Composition comprising active ingredient, oil and ionic liquid

Abstract

The present invention relates to a liquid composition comprising A) an organic active ingredient which is sparingly water-soluble and sparingly oil-soluble, in dissolved form, B) an oil which is soluble in water at 20 C. to at most 20 g/l, and C) an ionic liquid comprising a cation and an anion as described below. Also provided is a process for the preparation of the liquid composition, where the active ingredient, the oil and the ionic liquid are brought into contact; and also the use of the ionic liquid for increasing the solubility of the active ingredient in an oil.

Claims

1. A liquid composition comprising: A) an organic active ingredient in dissolved form, which is soluble in water at 20 C. to at most 10 g/l and is soluble in di butyl adipate at 20 C. to at most 10% by weight, wherein the active ingredient is a UV absorber selected from the group consisting of 2-(4-methoxyphenyl)-4,6-bis(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-[4-(2-methoxyethylcarboxyl)phenylarmino]-1,3,5 -triazine, 2,4-bis{[4-(tris(trimethylsiloxysilylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyI)-1,3,5-triazine, 2,4-bis{[4-(2methylpropenyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis{[4-( 1,1,1,3,5,5 ,5-heptamethyltrisilyl-2-methylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis{[4-(3 -(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-[4-ethylcarboxyl)phenylamino]-1,3,5-triazine, bis-ethylhexyloxyphenol methoxyphenyltriazine, tris-biphenyltriazine, and 2,4,6-trianilino-(p-carbo-2-ethylhexyl-1-oxy)-1,3,5-triazine; B) an oil that is soluble in water at 20 C. to at most 20 g/l, the oil selected from an aromatic hydrocarbon, an alkyl alkanoate, a fatty acid amide, or a dialkyl ester of an alkyldioic acid; and C) an ionic liquid comprising a cation and an anion, where the cation is selected from: an ammonium of the formula (I)
N.sup.+R.sup.1R.sup.2R.sup.3 R.sup.4(I) and R.sup.1, R.sup.2, R.sup.3 and R.sup.4, independently of one another, are C.sub.1-C.sub.20 alkyl or C.sub.1-C.sub.20 hydroxyalkyl; or an imidazolium of the formula (II) ##STR00006## and R.sup.5 is hydrogen or C.sub.1-C.sub.20 alkyl, R.sup.6 is C.sub.1-C.sub.20 alkyl, and R.sup.7 is C.sub.1-C.sub.20 alkyl.

2. The composition according to claim 1, where the cation is the imidazolium of the formula (II), and R.sup.5 is hydrogen or C.sub.1-C.sub.6 alkyl, R.sup.6 is C.sub.1-C.sub.6 alkyl, and R.sup.7 is hydrogen, and the anion is an alkyl carboxylate, polyether-containing carboxylate, or alkysulfonate.

3. The composition according to claim 1, where a weight ratio of the oil to the ionic liquid is in the range from 50:1 to 3:1, and the concentration of the UV absorber is from 1% to 10% by weight.

4. The composition according to claim 1, where the cation is the ammonium of the formula (I), and the anion is an alkyl carboxylate, polyether-containing carboxylate, or alkylsulfonate.

5. The composition according to claim 1, further comprising from 1 to 25% by weight of at least one surfactant.

6. The composition according to claim 5, where the surfactant comprises at least one nonionic surfactant selected from alkoxylates and optionally an anionic surfactant selected from sulfates.

7. The composition according to claim 1, where the anion is selected from a carboxylate, sulfonate, sulfate, phosphonate, phosphate, halogen, bis(trifluorosulfonyl)imide, aluminum tetrachloride, phosphorus fluoride, or dicyanimide.

8. The composition according to claim 1, where the anion is an alkyl carboxylate, polyether-containing carboxylate, or alkylsulfonate.

9. The composition according to claim 1, where the composition is a solution or dispersion, and comprises at most 5% by weight of water.

10. The composition according to claim 1, where the composition is a dispersion and comprises at least 5% by weight of water.

11. The composition according to claim 1, where the composition is a cosmetic.

12. The composition according to claim 1, where the active ingredient is soluble in water at 20 C. to at most 3 g/l and is soluble in dibutyl adipate at 20 C. to at most 3% by weight.

13. The composition according to claim 12, where the oil is soluble in water at 20 C. to at most 5 g/l.

14. The composition according to claim 11, where the oil is an ester or amide of a vegetable oil selected from the group consisting of rapeseed oil, soya oil, palm oil, sunflower oil, corn seed oil, linseed oil, colza oil, olive oil, cottonseed oil, rapeseed oil methyl ester, rapeseed oil ethyl ester, colza oil methyl ester, colza oil ethyl ester, almond oil, jojoba oil, orange oil, wheat germ oil, peach kernel oil, the liquid fractions of coconut oil, and any one mixture mixtures thereof.

15. The composition according to claim 1, where the ionic liquid has a melting point less than 30 C.

16. The composition according to claim 15, wherein, R.sup.1, R.sup.2, R.sup.3 and R.sup.4, are independently of one another selected from C.sub.1-C.sub.8 alkyl or C.sub.1-C.sub.8 hydroxyalkyl.

17. The composition according to claim 3, wherein the UV absorber is selected from 2,4,6-trianilino-p-(carbo-2-ethylhexyl-1-oxy)-1,3,5-triazine or bis-ethylhexyloxyphenol methoxyphenyl triazine.

Description

EXAMPLES

(1) Cetiol B: Cosmetic oil of bibutyl adipate, commercially available from BASF SE. Fluxapyroxad: Fungicide, 3-(difluoromethyl)-1-methyl-N-(3,4,5-trifluorobiphenyl-2-yl)pyrazole-4-carboxamide. Uvinul T150: 2,4,6-trianilino-p-(carbo-2-ethylhexyl-1-oxy)-1,3,5-triazine; CAS No. 88122-99-0, commercially available from BASF SE. Tinosorb S: bis-ethylhexyloxyphenol methoxyphenyl triazine (also known as bemotrizinol). Surf A: Ethoxylated Castor oil (40 EO) Surf B: Polyoxyl 40 Hydrogenated Castor Oil Surf C: Ethoxylated Tristyrylphenols Surf D: Ethoxylated Polyarylphenolsulphate Ammonium Salz Surf E: C10-Guerbet-alcohol Ethoxy-late (7 EO) Surf F: C10-Guerbet-alcohol Ethoxylate (3 EO) Surf G C13C15-oxoalcohol Ethoxylat (3 EO) Surf H: iso C12Alkylbenzene sulfonate Ca salt Surf I: C13-Oxoalkohol-ethoxylate (+3EO) Surf J: C13-Oxoalkohol-ethoxylate (+7EO) Surf K: C13-Oxoalkohol-ethoxylate (+10EO) Surf L: C13-Oxoalkohol-ethoxylate (+12EO) Surf M: C10C18-Alkohol-ethoxylate (+5EO)

Example 1

Increased Solubility of Agrochemical Active Ingredient

(2) The solubility was tested at 21 C. For this, increasing amounts of active ingredient were added stepwise to oil (Cetiol B or Solvesso), which comprised the ionic liquid, until the maximum solubility was reached. Alternatively, the oil, which comprised the ionic liquid, was saturated with the active ingredient and the soluble fraction of active ingredient was quantified by means of HPLC.

(3) The results are summarized in tables 1 to 3. In the first line of the tables, in each case the weight ratios of oil to IL are given.

(4) TABLE-US-00001 TABLE 1 Solubility [g/l] of fluxapyroxad with Cetiol B as oil. 100 90/10 80/20 60/40 20/80 100 Ionic liquid (IL) Oil Oil/IL Oil/IL Oil/IL Oil/IL IL Tetrabutylammonium 3.0 15.3 35.5 45.9 5.0 octadecanoate N-ethyl-N-methylimidazolium 3.0 20.7 46.7 48.7 9.5 isononanoate Tetrabutylammonium [2-(2- 3.0 16 27.5 40.8 38.3 9.5 methoxyethoxy)ethoxy]acetate N-butyl-N-methylimidazolium 3.0 23.7 50.6 54.9 42.4 acetate N-ethyl-N-methylimidazolium 3.0 25.6 54.9 56.2 47.2 acetate N-ethyl-N-ethylimidazolium 3.0 24.2 50.8 60.2 45.7 propionate N-butyl-N-methylimidazolium 3.0 29 43.1 44.1 5 dimethylphosphate N-ethyl-N-methylimidazolium 3.0 31.1 46.0 16.8 9.5 dibutylphosphate N-ethyl-N-methylimidazolium 3.0 35.9 50 28.4 26.9 heptanoate N-ethyl-N-methylimidazolium 3.0 34.3 49.5 25.7 20.8 octanoate N-propyl-N-propylimidazolium 3.0 35.4 49.6 59.2 36.7 acetate Cholinium octanoate 3.0 20.8 33.6 34.2 5

(5) TABLE-US-00002 TABLE 2 Solubility [g/l] of fluxapyroxad with Solvesso 200 ND as oil 100 90/10 60/40 20/80 100 Ionic liquid (IL) Oil Oil/IL Oil/IL Oil/IL IL Tetrabutylammonium 1.5 14.5 33.3 35.5 5 octadecanoate N-ethyl-N- 1.5 15.3 42.9 28.6 9.5 methylimidazolium isononanoate Tetrabutylammonium [2-(2- 1.5 18.4 9.5 methoxyethoxy)ethoxy] acetate N-ethyl-N-ethylimidazolium 1.5 21.3 50.5 39.4 45.7 propionate

(6) TABLE-US-00003 TABLE 3 Solubility [g/l] of fluxapyroxad with Agnique AMD 12 (N,N-dimethyldodecanamide, lauryl N,N-dimethylamide) as oil 100 90/10 60/40 20/80 100 Ionic liquid (IL) Oil Oil/IL Oil/IL Oil/IL IL Tetrabutylammonium 21.0 25.9 39.1 40.7 5 octadecanoate N-ethyl-N- 21.0 32 48.1 38.4 9.5 methylimidazolium isononanoate N-butyl-N- 21.0 36 55.9 43.1 1 methylimidazolium acetate N-ethyl-N- 21.0 38.2 40.4 39.5 1 methylimidazolium acetate Tetrabutylammonium [2-(2- 21.0 29.7 33.1 37.5 9.5 methoxyethoxy)ethoxy]acetate

Example 2

Increased Solubility of UV Absorber

(7) The solubilities were determined as in example 1 and the results were summarized in table 4 and 5.

(8) TABLE-US-00004 TABLE 4 Solubility [g/l] of Uvinul T150 with Cetiol B as oil 100 90/10 60/40 20/80 100 Ionic liquid (IL) Oil Oil/IL Oil/IL Oil/IL IL Tetrabutylammonium 14.2 28.6 39.4 1 octadecanoate N-ethyl-N- 14.2 32.4 45.7 34.8 1 methylimidazolium isononanoate N-butyl-N- 14.2 37.5 54.1 41.5 5 methylimidazolium acetate N-ethyl-N- 14.2 37.5 52.8 40.8 1 methylimidazolium acetate N-ethyl-N-ethylimidazolium 14.2 33.3 54.3 44.1 5 propionate Cholinium [2-(2- 14.2 21.3 1 methoxyethoxy)ethoxy]acetate

(9) TABLE-US-00005 TABLE 5 Solubility [g/l] of Tinosorb S with Cetiol B as oil 100 90/10 60/40 20/80 100 Ionic liquid (IL) Oil Oil/IL Oil/IL Oil/IL IL N-ethyl-N- 6.2 13.8 22.4 19.2 9.5 methylimidazolium isononanoate N-butyl-N- 6.2 11.7 14.3 12.4 1 methylimidazolium acetate N-ethyl-N-ethylimidazolium 6.2 13 21.9 1 heptanoate N-ethyl-N-ethylimidazolium 6.2 13 21.9 16.7 1 octanoate

Example 3

Aqueous Dilutions

(10) A mixture of 8 wt % N-butyl-N-methylimidazolium (BMIM) acetat, 20 wt % Fluxapyroxad, 72 wt % Cetiol B, and the surfactant as listed in the Table 6 were prepared. The mixture was diluted at room temperature with water in a weight ratio of 1 part of the mixture to 100 parts water yielding a homogenous dispersion.

(11) TABLE-US-00006 TABLE 6 composition of mixtures (in wt %) Surfactant 1 Conc. 1 Surfactant 2 Conc. 2 Surfactant 3 Conc. 3 Surf A 8 Surf A 3.8 Surf I 10.4 Surf A 4.2 Surf I 10.4 Surf E 2.5 Surf A 3.8 Surf F 10.5 Surf A 3.8 Surf G 10.5 Surf B 6 Surf I 8.3 Surf C 5.9 Surf H 8.2 Surf C 5.8 Surf H 8.4 Surf E 2.7 Surf D 12.7 Surf I 4.4 Surf D 8.1 Surf I 8.4 Surf D 4 Surf I 12.6

(12) TABLE-US-00007 TABLE 7 Composition of mixtures (in wt %) Surfactant 1 Conc. 1 Surfactant 2 Conc. 2 Ratio Surf A 4.1 Surf I 10.2 2.5 Surf A 5.2 Surf I 10.6 2 Surf A 8.1 Surf I 8 1 Surf A 10.4 Surf I 5.4 0.5 Surf A 10.7 Surf I 4.5 0.4

(13) TABLE-US-00008 TABLE 8 Composition of mixtures (in wt %) Surfactant 1 Conc. 1 Surfactant 2 Conc. 2 Surfactant 3 Conc. 3 Surf A 4.7 Surf I 12.4 Surf E 3 Surf A 4.5 Surf I 10.6 Surf E 3.6 Surf A 4.6 Surf I 10.4 Surf E 4.9 Surf A 4.5 Surf I 10.3 Surf E 5.9

(14) TABLE-US-00009 TABLE 9 Composition of mixtures (in wt %) Surfactant 1 Conc. 1 Surfactant 2 Conc. 2 Surfactant 3 Conc. 3 Surf A 4.7 Surf I 12.4 Surf E 3 Surf A 4.3 Surf I 10.5 Lutensol TO7 3.2 Surf A 4.5 Surf I 10.6 Surf K 3.3 Surf A 4.2 Surf I 10.2 Surf L 3.4 Surf A 4 Surf I 10.2 Surf M 3.4

Example 4

Aqueous Dilutions

(15) A mixture of 9 wt % cholinium octanoate, 10 wt % Fluxapyroxad, 81 wt % Cetiol B, and the surfactant as listed in the Table 6 were prepared. The mixture was diluted at room temperature with water in a weight ratio of 1 part of the mixture to 100 parts water yielding a homogenous dispersion.

(16) TABLE-US-00010 TABLE 10 Composition of mixtures (in wt %) Surfactant 1 Conc. 1 Surfactant 2 Conc. 2 Surfactant 3 Conc. 3 Surf A 4.4 Surf I 10.7 Surf A 4.2 Surf I 10.5 Surf E 1.8 Surf D 12 Surf I 4 Surf D 12 Surf I 4 Surf E 3

Example 5

Aqueous Dilutions

(17) A mixture of 8.5 wt % N-ethyl-N-methylimidazolium (EMIM) acetate, 15 wt % Fluxapyroxad, 76.5 wt % Cetiol B, and the surfactant as listed in the Table 6 were prepared. The mixture was diluted at room temperature with water in a weight ratio of 1 part of the mixture to 100 parts water yielding a homogenous dispersion.

(18) TABLE-US-00011 TABLE 11 Composition of mixtures (in wt %) Surfactant 1 Conc. 1 Surfactant 2 Conc. 2 Surfactant 3 Conc. 3 Surf A 4.4 Surf I 10.7 Surf A 4.2 Surf I 10.6 Surf E 2 Surf D 12 Surf I 4 Surf D 12 Surf I 4 Surf E 3

Example 6

Aqueous Dilutions

(19) A mixture of 8 wt % N-ethyl-N-methylimidazolium (EMIM) octanoate, 20 wt % Fluxapyroxad, 72 wt % Cetiol B, and the surfactant as listed in the Table 6 were prepared. The mixture was diluted at room temperature with water in a weight ratio of 1 part of the mixture to 100 parts water yielding a homogenous dispersion.

(20) TABLE-US-00012 TABLE 12 Composition of mixtures (in wt %) Surfactant 1 Conc. 1 Surfactant 2 Conc. 2 Surfactant 3 Conc. 3 Surf A 4.3 Surf I 10.6 Surf A 4.3 Surf I 10.4 Surf E 2 Surf D 12 Surf I 4 Surf D 12 Surf I 4 Surf E 3