DD211056A5 - MICROEMULSIONS - Google Patents

Abstract

The present invention relates to aqueous microemulsions of agrochemically active compounds and to processes for preparing these microemulsions. The aqueous microemulsions contain from 0.1 to 80% by weight of at least one agrochemically active substance which is sparingly soluble in water, an active substance for controlling pests in the household and hygiene sector and / or a pharmacologically active substance, 1 to 20% by weight. -% of an emulsifier mixture - and water and - optionally 1 to 30 wt .-% of at least one water-immiscible organic solvent and / or a solubilizer and - optionally 0.05 to 15 wt .-% of additives, wherein the sum of the components each 100 wt .-% entraegt.

Description

Berlin, 12 '12.1983 62 859/11

Mxkroemulsionen

The present invention relates to aqueous microerions of agrochemical active compounds "Active substances for controlling pests in the household and hygiene sector and / or pharmacologically active substances" The invention also relates to a method for producing these microemulsions and their use. "

Jss are already ül-in-water emulsions of numerous sparingly water-soluble agrochemical active ingredients known, which in addition to the active ingredients in each case either a surfactant and a thickener or a relatively large amount of surface-active substances (see "Dd-A 009 944 ₁ 011 611 DM3 and JP-a 122628-77) ο This addition of thickener or _e of large amounts of surfactants is associated with additional cost and thus represents "a serious Hachteil of the known oil-in-water Ünulsion, adding comes that the previously described preparation of such emulsions is not generally applicable, "In essence, then only those in water little soluble active ingredients that are liquid at room temperature or at least have a very low melting point, namely, is that the known oil-in-Wasaer ~ are ümulsion often not sufficiently stable at low temperatures, and _that's in ma Forced emulsification by means of homogenizers is required. _e

-2- 12.12.1983

62 859/11/38

Object of the invention

üb is to be described as extremely surprising that the inventive microemulsions are stable, because it was to be expected on the basis of the known prior art that such ^ emulsions, which have no thickening agent and only a small amount of surfactant, are not durable for a long time Thus, it is clear from DE-A 3 009 944 and Ι) ώ-3 011 611 that the oil-in-water emulsions described there necessarily contain a thickening agent as stabilizer. The emulsions disclosed in JP-A 122 628-77 have a very high proportion of surfactant in relation to the amount of active ingredient. The excellent stability of the microemulsions according to the invention could therefore not be foreseen.

Explanation of the essence of the invention

We have now found aqueous microemulsions which

-: 0.1 to 80 wt _# -% of at least one sparingly water-soluble agrochemical active substance, an active substance for controlling pests in the household and hygiene sector and / or a pharmacologically active substance,

- 1 to 20 wt - . % Of a Smulgatorgemisches from

a) at least one alkylaryl polyglycol ether of the formula

CX-U) - (Y) _n -H (I),

'm' 'n

-3- 12.12.1983

62 859/11/38

in which

R is alkyl having 8 to 20 carbon atoms,

X and Y are each a -CH ₂ - ₂ -GH ₂ -CH-O or -CH-CHg-O Grappe CH ₃ CH ₃

"but where I and Y are not equal

represent an oxyethylene or oxypropylene unit ^

m is from 10 to 45, and η is from 10 to 45,

at least one alkylaryl sulfonic acid salt of the formula

rL ((I) -SO- Me (II),

in which

R is alkyl of 8 to 35 carbon atoms and Me v / is an alkali metal cation, one equivalent of an alkali earth metal cation or a cation of the formula

-4-12,12,1983

62 859/11/38

R "Η · - N - R" ¹ Θ

stands in which

R ¹ , R ^M , R ^tM and R are independently hydrogen, alkyl of 1 to 4 carbon atoms or hydroxyalkyl of 1 to 4 carbon atoms

or b) at least one alkylaryl polyglycol ether of the formula

0- (CH ₂ -CH ₂ -O) - H

(III)

in which

p represents the numbers from 5 to 20 and q represents numbers from 1 to 3,

and at least one alkylarylsulfonic acid salt of the formula

12.12.1983 62 859/11/38

in which

R and Mew have the abovementioned meaning _g

- as well as water and

- 'optionally 1 to 30 Gfew * -% of at least one water-immiscible organic solvent and / or a Solubilisatora and

- if necessary 0 _? 05 to 15% by weight »- # of additives

with the sum of the components being 100% by weight, »

Furthermore, it was found that the microemulsions according to the invention can be prepared by dissolving a homogeneous mixture of

- at least one agrochemical active substance which is sparingly soluble in water, an active substance for combating pests in the household and hygiene sector and / or a pharmacologically active substance »

- A Ümulgatorgemisch

12.12.1983 62 859/11/38

a) at least one alkylaryl polyglycol ether of the formula

.O- (X) _m - (Y) _n -H

in which

R, X, Y, m and η are as defined above, and

at least one Alkylarylsulfonsäure * salt of the formula

R ¹ -

- SO,

me

(ID,

in which

R ¹ and Me © have the meaning given above, or

b) at least one alkylaryl polyglycol ether of the formula

0- (0H ₂ -CH ₂ -O) -H

(CH ₀ -

) (HD,

in which

-7- 12o12 ₀ 1983

62 859/11/38

ρ and q have the meaning given above,

and

at least one Alkvlaryl-sulfonic acid salt of the formula

SO ₂ ^w Me ^ (II),

in which

R ¹ and Mew have the meaning given above _s

optionally at least one water-immiscible organic solvent and / or a solubilizer and

- optional additives

with stirring in optionally containing additives V / asaer gives »

Finally, it was found that the erf ^ indungsgexnäßen microemulsions ") can be used based on the contained active ingredients for various purposes in agriculture and .Gartenbau in the household and hygiene sector or in the medical field _e

The microemulsions according to the invention are distinguished by a number of advantages

-8- 12.12.1983

62 859/11/38

Preparation of a costly addition of thickeners or large amounts of emulsifiers. Furthermore, these emulsions contain either no or only an extremely small amount of organic solvents. They are therefore nonflammable, free or at least virtually free from odor nuisance by organic solvents and have lower toxicity or phytotoxicity than corresponding .formulations, the organic Solvent contained in the usual concentrations. In addition, the microemulsions according to the invention are stable under the conditions prevailing in practice. "In the case of long-term storage, these emulsions remain unchanged both at temperatures of 50 ^° C. and at low temperatures." Finally, the microemulsions according to the invention can be prepared in a simple manner Forced emulsification by means of homogenizers is not required. In addition, there is a very considerable advantage that solid or liquid, sparingly soluble in water active ingredients can be equally well emulsified at room temperature »Furthermore microemulsions of the invention have a relatively low viscosity, so that a precise Dosage does not cause any difficulties. Finally, the microemulsions according to the invention are completely transparent preparations which can be easily diluted with water in any desired ratio before use, with stable, sprayed possible formulations are created «,

The microemulsions according to the invention comprise at least one agrochemically active substance which is sparingly soluble in water, an active substance for controlling pests in the household and hygiene sector and / or a pharmacologically active substance

-9- 12o12

62 859/11/38

Stoff «, These active substances are in the oil phase in the liquid state before _e

As active ingredients are both those substances in embossing, which are liquid at room temperature ₉ as well as those ₉ which are solid at room temperature "condition for liquid drugs is only that they are sparingly soluble in water." Under such substances here are substances to ver _s are soluble in water at 20 ⁰ G to a maximum of Q _S 5 per cent. In addition, most active substances must, however, be sufficiently soluble in a water-immiscible organic solvent and / or a solubilizer.

Agrochemical substances in the present case to understand all commonly used in drugs Pflanzensohuta _e These include, for example, insecticides, acaricides ^ Hematizide, fungicides, herbicides, growth regulators and fertilizer as examples of such drugs may be mentioned in detail?

0 j O-The ethyl-O- (4-nitro-phenyl) -thiono-phosphoric acid ester; 0,0-dimethyl-0- (4-nitro-phenyl) -thiono-organophosphate; 0- (ethyl) -0- (4-methylthio-phenyl) -S-propyl dithiophosphate; (0, O-Diethylthionophosphoryl) -e ^ -oximino-phenylessigsäurenitrilj

2-isopropoxyphenyl-N-methylcarbamate 3-methylthio-4-amino-6-tert-butyl-1,2,4-triazin-5-one 3-methylthio-4-isobutylideneamino-6-tert-butyl 1,2,4-triazin-5-one;

-10- 12.12.1983

62 859/11/38

2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine; 2,3-dihydro-2,2-d-imethyl-7-benzofuranylmethyl-carbamate} 3,5-dimethyl-4-niethylthiophenyl-ii-methyl-carbamate; 0,0-The thy 1-0- (3-chloro-4-methyl-7-cumarinyl) -thiophosphate;

mthane-2,3,4-benzo-dioxathiepine-3-oxide j M, 5,6,7,8,8-heptachloro-4,7-endo-methylene-3A, 4,7,7A-tetrahydroindene;

2- (2-Puryl) -benzimidazole;

5-amino-1-bis (dimethylamido) -phosphoryl-3-phenyl-1,2,4-triazole;

4-Hydroxy-3- (1,2,3,4-tetrahydro-1-naphthyl) coumarin; 3-2fT, 2-Bia (etiioxycarbonyl) -ethyl7-0,0-dimethyl-dithiophosphoric acid esters;

0,0-dimethyl-0- (4-methylmercapto-3-methyl-phenyl) -thionophoaphorsäureester;

0- ^ thyi-0- (2-isopropyloxyoarbonyl-phenyl) -lJ-isopropylthionophoaplioraäureesteramid;

1- (4-chlorophenoxy) -3,3-dimethyl-1 (i, 2,4-triazol-1-yl) -2-butanone;

(S) -OC-cyano-3-phenoxybenzyl (1H) -cic-3- (2,2-dibromovinyl) - 2, 2-dimethylcyclopropanecarboxylate;

2,2-Dimethyl-3- (β-β-dichlorovinyl) -cyclopropanecarboxylic acid cyano-3-phenoxy-4-fluoro-benzyl ester.

Active ingredients for combating pests in the household and hygiene sector are to be understood in the present case as meaning all active substances which are sparingly soluble in water and which are suitable for such indications. As examples of such agents may be mentioned in detail!

2-isopropoxyphenyl-N-methylcarbamate;

-11 »12.12.1983

62 859/11/38

0,0-Diethyl-O- (4-nitro-phenyl) -tiaionophosphoric acid ester O, O-dimethyl-O- (4-nitrophenyl) -thionophosphoric acid ester

phosphorsäureester5

0.0-dimethyl-0-3-never methyl-4-hydroxyphenyl) -thionophosphoric acid ester;

0, O-dimethyl-O- (4-methyl-mercapto-3-methylphenyl) -thionoplioic acid ester; ^ - "hexachlorocyclohexane;

(Gy clohex-1-ene-1, α-dicarboximiclomethyl) -2,2-dimethyiyl-3- (2-methylpropenyl) cyclopropanecarboxylate

Pharmacologically active substances are to be understood in the present case preferably in the veterinary field applicable j water-sparingly soluble substances. As an example of such active substances may be called «

2,2 ~ Dimethyl-3-Zβ "(p- * chlorophenyl) -β-chlorovinyl-7-cyclopropanecarboxylic acid ~ 5-cyano-3-phenoxy-4-fluoro-benzyl ester.

The iimulgator mixtures contained in the microemulsions according to the invention consist either of at least one alkylaryl polyglycol ether of the formula (I) and of at least one alkylaryl sulphonic acid salt of the formula (II) or of at least one alkylaryl polyglycol ether of the formula (III) and at least one alkylarylsulphonic acid Salt of the formula (II).

The alkylaryl polyglycol ethers of the formula (I) are generally defined by the formula given. In this formula, R is preferably alkyl having 10 to 18 carbon atoms. »

-12- 12.12.1983

62 859/11/38

X and Y are each a -GH ₀ -GH ₀ -O-, -CH ₀ -CH-O-

d. C d%

CH ₃

or -CH-CH ₀ -O-group, but wherein X and Y are not at the same

time for an oxyethylene or oxypropylene unit. The index m preferably represents the numbers from 12 to 30 »and the index η preferably represents numbers from 12 to 40. The numbers for the indices m and η represent average values.

The emulsifiers of this type used in practice are generally mixtures of several compounds of the formula (I). In particular, these are mixtures of substances of the formula (I), which are characterized by the number of oxyethylene or oxypropylene units differ. As a result, fractions are also calculated as mean values for the indices m and η. Examples include substances which give the following average compositions:

0 (CH ₂ -CHO) ₂₀ - (CH ₂ -CH ₂ O) ₃₀ -H CH ₃

O (CH-CH ₂ O-) ₂₇ 5-

CH ₃

C ₉ H ₁₉ '' ^CH 3

O- (CH ₂ -CHO) ₂₄ - (CH ₂ -CH ₂ O) ₃₆ -

12.12.1983 62 859/11/38

CH ₃

CH ₃

, -O- (CH ₂ -CH ₂ O) ₂₇ - (CH ₂ -CHO) ₂₇ -H

CH ₃

The alkylaryl polyglycol ethers of the formula (I) are known.

The alkylaryl-sulphonic acid salts contained in the microemulsions according to the invention are generally defined by the formula (II). In this formula, R preferably represents straight-chain or branched alkyl having 9 to 30 carbon atoms. Me ® is preferably a sodium cation, one equivalent of an Caloiumkations or a cation of the formula

R "

H · -M - E ¹ ",

R ¹ , R ", R" ¹ and R are independently preferably

are hydrogen, alkyl having 1 or 2 carbon atoms or hydroxyalkyl having 1 to 2 carbon atoms *

-14- 12.12.1983

62 859/11/38

Specific examples of alkylaryl-sulfonic acid salts of the formula (II) are:

4- (n-nonyl) ~ phenyl-sulfonic acid liatriumsalz; 4- (n-dodecyl) -phenyl-sulfonic acid calcium salt; 4- (tetrapropylene) -phenyl-sulfonic acid sodium salt; 4- (n-Uonyl) -phenyl-sulfonic acid-Galciumsalz} 4- (i-dodecyl) -phenyl-sulfonic acid ammonium salt; 4- (n-Dodexyl) -phenyl-sulfonic acid (2-hydroxyethyl) ammonium salt.

The alkylaryl-sulfonic acid salts of the formula (II) are known. They are generally referred to as 50 to 75% solutions in organic solvents, ζ. B, η- or i-butanol or Benzylalkoholι used, but in principle can also be used without solvent.

The alkylaryl polyglycol ethers of the formula (III) are generally defined by the formula given. In this formula, the index ρ preferably represents numbers from 8 to 18, and the index q preferably represents numbers from 1 to 2. The numbers for the indices ρ and q represent average values.

The emulsifiers of this type used in practice are generally mixtures of several compounds of the formula (III). In particular, these are mixtures of substances of the formula (III), which differ by the number of oxyethylene units or by the degree of substitution on the phenyl radical. As a result, broken numbers can also be calculated as mean values for the indices ρ and q. For example, mention may be made of substances for themselves

12.12.1983 62 859/11/38

the following average compositions give:

1.35

0- (CH ₂ -CH ₂ -O) ₁₂ -H

The alkylaryl polyglycol ethers of the formula (III) are likewise known.

As organic solvents which may optionally be contained in the microemulsions according to the invention. All common, water-immiscible organic oil solvents come into question. Preferably mentioned are aromatic hydrocarbons such as xylene, toluene and dimethylnaphthalene, further chlorinated aromatic hydrocarbons such as chlorobenzenes, also aliphatic ^ hydrocarbons such as gasoline and petroleum ether, furthermore halogenated aliphatic hydrocarbons such as methylene chloride and chloroform, moreover cycloaliphatic

-16- 12.12.1983

62 859/11/38

Hydrocarbons, such as cyclohexane, also alcohols and ketones, such as n-butanol, n-hexanol, iso-hexanol, n-octanol, cyclohexanol, benzyl alcohol, di-n-butyl ketone and isophorone, and further üther and iist.er, such as Glycol monomethyl ether and glycol monoethyl ethyl ether acetate and also triethyl phosphato

Suitable solubilizers which may be present in the microemulsions according to the invention are all customary solubilizers. "Preferably usable are alkylphenols or cresols which are condensed per mole with 1 to 8 moles of ethylene oxide." In this context, p-krool, which is per Mol is condensed with 1 to 8 moles of ethylene oxide.

As additives which may optionally be present in the microemulsions according to the invention, preservatives, dyes, cold stabilizers and synergists are suitable,

Examples of preservatives are 2-hydroxybiphenyl and sorbic acid. Examples of dyes include azo dyes and phthalocyanine dyes. Examples of cold stabilizers include urea, sugars and salts, such as ammonium sulfate and sodium oleate. An example of a synergist is 3,4-methylenedioxy-6-propyl-benzyl-n-butyl-diethylene glycol ether (piperonyl butoxide).

In the microemulsions according to the invention, the percentage proportions of the components contained within certain

-17- 12.12.1983

62 859/38/11.

Ranges are varied. The proportion of active ingredient or active ingredients is generally between 0.1 and 80% by weight, preferably between 5 and 80% by weight. The proportion of J & aulgator-Gemiach is generally from 1 to 20 percent by _e -%, preferably 3 to 16 wt% _e ~, wherein the ratio of ^ mulgato.ren each other can likewise be varied within a certain range. In general, accounted for 1 part of iimulgator of the formula (I) 0.2 to 1.2, preferably 0.4 to 1 part of Jimulgator of formula (II), Further accounts for 1 part Jiimulgator of formula (III) in general 0 , 1 to 1.2 parts, preferably 0.2 to 1.0 parts of Jimulgator of formula (II).

Water-immiscible organic solvents and / or solubilizers can be present in proportions of from 1 to 30% by weight, preferably from 5 to 20% by weight. Additives can be present in proportions of from 0.05 to 15% by weight, preferably

0.1 to 10 wt _e - $ be included. The percentage of water in the microemulsions according to the invention is calculated in each case as the difference between 100% by weight and the sum of the percentages of the other components.

In the microemulsions according to the invention, the ratio of active ingredient (s), optionally in admixture with organic dolvents and / or solubilizers, may be varied on the one hand to form a mixture of emulsifiers, and on the other hand within a certain range. In general, for every 1 part -binulgatorgemisch 1 to 15 weight parts by _e, preferably 2 to 10 parts by weight of active ingredient (s), optionally in admixture with organic solvents and / or solubilizers "

-18- 12.12.1983

62 859/11/38

In the case of the preparation of the microemulsions according to the invention, it is possible with preference to use all those components which have already been mentioned as preferred in connection with the description of the microemulsions according to the invention.

Is used in the inventive method a Varkstoff which up to 40 ⁰ G in the liquid state at temperatures, so the addition of a little water-miscible organic solvent and / or a solubilizer is in general unnecessary ·

On the other hand are used in the inventive method an active ingredient, present at temperatures up to 40 ⁰ C in the solid state, so it is necessary to dissolve the active substance before the ümulgierung in a little water miscible organic solvent and / or solubilizer. The amount of organic Sovens and / or solubilizer is calculated so that it was just sufficient for the solution of the solid substance

The reaction temperatures can be varied within a substantial range in the process according to the invention. In general, one works at temperatures between 10 ⁰ C and 80 ⁰ G, preferably between 20 ⁰ C and 60 ⁰ C.

In carrying out the method according to the invention is generally carried out so that first a homogeneous solution of one or more active ingredients ümulgat or mixture, optionally water-immiscible organic solvent and / or solubilizer and optionally additives and this mixture is then stirred

-19- 12 * 12.1983

62 859 / .11 / 38

in optionally containing additives water "The amounts of the components are chosen so that the components are present in the resulting microemulsion in the particular desired concentration," The order in which the components of the organic phase are combined, is variable The addition of organic Phase to the aqueous phase is advantageously carried out slowly with uniform stirring with conventional stirring equipment, this forms a finely divided, transparent microemulsion, which optically no longer differs from a solution ·

The microemulsions according to the invention can be applied either in the prepared form or after prior dilution. The application rate depends on the concentration of the active ingredients in the microemulsion and on the respective indication,

The application of the microemulsions according to the invention is carried out by the customary methods, for example by spraying, spraying or pouring.

The preparation of the microemulsions according to the invention is evident from the following examples.

Production Examples Example 1

70 g of the insecticidal active ingredient 0.0-Dimethy1-0- (4-methylmercapto-3-3iethyl-phenyl) -thionophosphorsäureester are added with stirring at temperatures between 20 ⁰ G and 40 ⁰ G with 8 g of a Ümulgator mixture that

-20- 12.12.1983

62 859/11/38

- consists of 6 parts by weight of an ionylphenol polyglycol ether having an average of 27 oxyethylene and 27 oxypropylene units per molecule,

- 4 parts by weight of em 4- (n-dodecyl) phenyl sulfonic acid calcium salt (dissolved in n-butanol)

consists. The resulting homogeneous solution is added within 2 minutes with vigorous stirring in 22 g of demineralized water. After completion of the addition, stirring is continued for 5 minutes. Jis forms a transparent microemulsion which showed no physical or chemical changes even after storage for several weeks at elevated temperature

Example 2

50 g of 0.0-dimethyl-O- (4-methylmercapto-3-niethyl-phenyl) -thionophosphorsäureester are added with stirring at temperatures between 20 and 40 ⁰ C with 14.0 g einea ininggatorgemisches, the

- consists of 10 parts by weight of an alkylaryl polyglycol ether, the average composition of which is given by the following formula:

-21- 12.12.1933

62 859/11/38

to 4 parts by weight of the 4- (n-dodecyl) -phenylsulfonic acid calcium salt (dissolved in n-butanol)

The resulting homogeneous solution is added within 2 minutes with vigorous stirring in 36 g of demineralized water After completed addition is stirred for 5 minutes <> i) s' forms a transparent microemulsion, even after weeks of storage at elevated temperature no physical or chemical changes shows.

Claims (3)

-22- 12.12.1983 62 859/11/38 Claim for invention - 1 to 20% by weight of a mixture of emulsifiers a) at least one alkylaryl polyglycol ether of the formula in which R is alkyl of 8 to 20 carbon atoms, X and Ϊ are each a ₂₂ CH ₀ -CH-O- or -CH-CHo-O-group CH ₃ CH ₃ but X and Ϊ are not simultaneously an oxyethylene or oxypropylene unit, m stands for numbers from 10 to 45 and η stands for numbers from 10 to 45 and -23- 12/12/1983 62 859/11/38 at least one Alkylarylaulfonaäure salt of Pormel RVi) N-SO ₃ Me in which R ^{1 is} alkyl having 8 to 35 carbon atoms and 'for an alkali metal cation, one equivalent of a kalkalkalimetallkations or for a cation of the formula R "
£ i «- N - R ¹¹¹ ® in which IV
R ¹ , R ", R" ¹ and R independently of one another Are hydrogen, alkyl of 1 to 4 carbon atoms or hydroxyalkyl of 1 to 4 carbon atoms, or b) at least one alkylaryl polyglycol ether of the formula -24- 12.12.1983 62 859/11/38 0- (CH ₂ -GH ₂ -O) -H in which ρ stands for the numbers from 5 to 20 and q stands for numbers from 1 to 3, and at least one alkylarylsulfonic acid salt of the formula _(ΙΙ) in which R and Me © have the abovementioned meaning, - as well as water and - if appropriate, 1 to 30 percent by _e -% of at least one slightly water-miscible organic solvent and / or a solubilizer and -25 »12.12.1983 62 859/11/38 optionally 0.05 to 15% by weight of additives, wherein the sum of components each 100 wt _o - is #. 1. Aqueous microemulsions, characterized by a content of 0.1 to 80% by weight of at least one agrochemically active compound which is sparingly soluble in water, an active substance for controlling pests in the household and hygiene sector and / or a pharmacologically active substance, 2. A process for the preparation of aqueous microemulsions according to item 1, characterized in that one comprises a homogeneous mixture at least one agrochemically active substance which is sparingly soluble in water, an active substance for controlling pests in the household and hygiene sector and / or a pharmacologically active substance, - an emulsifier mixture a) at least one alkylaryl polyglycol ether of the formula 0- (X) _n - (Y) _n -H (I), in which R, X ₉ ¥, m and η are as defined above, and at least one alkylarylsulfonic acid salt of the formula 12.12.1983 62 859/11/38 R ^l -I ( >) - SO ₂ Me (ID, in which R 'and Me vt> have the abovementioned meaning, or b) at least one alkylaryl polyglycol ether of the formula P- (CH ₂ -CH ₂ -O) _p -H in which ρ and q have the abovementioned meaning and at least one alkylaryl-sulfonic acid salt of the formula -27- 12ο12ο1983 62 859/11/38 Me (II), in which R and MeO have the abovementioned meaning, optionally at least one water-immiscible organic solvent and / or a solubilizer and optionally additives with stirring in optionally containing additives water, 3. Use of aqueous microemulsions according to item 1, characterized in that they are used in agriculture and horticulture, in the household and hygiene sector and / or in the medical field »