Process For The Co-Encapsulation Of Biocidally Active Compounds In Clay Minerals Functionalized By Nitrogen Compounds

Abstract

This invention relates to a process for the co-encapsulation of biocidally active ingredients in a clay mineral, the process comprising the step of bringing the clay mineral into contact with a biocidally active nitrogen compound that contains at least one hydrocarbon group with 6 to 20 carbon atoms, and at the same time or subsequently with at least one biocidally active compound selected from the group consisting of 2-n-octyl-4-isothiazoline-3-one, 3-iodopropenylbutyl-carbamate and tetrahis(hydroxymethyl)phosphonium sulfate. And the use of such encapsulated product in water based paints, coatings and varnishes.

1 .- 16 . (canceled) 
     
     
         17 . A biocidally active clay mineral comprising biocidally active nitrogen compound having at least one hydrocarbon group with 6 to 20 carbon atoms and at least one of 2-n-octyl-4-isothiazoline-3-one (OIT), 3-iodopropenylbutylcarbamate (IPBC) and tetrakis(hydroxymethyl)phosphonium-sulfate (THPS) encapsulated in a clay mineral. 
     
     
         18 . A water based paint, coating or varnish, comprising a biocidally active clay mineral, prepared by bringing a clay mineral into contact with a biocidally active nitrogen compound that contains at least one hydrocarbon group with 6 to 20 carbon atoms, and at the same time or subsequently bringing the clay mineral into contact with at least one biocidally active compound selected from the group consisting of 2-n-octyl-4-isothiazoline-3-one (OIT), 3-iodopropenylbutylcarbamate (IPBC) and tetrakis(hydroxymethyl)phosphonium-sulfate (THPS). 
     
     
         19 . (canceled) 
     
     
         20 . The biocidally active clay mineral according to  claim 17 , wherein the clay mineral further comprises at least one smectite group mineral in a concentration ranging between 60-95 wt.-%, relative to the total weight of the clay mineral. 
     
     
         21 . The biocidally active clay mineral according to  claim 17 , wherein the biocidally active nitrogen compound is a quaternary ammonium compound according to the formula
   [R 1 R 2 R 3 R 4 N] + X −   (1)
   wherein   R 1 , R 2 , R 3 , and R 4  independently are linear, branched, cyclic, saturated or unsaturated hydrocarbon groups containing between 1 and 30 carbon atoms, and   X is an anion,   with the proviso that at least one of R 1 , R 2 , R 3  and R 4  contains at least 6 and at most 20 carbon atoms.   
     
     
         22 . The biocidally active clay mineral according to  claim 21 , wherein the sum of the number of carbon atoms in R 1 , R 2 , R 3 , and R 4  ranges from 9 to 30. 
     
     
         23 . The biocidally active clay mineral according to  claim 17 , wherein the biocidally active nitrogen compound is an alkylamine of the formula
   [R 1 R 2 R 3 N]  (7)
   wherein R 1 , R 2  and R 3  independently are hydrogen, linear or branched C 6 -C 20  saturated or unsaturated hydrocarbon groups.   
     
     
         24 . The biocidally active clay mineral according to  claim 17 , wherein the biocidally active nitrogen compound is an etheramine of the formula 
       
         
           
           
               
               
           
         
         or an etheramine salt corresponding to of the formula 
       
       
         
           
           
               
               
           
         
         wherein 
         R 1  is (C 2 -C 30 )-alkyl or C 5 - to C 12 -cycloalkyl, 
         R 2  is H, CH 3 , CH 2 CH 3  or (CH 2 ) 2 CH 3 , 
         n is 1, 2, 3, 4 or 5, and 
         X is an anion such that the etheramine is water soluble. 
       
     
     
         25 . The biocidally active clay mineral according to  claim 17 , wherein the biocidally active nitrogen compound is an ether diamine of the formula 
       
         
           
           
               
               
           
         
         or an etherdiamine salt of the formula 
       
       
         
           
           
               
               
           
         
         wherein for both formula 10a and 10b 
         R 1  is (C 2 -C 30 )-alkyl or C 5 - to C 12 -cycloalkyl; 
         R 2 , R 3  are H, CH 3 , CH 2 CH 3  or (CH 2 ) 2 CH 3 , 
         n, o are 1, 2, 3, 4 or 5 and 
         X is an anion such that the etheramine compound is water soluble. 
       
     
     
         26 . The biocidally active clay mineral according to  claim 17 , wherein the biocidally active nitrogen compound is a sternamine of the formula 
       
         
           
           
               
               
           
         
         wherein 
         R 1  is (C 2 -C 30 )-alkyl or C 5 - to C 12 -cycloalkyl; 
         R 5  corresponds to the formula 
       
       
         
           
           
               
               
           
         
         R 2 , R 3 , R 4 , R 6  are H, CH 3 , CH 2 CH 3  or (CH 2 ) 2 CH 3 , 
         n, o, p, q are 1, 2, 3, 4 or 5, 
         or a salt obtainable from the compounds of formula 11 by protonation of the free NH 2  groups. 
       
     
     
         26 . The biocidally active clay mineral according to  claim 17 , further comprising a further biocidally active compound, into contact with the clay mineral, wherein the further biocidally active compound is selected from the group consisting of Ethanol, 1-Propanol, 2-Propanol, 1,2-Propanediol, 2-Phenoxyethanol, 1-Phenoxypropanol, Formaldehyde, Glutaraldehyde, Acetaldehyde, Glyoxal, Ethylene Glycol hemiformal, Ethylene Glycol bishemiformal, 1,3-dioxolane, 3,3′-Methylenebis(5-methyl-1,3-oxazolidine), Hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, Hexahydro-1,3,5-tris(2-hydroxypropyl)-s-triazine, Bis(tetrakis(hydroxymethyl)phosphonium)sulfate, 1,3-Bis(hydroxymethyl)5,5-dimethyl-2,4-dioxoimidazolidine), 6-Acetoxy-2,4-dimethyl-1,3-dioxane, 2,5-Dimethoxytetrahydrofuran, Phenol, Chloromethylphenol, 4-Chlorophenol, Formic acid, Acetic acid, sorbic acid, benzoic acid, boric acid, Ethyl formate, Benzyl bromoacetate, dimethyl dicarbonate, N′-(3,4-dichlorophenyl)-N,N-dimethylurea, N′-(4-chlorophenyl)-N′-(3,4-dichlorophenyl)urea), 3-lodopropynylphenylcarbamate, 3-lodopropynylcarbamate, Methyl-N-(2-benzimidazolyl)carbamate, 4,4′-Diamidinophenoxypropane, 4,4′-Diamidino-2,2′-dibromodiphenoxypropane, Pyridine-N-oxides, 8-Quinolinol, 1-[2-(2,4-Dichlorophenyl)-4-propyl-1,3-dioxolan-2yl-methyl]1H-1,2,4-triazole, 2-methyl-4-isothiazolin-3-one, 5-Chloro-2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-(n-octyl)4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one), N,N,dimethyl-N′-tolyl-N′-dichlorofluromythylthiosulphamide, 2-Bromoacetamide, 2,2-Dibromo-3-nitrilopropionamide, 2-bromo-2-nitro-propan-1-ol, 2-bromo-2-nitropro-pane-1,3-diol, poly(hexamethylenebiguanide) hydrochloride, sodium ethylmercury thiosalicylate, trichloromelamine and 1,3-dichloro-5,5-dimethylhydantoin. 
     
     
         27 . The biocidally active clay mineral according to  claim 17 , further comprising the step of bringing a metal ion into contact with the clay mineral, wherein the metal ion is selected from the group consisting of silver, copper, zinc, molybdenum and titanium ions. 
     
     
         28 . The biocidally active clay mineral according to  claim 17 , wherein the combined amount of
 a) the biocidally active nitrogen compound that contains at least one hydrocarbon group with 6 to 20 carbon atoms and   b) any other biocidally active compounds   in the finished biocidally active clay mineral is from 1 to 60 wt.-%, relative to the weight of the finished biocidally active clay mineral.   
     
     
         29 . The biocidally active clay mineral according to  claim 17 , wherein the weight ratio between the biocidally active compound and the biocidally active nitrogen compound that contains at least one hydrocarbon group with 6 to 20 carbon atoms is in the range of 1:10 to 10:1. 
     
     
         30 . The biocidally active clay mineral according to  claim 27 , wherein the total amount of the metal ions, is between 0.5 and 21 wt.-%, the wt.-% being relative to the combined weight of
 a) the biocidally active nitrogen compound that contains at least one hydrocarbon group with 6 to 20 carbon atoms and   b) the metal ions, and,   c) any other biocidally active compounds.