to dry without rinsing them, this process being characterized in that a detergent composition is applied, further exhibiting insect repellent properties, such as than the composition according to the invention defined above.

Finally, a subject of the present invention is also the use, in a liquid detergent composition for solid surfaces, of a combination of less than 2.5% by weight, relative to the total weight of the composition, of a first insect repellent agent. as a mixture of N, N-diethyl-m-toluamide (DEET), 2-ethylhexanediol-1,3 (EHD) and dimethyl phthalate (PDM), and less than 0.5% in weight, relative to the total weight of the composition, of a second insect repellent in the form of one or more compounds selected from the group consisting of isobornyl acetate, D-limonene, lilial, terpineol and terpenyl acetate, to impart insect repellent properties to the liquid detergent composition.

More particularly, preferably, this use is characterized in that the said second insect repellent agent is a mixture of isobornyl acetate, D-limonene, lilial, terpineol and terpenyl acetate.

The present invention will now be illustrated with the aid of examples which should in no case be interpreted in a limiting manner as regards the scope of the invention.

Examples - Repulsion test
Different compositions were produced (see Table 1) in order to test their respective repellency capacity under the following conditions.

1) Material and method
The tests were carried out using Calliphora vo mito na flies, that is to say diptera belonging to the Calliphondae subfamily, more commonly called "blue flies" or "meat flies". These flies are present inside homes from spring to late fall, depending on the region.

They are quite undesirable from a hygienic point of view as they lay their eggs on meat.

The rearing of flies in the Laboratory was carried out in an air-conditioned room at 25 + 1 "C with a photoperiod of 12 hours of light (photophase: 7 to 19 hours). Flies living in groups, each composition was tested with 20 batches of 10 adult flies (male and female) approved for 5 days.

The compositions studied, in concentrated form, were tested in diluted form at the rate of 4 plugs (120 ml) of concentrated composition per liter of water.

Rectangular experimental enclosures (length x width x height: 20 x 20 x 8 cm) were used, divided into two equal compartments by means of a removable partition. The walls and floor of these speakers were covered with vinyl paper and the ceiling was made of glass. An orifice located in the center of one of the walls allows the introduction of insects directly into the center of the experimental chambers, without outside intervention.

Just before the start of the experiment (5 min) the ceiling, the walls and the floor of one of the compartments of the enclosure were cleaned with one of the compositions studied at a rate of 0.5 cm2 of composition / cm2 surface area to be cleaned. The movable partition was then removed and the insects were placed in front of the entry port of the enclosure. At time to (5 min after the end of the cleaning), the insects were brought into the chamber which thus began their exploration in the experimental chambers.

The choice of insects for the neutral compartment or the compartment cleaned with the studied composition is noted every half hour for 4 hours.

The repelling activity of the compositions studied, including that known as “control” (without any insect repellent agent) was expressed relative to that of distilled water as a control.

The results obtained were converted into the percentage of insects (P) present in the cleaned compartment (by undesirable atractive action of the composition studied) and present in the neutral zone (N) by repelling action of the composition studied).

The repellency rate was thus calculated using the following formula
T (%) = 100 - 2P in which P represents the percentage of insects which have settled in the compartment cleaned by the composition studied.

Thus, the value of T is 0% if the individuals distribute themselves equally in the two compartments (P = 50%). It is 100% if all the insects have chosen the neutral compartment (P = 0%) and -100% if all the insects settle undesirably in the cleaned compartment (P = 100%).

2) Results
The compositions studied and the results obtained are collated in the following table.

In this table, the component called “UNIREP U-18” represents a mixture, as marketed by the company INDUCHEM (Dubendorf, Switzerland).

From the results appearing in this table, it can be seen that the liquid detergent composition according to the invention exhibits a completely surprising and unexpected repellency rate with regard to the respective repellency rates of the compositions containing only one of the two. insect repellent agents within the meaning of the invention (respectively component "UNIREP U-18" and mixture of isobornyl acetate, dlimonene, lilial, terpineol and terpenyl acetate).

In particular, it is clear that it was not at all obvious to obtain an AT repellency increment of +3.6 corresponding to the composition according to the invention, by combining the respective insect repellent agents of compositions A and B which have a repelling increment A T of 4.9 and -5.5, respectively.

Ingredients Compositions (relative% by weight)
AB control according to the invention
Sodium olefin sulphonate SAS 60 3 3 3 3
Alcohol (C9-C11) + 6EO (nonionic) 1 1 1 1
Butyldiglycol 2 2 2 2
Preservative 0.05 0.05 0.05 0.05
Colorant 0.010 0.010 0.010 0.010
Isobornyl acetate - - 0.08 0.08
D-limonene - - 0.032 0.032
Lilial - - 0.024 0.024
Terpineol - - 0.024 0.024
Terpenyl acetate - - 0.020 0.020
Other perfume ingredients 0.220 0.220 0.220 0.220
UNIREP U-18 - 1 - 1
Water 93.72 92.72 93.54 92.54
Repelance rate (T) +43.3 +42.4 +37.8 +46.9
Repulsion increment (#T) - -0.9 -5.5 +3.6

Claims (6)

1. Liquid detergent composition for solid surfaces, also having insect repellent properties, characterized in that it contains a combination of less than 2.5% by weight, relative to the total weight of the composition, of a first insect repellent in the form of a mixture of N, N-diethyl-m-toluamide (DEET), 2ethylhexanediol-1,3 (EHD) and dimethyl phthalate (PDM), and less than 0.5% in weight, relative to the total weight of the composition, of a second insect repellent in the form of one or more compounds selected from the group consisting of isobornyl acetate, D-limonene, lilial, terpineol and terpenyl acetate. 2. Composition according to Claim 1, characterized in that the said second insect repellent agent is a mixture of isobornyl acetate, D-limonene, lilial, terpineol and terpenyl acetate. 3. Composition according to Claim 1 or 2, characterized in that it also contains butyldiglycol, - in a proportion of between approximately 0.5 and approximately 5% by weight, relative to the total weight of the composition. A method of imparting insect repellant properties to solid surfaces at the same time as they are cleaned, comprising the steps of applying by rubbing onto the solid surfaces an amount between 1 mg / cm2 and 10 mg / cm2 of a composition. detergent, further exhibiting insect repellent properties, then allowing the rubbed surfaces to dry without rinsing them, method characterized in that a detergent composition is applied, further exhibiting insect repellent properties, such as that defined in any one of claims 1 to 3. 5. Use in a liquid detergent composition for solid surfaces, of a combination of less than 2.5% by weight, relative to the total weight of the composition, of a first insect repellent agent in the form of a mixture of N , N-diethyl-m-toluamide (DEET), 2-ethylhexanediol-1,3 (EHD) and dimethyl phthalate (PDM), and less than 0.5% by weight, relative to the total weight of the composition , a second insect repellent in the form of one or more compounds selected from the group consisting of isobornyl acetate, D-limonene, lilial, terpineol and terpenyl acetate, to impart insect repellent properties to the liquid detergent composition. 6. Use according to claim 5, characterized in that said second insect repellent agent is a mixture of isobornyl acetate, D-limonene, lilial, terpineol and terpenyl acetate.