Patent Description:
In recent years, there has been an inclination to put environmentally friendly biocidal agents on the market. Plant extracts and their active ingredients have exhibited biocidal activity for different types of pests and pathogens, particularly in agricultural crops.

In particular, as described in <CIT>, diallyl sulfides present in garlic oil and garlic extracts have exhibited repellant properties.

<CIT> discloses a stable biocidal microemulsion composition comprising: garlic and tea extracts and as auxiliaries: i) at least one non-ionic surfactant; ii) at least one anionic surfactant; iii) a polar solvent; iv) an antifreeze.

<NPL> discloses a stable biocidal microemulsion comprising: garlic oil, oleic acid, ethoxylated castor oil, n-butanol and water.

<CIT> discloses a stable microemulsion formulation for volatile pesticides comprising: <NUM>) <NUM>-<NUM> % pesticide; <NUM>) <NUM>-<NUM> % of one or more non-polar solvents containing oxygen atoms (e.g. mixture of dimethyl glutarate, dimethyl succinate and dimethyl adipate and/or <NUM>-ethylhexanol); <NUM>) <NUM>-<NUM> % of water soluble polyol; <NUM>) <NUM>-<NUM> % of one or more nonionic surfactants having a HLB from <NUM> to <NUM>; <NUM>) <NUM>-<NUM> % of one or more anionic surfactants; <NUM>) <NUM>-<NUM> % water.

<CIT> discloses the use of diallyl sulfides against tetranychid mites.

Certain natural products are also known to be toxic for some mammals and the environment. Pyrethrins isolated from Tanacetum cinerariifolium have been used as an insecticide because they attack the nervous system of insects, although different studies show pyrethrin intoxication in mammals and pyrethrin toxicity in bees.

Extracts from the Liliaceae family, comprising diallyl sulfides and alkylcysteine sulfoxides, are to known to exhibit biocidal activity but are unstable.

The state of the art describes a variety of surface active agents: anionic compounds, cationic compounds, non-ionic compounds, ampholytes, or mixtures thereof.

Non-ionic surfactants include, among others: alcohols, phenols, polyoxyalkylene ethers having mixtures of oxyalkylene, carboxylate, and sulfonates groups of polyoxyalkylene glycols, amine oxides, sulfoxides, polysorbates, alkyl polyglucosides, synthetic resins, phosphoric acid esters, phosphine oxides, lignin derivatives, silicon compounds, ethoxylated seed oils, products of an undetermined composition, etc..

The hydrophilic-lipophilic balance or HLB of a surfactant is a measure of the degree to which it is hydrophilic or lipophilic, determined by means of calculating values for the different regions of the molecule. HLB can be calculated by means of the methods described by Griffin or Davies. HLB values range from <NUM> for anti-foaming agents to <NUM> for solubilizers.

Document <CIT> describes an insecticidal composition against red spider mites comprising garlic extracts and pyrethrins. Accordingly, this formulation can lead to intoxication in mammals.

The document closest to the invention, i.e., document <CIT>, describes a composition against red spider mites comprising juice obtained by means of crushing and fermenting garlic, chili, and castor oil. This document does not describe the stability of the components nor does it quantify the effectiveness of the formulation.

The problem solved by the invention relates to finding a biocidal composition comprising diallyl sulfides which is stable over time. The solution found by the inventors is a composition comprising:
ii) a polar diluent comprising dialkyl succinates, dialkyl glutarates or dialkyl adipate; iii) surface active agents comprising: (a) at least one non-ionic surfactant with an HLB value between <NUM> and <NUM> and (b) at least one anionic surfactant; and iv) <NUM>-ethyl-<NUM>-hexanol.

The non-ionic surfactants are selected from:.

The anionic surfactants comprise alkylsulfosuccinate salts, alkylbenzene sulfonate salts, or ethoxylated aryl alkyl phosphate esters.

The concentrations of allyl sulfide of the described formulations remained unchanged for <NUM> days stored at <NUM>. It can thus be extrapolated that the formulations will be stable for at least two years at room temperature.

Another problem solved by the invention relates to finding a pyrethrin-free biocidal composition against red spider mites that is not toxic for mammals or the environment.

The formulations described in the invention showed an efficacy statistically similar to those obtained by fenpyroximate or abamectin, which are toxic reference biocidal agents.

The described formulations were also effective against different lepidopterous species affecting horticultural crops, such as, Spodoptera exigua and Mamestra brassicae, Helicoverpa armigera, Tuta absoluta, Pieris rapae, or Phyllocnistis citrella); tetranychid mites, such as Tetranychus urticae, Panonychus citri, Eutetranychus orientalis; and thrips, such as, Frankliniella occidentalis, Thrips tabaci, or Pezothrips kellyanus.

In the drawings, the reference MEGE corresponds to microemulsion formulations and the reference ECGE corresponds to emulsifiable formulations.

wherein the surface active agents comprise at least one non-ionic surfactant with an HLB value between <NUM> and <NUM> and at least one anionic surfactant, all components as defined below and in claims.

The diallyl sulfides comprise diallyl sulfide, diallyl disulfide, diallyl trisulfide, diallyl tetrasulfide defined by the formula:
<CHM>
where R is
<CHM>
<CHM>
<CHM>
<CHM>.

Preferably, the biocidal compositions comprise Allium sativum extracts obtainable by means of methods known to one skilled in the art, as described in detail in Example <NUM>, and said compositions being quantified in diallyl sulfides.

The polar diluents comprise dialkyl succinates, dialkyl glutarates, dialkyl adipate, and optionally water and glycols. Preferably, the polar diluents are mixtures of methyl succinate, methyl glutarate, dimethyl adipate, and optionally water and propylene glycol, which are biodegradable diluents.

The non-ionic surface active agents are selected from:.

Preferably, the polyoxyethylene sorbitan esters are polyoxyethylene (<NUM>) sorbitan monolaurate and polyoxyethylene (<NUM>) sorbitan monooleate, wherein the HLB value for polyoxyethylene (<NUM>) sorbitan monolaurate is <NUM> and the HLB value for polyoxyethylene (<NUM>) sorbitan monooleate is <NUM>.

Preferably, the ethoxylated oils are castor oil with <NUM> moles of ethylene oxide or castor oil with <NUM> moles of ethylene oxide, both with <NPL>; wherein the HLB value for ethoxylated castor oil with <NUM> moles of ethylene oxide is <NUM>, whereas the HLB value for castor oil with <NUM> moles of ethylene oxide is <NUM>.

Preferably, the ethoxylated fatty acid is polyethylene glycol laurate (<NUM>) with an HLB value of <NUM>.

Preferably, the ethoxylated fatty acid alcohol is ethoxylated isotridecyl alcohol with <NUM> moles of ethylene oxide with an HLB value of <NUM>.

The anionic surfactants are selected from alkylsulfosuccinate salts, alkylbenzene sulfonate salts, or ethoxylated aryl alkyl phosphate esters.

Preferably, the anionic surfactants are sodium dioctyl sulfosuccinate, calcium dodecylbenzene sulfonate, or aryl alkyl phosphate ester <NUM> OE.

The C4-C9 alkanol is <NUM>-ethyl-<NUM>-hexanol.

The compositions described in the invention are formulated as an emulsifiable concentrate or microemulsions.

Preferably, the emulsifiable concentrated compositions use a mixture of dimethyl succinate, dimethyl glutarate, and dimethyl adipate as a diluent.

The described compositions are effective for treatment against tetranychid mites (Tetranychus urticae, Panonychus citri, Eutetranychus orientalis), lepidopterous larvae (Spodoptera exigua, Mamestra brassicae, Helicoverpa armigera, Tuta absoluta, Pieris rapae, Phyllocnistis citrella), and thrips (Frankliniella occidentalis, Thrips tabaci, Pezothrips kellyanus.

Biocidal microemulsion compositions are described below. All concentrations are expressed in weight/weight. The table describes the HLB (hydrophilic-lipophilic balance) value for non-ionic surfactants.

Emulsifiable biocidal compositions are described below. All concentrations are expressed in weight/weight. The described compositions are applied after diluting in water. The table describes the HLB (hydrophilic-lipophilic balance) value for non-ionic surfactants.

The formulations were diluted in water to create an emulsion and for subsequent application.

An accelerated stability study was performed and the allyl sulfide content in the emulsifiable formulation was determined according to Table <NUM>:.

wherein the concentration of allyl sulfides in the preceding composition is described in detail in Table <NUM>.

An accelerated stability study was performed and the allyl sulfide content in the composition in the form of the microemulsion described in detail in Table <NUM> was determined.

wherein the concentration of allyl sulfides in the preceding composition is described in detail in Table <NUM>:.

A study was performed to evaluate the efficacy of the emulsifiable compositions and the microemulsion compositions. The number of individual red spider mites per leaf was significantly reduced, particularly at medium and high doses of the microemulsions (<NUM> and <NUM>/Ha) and at a high dose of the emulsifiable compositions (<NUM>/Ha).

The formulations used for the efficacy studies were: Microemulsion compositions according to Table <NUM>.

wherein the concentration of allyl sulfides in the composition is described in detail in Table <NUM>.

The emulsifiable composition used is described in detail in Table <NUM>.

wherein the concentration of allyl sulfides is described in detail in Table <NUM>.

A study was performed to evaluate the efficacy of the emulsifiable compositions and the microemulsion compositions described above (Tables <NUM>-<NUM>). Medium and high doses of the microemulsion compositions (<NUM> and <NUM>/Ha) and a high dose of the emulsifiable formulations (<NUM>/Ha) reached efficacies of <NUM>-<NUM>%, which are statistically similar to those obtained by the reference (fenpyroximate).

An efficacy study in peach red spider mites was performed on the compositions described in detail in Tables <NUM>-<NUM>.

It was observed that the spider mite populations exhibit a less pronounced increase in the treatments of the microemulsion formulation and significant differences are observed with the control populations after the third application of the product.

The efficacies obtained using the microemulsion formulation reach mean values for the medium (<NUM>/Ha) and high (<NUM>/Ha) doses, with a maximum efficacy of <NUM>%.

The severity of the formulation described in Tables <NUM>-<NUM> (<NUM>, <NUM>, and <NUM>/hl) at <NUM> doses was studied. The results show a decrease in red spider mite populations. Seven days after the second application (7DD2A), the medium and high doses have populations similar to those of the reference (abamectin).

Efficacy after <NUM> applications was studied, with the medium and high doses of the formulation described in Tables <NUM>-<NUM> showing efficacies of the order of <NUM>-<NUM>%, which are similar to those of the reference (abamectin).

Garlic extract is obtained from any variety of Allium sativum cultured without pesticide residues.

Dry and chopped cloves of garlic are extracted by means of a stream of water vapor. Water is eliminated from the obtained oil by condensation. The obtained oil has a density of <NUM>-<NUM>/ml and an Oil refractive index of <NUM>-<NUM>.

An efficacy study was performed in lettuce worms (Spodoptera exigua) for different compositions as described in detail below.

The results obtained for formulations containing garlic extracts, quantified in allyl polysulfides, were equivalent to the results obtained with the reference product (azadirachtin) at <NUM> and <NUM> days of application. <FIG> and <FIG>.

An efficacy study was performed in pepper worms (Mamestra brassicae) and other worms for the different compositions as described in detail below:.

The results obtained for formulations containing garlic extracts, quantified in allyl polysulfides, were equivalent to the results obtained with the reference products Bacillus thuringiensis subspecies Aizawai (<NUM> MIU/g).

A study was performed to evaluate the efficacy of emulsifiable compositions versus a composition in the form of a microemulsion, using a <NUM>% emulsifiable azadirachtin concentrate as a reference product. The different compositions are described in detail below.

Claim 1:
A biocidal composition comprising:
- at least one diallyl sulfide of formula
<CHM>
where R is selected from
<CHM>
<CHM>
<CHM>
- a polar diluent which comprises: dialkyl succinates, dialkyl glutarates, or dialkyl adipate,
- surface active agents,
- a C4-C9 alkanol which is <NUM>-ethyl-<NUM>-hexanol, characterized in that the surface active agents comprise:
- at least one non-ionic surfactant with an HLB value between <NUM> and <NUM>,
- at least one anionic surfactant selected from the group consisting of alkylsulfosuccinate salts, alkylbenzene sulfonate salts and ethoxylated aryl alkyl phosphate esters.