Process for the co-encapsulation of biocidally active compounds in clay minerals functionalized by nitrogen compounds

• US 9,228,121 B2
• Filed: 02/15/2011
• Issued: 01/05/2016
• Est. Priority Date: 02/23/2010
• Status: Expired due to Fees

• Current Assignee: Clariant S/A (Clariant AG)
• Original Assignee: Clariant S/A (Clariant AG)
• Inventors: de Oliveira Filho, Antonio Pedro, Da Silva, Wagner Claudio, Gallotti, Manlio, Menezes, Alexandra Paschoalin, Framesqui Righi, Karine, Da Silva Rios, Marcia Regina
• Primary Examiner(s): SANDERS, KRIELLION ANTIONETTE
• Application Number:
  US13/580,546
• Publication Number:
  US 20120316259A1
• Time in Patent Office: 1,785 Days
• Field of Search: 524/83, 524/236, 524/403
• US Class Current: 1/1
• CPC Class Codes: A01N 2300/00 Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
• CPC Class Codes: A01N 25/08 containing solids as carriers or diluents
• CPC Class Codes: A01N 25/12 Powders or granules A01N25/26 takes precedence
• CPC Class Codes: A01N 25/26 in coated particulate form
• CPC Class Codes: A01N 33/04 Nitrogen directly attached to aliphatic or cycloaliphatic carbon atoms
• CPC Class Codes: A01N 33/08 containing oxygen or sulfur
• CPC Class Codes: A01N 33/12 Quaternary ammonium compounds
• CPC Class Codes: A01N 43/80 five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
• CPC Class Codes: A01N 47/12 containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
• CPC Class Codes: A01N 57/34 having phosphorus-to-halogen bonds; Phosphonium salts
• CPC Class Codes: A01N 59/16 Heavy metals; Compounds thereof
• CPC Class Codes: C08K 3/346 Clay
• CPC Class Codes: C08K 9/04 Ingredients treated with organic substances treated with macromolecular compounds C08K9/08
• CPC Class Codes: C09D 5/14 Paints containing biocides, e.g. fungicides, insecticides or pesticides C09D5/16 takes precedence
• CPC Class Codes: C09D 7/62 modified by treatment with other compounds
• CPC Class Codes: C09K 8/03 Specific additives for general use in well-drilling compositions

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.

Claims

1. A process for the co-encapsulation of biocidally active ingredients in a clay mineral, wherein the process comprises the steps of bringing the clay mineral into contact with a biocidally active nitrogen compound according to formula (4)

[R¹R²(CH₃)₂N]⁺X⁻

 

 

(4)

wherein

R¹ is benzyl,

R² is a linear C₁₂ to C₁₈ hydrocarbon group and

X⁻

is chloride 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, 3-iodopropenylbutyl-carbamate, tetrakis(hydroxymethyl)-phosphonium sulfate and mixtures thereof.

2. The process according to claim 1, wherein the clay mineral comprises at least one smectite group mineral in a concentration ranging between 60-95 wt.-%, relative to the total weight of the clay mineral.

3. The process according to claim 1, wherein the biocidally active compound is selected from the group consisting of a binary combination of 2-n-octyl-4-isothiazoline-3-one and 3-iodopropenylbutyl-carbamate, 2-n-octyl-4-isothiazoline-3-one and tetrakis(hydroxymethyl)-phosphonium sulfate, 3-iodopropenylbutyl-carbamate and tetrakis(hydroxymethyl)-phosphonium sulfate, 2-n-octyl-4-isothiazoline-3-one and tetrakis(hydroxymethyl)-phosphonium sulfate and a ternary combination of 2-n-octyl-4-isothiazoline-3-one, 3-iodopropenylbutyl-carbamate and tetrakis(hydroxymethyl)-phosphonium sulfate.

4. The process according to claim 1, further comprising the step of bringing 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-dichorophenyl)-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.

5. The process according to claim 1, 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.

6. The process according to claim 1, wherein the combined amount of

a) the biocidally active nitrogen compound according to formula (4) and

b) OIT, IPBC or THPS or their mixture, and 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.

7. The process according to claim 1, wherein the weight ratio between the biocidally active compound and the biocidally active nitrogen compound according to formula (4) is in the range of 1:

10 to 10;

1.

8. The process according to claim 5, 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 according to formula (4)

b) the metal ions, and,

c) any other biocidally active compounds.

9. The process according to claim 4, 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.

10. The process according to claim 5, wherein the combined amount of

a) the biocidally active nitrogen compound according to formula (4),

b) metal ions, and,

c) any other biocidally active compound

in the finished biocidally active clay mineral is from 1 to 60 wt.-%, relative to the weight of the finished biocidally active clay mineral.

11. The process according to claim 9, 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 according to formula (4),

b) the metal ions, and,

c) any other biocidally active compound.

12. The process according to claim 9, wherein the total amount of any other biocidally active compound which is different from a biocidally active nitrogen compound according to formula (4), or 2-n-octyl-4-isothiazoline-3-one (OIT), 3-iodopropenylbutylcarbamate (IPBC) and tetrakis(hydroxymethyl)phosphoniumsulfate (THPS), 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) metal ions, and,

c) any other biocidally active compounds.