US3622377A - Process for applying copper 8-quinolinolate to cellulosics from solvent system - Google Patents

Process for applying copper 8-quinolinolate to cellulosics from solvent system Download PDF

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US3622377A
US3622377A US853536A US3622377DA US3622377A US 3622377 A US3622377 A US 3622377A US 853536 A US853536 A US 853536A US 3622377D A US3622377D A US 3622377DA US 3622377 A US3622377 A US 3622377A
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percent
copper
resin
quinolinolate
solution
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Charles J Conner
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507Polyesters
    • D06M15/51Unsaturated polymerisable polyesters

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  • This invention relates to a process for solubilizing a difiiculty soluble fungicide for application to cellulosic textiles. Specifically, this invention relates to the direct Solubilizing of copper 8-quinolinolate in acetic acid-xylene solvent mixtures. More specifically, this invention relates to a process of making this excellent fungicide easy to apply to cellulosic textiles from solution at room temperature, by conventional techniques, such as the pad-dry-cure method of treating fabrics, where the solvent evaporates and is capable of being reclaimed by condensation.
  • a fifth object is to provide a novel solvent system for copper 8-quinolinolate and pinene polymer resins for application to cellulosic fabric from a single bath to produce a fungicidal coating with water resistance.
  • copper 8-quinolinolate is a recognized fungicide useful in applications to cellulosic materials, but it is very difficulty soluble in organic solvents, demonstrating little or no direct solubilization, requiring that this fungicide be applied only from emulsion, double decomposition, or dispersion systems where maximum in situ deposition and minimum particle size have not been attained.
  • the discovery of a suitable nondegrading organic solvent system for the application of copper 8-quinolinolate to cellulosics has several values relative to utility.
  • the solvent can be reclaimed by condensation from the wet padded cellulosic fabric during drying, and again used in formulating more copper 8-quinolinolate solution.
  • the solvent system which is the instant invention, wets the entire cellulosic material uniformly, and results in a more uniform treatment. Waxes and resins can be incorporated into the solvent system to produce water resistant fungicidal treatments applicable from a single bath. While prior art has shown that copper 8-quinolinolate is soluble to the extent of about 5 percent in hot (110 C.) glacial acetic acid, we have learned that on cooling the solution to room temperature (25 C.) most of the compound separates from solution as crystals.
  • Soil BurialCompost soil, sand F. and 90 percent relative humidity.
  • a process for imparting water and rot resistance to a cellulosic material from a single-bath solution comprising:
  • a process for imparting fungicidal properties to a cellulosic textile comprising:

Abstract

Copper 8-quinolinolate was dissolved in acetic acid-xylene solvent mixtures and applied at room temperature (25* C.) to cotton fabrics by pad-dry-cure method to produce treated fabrics with excellent fungicidal properties from the in situ deposition of the fungicide in fine particle size for better uniformity and penetration of treatment.

Description

United States Patent Charles J. Conner Metairie, La.
Aug. 27, 1969 Nov. 23, 1971 The United States of America as represented by the Secretary of Agriculture Inventor Appl. No. Filed Patented Assignee PROCESS FOR APPLYING COPPER 8- QUINOLINOLATE TO CELLULOSICS FROM SOLVENT SYSTEM [56] References Cited UNITED STATES PATENTS 2,608,556 8/1952 Kalberg 117/138.5 X 2,721,824 10/1955 Feigin et a1. 424/245 2,756,175 7/1956 Goldstein et a1 117/138.5 X 2,799,615 7/1957 Heymons et a1. 424/245 3,033,865 5/1962 Fronmuller et al.. 117/l38.5 X 3,307,970 3/1967 Grier 117/138.5
Primary Examinerwilliam D. Martin Assistant Examiner-Theodore G. Davis Attorneys-R. Hofiman and W. Bier ABSTRACT: Copper 8-quinolinolate was dissolved in acetic acid-xylene solvent mixtures and applied at room temperature (25 C.) to cotton fabrics by pad-dry-cure method to produce treated fabrics with excellent fungicidal properties from the in situ deposition of the fungicide in fine particle size for better uniformity and penetration of treatment.
PROCESS F OR APPLYING COPPER 8-QUINOLINOLATE T CELLULOSHCS FROM SOLVENT SYSTEM A nonexclusive, irrevocable, royalty-free license in the invention herein described throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.
This invention relates to a process for solubilizing a difiiculty soluble fungicide for application to cellulosic textiles. Specifically, this invention relates to the direct Solubilizing of copper 8-quinolinolate in acetic acid-xylene solvent mixtures. More specifically, this invention relates to a process of making this excellent fungicide easy to apply to cellulosic textiles from solution at room temperature, by conventional techniques, such as the pad-dry-cure method of treating fabrics, where the solvent evaporates and is capable of being reclaimed by condensation.
The main object of the instant invention is to provide a means of directly solubilizing copper 8-quinolinolate at room temperature for nondegrading cellulosic treatments.
A second object of the instant invention is to provide a means of applying the fungicide to fabrics, in order to impart to cellulosic fabrics better rot and weather resistance, through in situ deposition of the fungicide in fine particle size throughout the treated fabric.
A third object is to provide a practical method of quantitatively applying copper 8-quinolinolate from solution in organic solvents at room temperature.
A fourth object is to provide a novel solvent system for copper 8-quinolinolate and alkyd resins for application to cellulosic fabric from a single bath to produce a fungicidal coatmg.
A fifth object is to provide a novel solvent system for copper 8-quinolinolate and pinene polymer resins for application to cellulosic fabric from a single bath to produce a fungicidal coating with water resistance.
Another object includes the preparation of a solvent system for combined applications of paints or other coatings which require the inclusion of a good fungistatic agent.
The prior art teaches that copper 8-quinolinolate is a recognized fungicide useful in applications to cellulosic materials, but it is very difficulty soluble in organic solvents, demonstrating little or no direct solubilization, requiring that this fungicide be applied only from emulsion, double decomposition, or dispersion systems where maximum in situ deposition and minimum particle size have not been attained. Many emulsion and dispersion systems exist for the application of copper 8- quinolinolate to cellulosics. Although solubilized by mineral acids, the solutions thus produced degrade cellulose. The discovery of a suitable nondegrading organic solvent system for the application of copper 8-quinolinolate to cellulosics has several values relative to utility. The solvent can be reclaimed by condensation from the wet padded cellulosic fabric during drying, and again used in formulating more copper 8-quinolinolate solution. The solvent system, which is the instant invention, wets the entire cellulosic material uniformly, and results in a more uniform treatment. Waxes and resins can be incorporated into the solvent system to produce water resistant fungicidal treatments applicable from a single bath. While prior art has shown that copper 8-quinolinolate is soluble to the extent of about 5 percent in hot (110 C.) glacial acetic acid, we have learned that on cooling the solution to room temperature (25 C.) most of the compound separates from solution as crystals. This is impractical for fabric treat ments, since as the solutions cool in a padding operation the deposition of crystals of copper 8-quinolinolate would produce an irregular and nonuniform treatment. The solution must be stable at what is commonly referred to as room temperature, which is about 25 C. for utility in conventional processing of cellulosic fabrics.
In the process of investigative work which led to the instant invention, it was discovered that when the hot glacial acetic acid solubilized copper 8-quinolinolate, the solution could be stabilized by adding an equal volume of xylene containing a small quantity of acetic anhydride to remove a fractional percentage of water in the acetic acid, and that the solution of copper 8-quinolinolate could then be cooled to room temperature (25 C.) and used for periods of 8 hours without any indication of crystal formation or any other such phenomenon which would interfere with the application of the ingredients to cotton fabrics, paper, rope, and other cellulosic materials by conventional wetting and drying in air or oven. The fabrics and other cellulosic materials so treated were evaluated through outdoor weathering and soil burial (for rot resistance) and found to have very good fabric protection, as deten'nined by tests.
Other preparations were fonnulated to include alkyd resins, polycoumarone-indene resins, and polypinene resins in the same bath with the copper 8-quinolinolate. These treatments were applied separately to cotton duck to give a copper 8- quinolinolate fungicide treatment with water resistance characteristics. By incorporating a ground pigment with the resin-copper 8-quinolinolate solution a paint was formulated to impart fungicidal characteristics with light screening pigment and resin binder.
in general, the invention can be best described as a novel direct solubilization and applicational process for applying copper 8-quinolinolate to cellulosics from an organic solvent system at room temperature, where other resins and paints are compatible, to produce good uniformity and maximum penetration of fungicide through in situ deposition of copper 8-quinolinolate within the treated cellulosic, on evaporation of the solvent. in solution, the fungicide is reduced to the ideal applicational state for maximum penetration and uniformity or treatment, while the cure-evaporated solvents can be reclaimed by condensation, to be used again to solubilize other copper 8-quinolinolate.
The following examples are presented to illustrate the in vention and certain aspects of its usefulness. These are not to be interpreted as limiting the invention in any manner whatever.
The tests applicable to the treatments on cotton fabrics are the following:
Breaking Strength-Scott Tensile Test (ASTM D39-40).
Soil BurialCompost, soil, sand F. and 90 percent relative humidity.
Water Resistance-Bead test and pouring water across the treated fabric surface, followed by observation for wet-in and wet through.
EXAMPLE I Solubilizing Copper 8-Quinolinolate:
Fifty milliliter of glacial acetic acid (99.5 percent) were poured into a 300 ml. Erlenmeyer flask. A 2.0 gram sample of powdered copper-8 was added, and the mix gradually heated to a boil and boiled for 1 minute, while stirring. All of the solid dissolved and a dark green solution was produced. While the solution was almost boiling C.), 50 ml. of xylene were added and mixed by stirring. A dark green solution resulted, which remained unifonn when cooled to room temperature. After standing for 1 hour at room temperature, a little sediment of copper-8 was noted, and most of the copper-8 remained in solution.
EXAMPLE 2 Solubility of Copper-8 in the Cold (25 C.
2.0 grams of copper-8, 50 ml. of glacial acetic acid (995 percent) and 50 ml. of xylene were mixed and stoppered in a flask. Solubility was observed over 24 hours. At the end of this time, the solid dissolved, and a deep green solution resulted.
EXAMPLE 3 Solubilizing Copper-8 with Acetic Acid, Acetic Anhydride and Xylene:
The presence of 0.5 percent water in 99.5 percent glacial acetic acid was eliminated by adding a small amount of acetic The presence of water in the solvent system reduced the stathus prevented precipitation of solid copper-8 The following formulation was effectively prepared and demonstrated:
A. 3.0 grams copper 8-quinolinolate powder 18 percent Cu) B. (45 ml. glacial acetic acid [99.5 percent] or 47.5 grams mixed ml. acetic anhydride or 5.5 grams C. 50 ml. xylene or 44.0 grams The copper-8 was weighed into a Pyrex Erlenmeyer flask. The mixture of glacial acetic acid and acetic anhydride added, and the flask heated just to a boil for 2 minutes. All of the copper-8 dissolved with the temperature at 1 C. The flask was then cooled to 90 C., when 50 ml. of xylene were added and stirred in to form a uniform solution (dark green). When cooled to room temperature (25 C.) complete solution of the copper-8 had been effected, and a dark green solution resulted 100 grams).
EXAMPLE 4 Padding with the Copper-8 Solution from Example 3:
A 1 yard X 8 inch piece of scoured army duck was wetted with the solution and padded twice through tight rolls to remove excess solution. The wet sample was then oven dried at 120 C./5 minutes. A deep yellow copper-8 fabric treatment was effected with the fabric. The solution represents 3 percent copper-8, the add-on was 0.37 percent copper as metal with a 70 percent wet pickup.
EXAMPLE 5 Poly a-pinene Resin (Piccoflex 120 Resin) Copper-8 Solubility:
Solution from example 2 was treated with 2 grams of Piccoflex I Resin, resulting in the solubility of the resin in the was poured over it.
EXAMPLE 6 Poly-Coumarone-lndene Solubility:
Solution from example 2 was treated with 1 gram of Nevillac Hard Resin, producing a solution of the resin and copper- 8. This solution was applied to 80 80 cotton fabric 8 inches X 4 inches, blotted, and allowed to air dry for 4 hours. A yellowbrown fabric treatment was uniformly produced. Water re sistance was demonstrated after 8 hours drying, by flowing water over the treated fabric surface.
(Nevillac Hard Resin) Copper-8 EXAMPLE 7 EXAMPLE 8 Soil Burial (Rot Resistance) Results tion:
with Copper-8 Solu- The solution from example 2 was used to pad scoured 9 oz. duck. The wet padded and squeezed duck was oven dried at 120 C./5 minutes to give a 0.2 percent copper metal add-on. The fabric was soil buried for 6 weeks and examined after EXAMPLE 9 some algae growths and negligible mildew after 15 months exposure, and retained 38 percent strength.
EXAMPLE l0 Demonstration of Effect of Solvent Copper-8 Treatment on Cotton 9 oz. Duck and 8O Printcloth:
Untreated cotton 9 oz. scoured duck, having an initial breaking strength of 137.0 pounds, and cotton 80X80 printcloth (untreated) having an initial breaking strength of 48.4 pounds, were treated with the copper-8 solution described in example 2, followed by squeezing out excess solution to give a 50 percent wet pickup, and oven drying at 130 C. for 4 minutes. The samples were then tested for percent retained tensile breaking strength. The 80X80 printcloth retained percent strength, while the scoured duck retained 95 percent strength, demonstrating that the treatment did not adversely affect the fabrics for utility.
lclaim:
11. A process for imparting water and rot resistance to a cellulosic material from a single-bath solution, comprising:
a. forming a single bath solution by mixing (1) a resin selected from the group consisting of an alkyd resin, a polypinene resin, and a cumarone-indene resin, with (2) a solution containing about from 1.00 percent to 3.00 percent, by weight, of copper 8-quinolinolate fully dissolved in a water-free glacial acetic acid to xylene mixture in molar ratios, respectively, of about 1.5: 1.0 to 2.0: 1.00.
b. impregnating the cellulosic material with the single-bath solution thus formed to about a 70 percent wet pickup, and
c. drying the wet, impregnated cellulosic material for about 5 minutes at about from to C.
2. The process of claim 1 wherein the resin is an alkyd resin.
3. The process of claim 1 wherein the resin is a polypinene resin.
4. The process of claim 1 wherein the resin is a cumaroneindene resin.
5. A process for imparting fungicidal properties to a cellulosic textile comprising:
a. impregnating the cellulosic textile with a water free glacial acetic acid to xylene mixture in molar ratios respec- .0 to 20:10, containing about quinolinolate fully dissolved therein, to obtain a wet pickup of about 70 percent, and b. drying the wet impregnated cellulosic textile for about 5 minutes at about from 120 to 130 C. 6. A process for imparting fungicidal properties to a cellulosic textile comprising:
a. impregnating the cellulosic textile with a water free glaquinolinolate fully dissolved therein, to obtain a wet cent, by weight, of copper 8-quinolinolate fully dissolved pickup fa ut 70 p r t, and in a water-free glacial acetic acid to xylene mixture in b. air drying the wet, impregnated cellulosic textile for molar i respectively, ofabout l 5;l.0 to 2.0:l.0,
about 4 houm 'f abolft b. impregnating the cellulosic material with the single-bath 7. process for imparting water and rot resistance to a cel- 5 solution thus formed to about a 70 percent wet pickup lulosic material from a single-bath solution, comprising: and
a. forming a single-bath solution by mixing (l) a resin t Selected from the g p consisting of an alkyd resin. a 0. air drying the wet, impregnated cellulosic material for polypinene resin, and a cumarone-indene resin, with (2) a about 4 hours at about 25 solution containing about from 1.00 percent to 3.00 per- 10

Claims (6)

  1. 2. The process of claim 1 wherein the resin is an alkyd resin.
  2. 3. The process of claim 1 wherein the resin is a polypinene resin.
  3. 4. The process of claim 1 wherein the resin is a cumarone-indene resin.
  4. 5. A process for imparting fungicidal properties to a cellulosic textile comprising: a. impregnating the cellulosic textile with a water free glacial acetic acid to xylene mixture in molar ratios respectively of about from 1.5:1.0 to 2.0:1.0, containing about from 1.00 percent to 3.00 percent by weight of copper 8-quinolinolate fully dissolved therein, to obtain a wet pickup of about 70 percent, and b. drying the wet impregnated cellulosic textile for about 5 minutes at about from 120* to 130* C.
  5. 6. A process for imparting fungicidal properties to a cellulosic textile comprising: a. impregnating the cellulosic textile with a water free glacial acetic acid to xylene mixture in molar ratios respectively of about from 1.5:1.0 to 2.0:1.0, containing about from 1.00 percent to 3.00 percent by weight of copper 8-quinolinolate fully dissolved therein, to obtain a wet pickup of about 70 percent, and b. air drying the wet, impregnated cellulosic textile for about 4 hours at about 25* C.
  6. 7. A process for imparting water and rot resistance to a cellulosic material from a single-bath solution, comprising: a. forming a single-bath solution by mixing (1) a resin selected from the group consisting of an alkyd resin, a polypinene resin, and a cumarone-indene resin, with (2) a solution containing about from 1.00 percent to 3.00 percent, by weight, of copper 8-quinolinolate fully dissolved in a water-free glacial acetic acid to xylene mixture in molar ratios, respectively, of about 1.5:1.0 to 2.0:1.0, b. impregnating the cellulosic material with the single-bath solution thus formed to about a 70 percent wet pickup, and c. air drying the wet, impregnated cellulosic material for about 4 hours at about 25* C.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040258767A1 (en) * 2003-04-09 2004-12-23 Leach Robert M. Micronized wood preservative formulations
US20050118280A1 (en) * 2003-04-09 2005-06-02 Leach Robert M. Micronized wood preservative formulations
US20060112850A1 (en) * 2004-10-14 2006-06-01 Jun Zhang Micronized wood preservative formulations in organic carriers
US8158208B2 (en) 2004-05-17 2012-04-17 Osmose, Inc. Method of preserving wood by injecting particulate wood preservative slurry
US8409627B2 (en) 2003-06-17 2013-04-02 Osmose, Inc. Particulate wood preservative and method for producing the same
US8637089B2 (en) 2003-04-09 2014-01-28 Osmose, Inc. Micronized wood preservative formulations

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2608556A (en) * 1950-07-10 1952-08-26 Scient Oil Compounding Company Preparation of a soluble metal quinolinolate
US2721824A (en) * 1952-08-01 1955-10-25 Geigy Chem Corp Solubilization of copper-8-quinolinolate
US2756175A (en) * 1952-07-02 1956-07-24 Sun Chemical Corp Fungicidal compositions comprising copper-8-quinolinolate solubilized with heavy metal salts of alkyl phosphoric acid esters
US2799615A (en) * 1953-05-23 1957-07-16 Riedel De Haen Ag Process of preparing fungicidal 8-hydroxyquinoline compositions
US3033865A (en) * 1959-04-09 1962-05-08 Augustus S Wittnebel Solubilizing copper-8-quinolinolate
US3307970A (en) * 1961-11-30 1967-03-07 Merck & Co Inc Preparations for the production of metal 8-hydroxy quinolinates and process for utilizing same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2608556A (en) * 1950-07-10 1952-08-26 Scient Oil Compounding Company Preparation of a soluble metal quinolinolate
US2756175A (en) * 1952-07-02 1956-07-24 Sun Chemical Corp Fungicidal compositions comprising copper-8-quinolinolate solubilized with heavy metal salts of alkyl phosphoric acid esters
US2721824A (en) * 1952-08-01 1955-10-25 Geigy Chem Corp Solubilization of copper-8-quinolinolate
US2799615A (en) * 1953-05-23 1957-07-16 Riedel De Haen Ag Process of preparing fungicidal 8-hydroxyquinoline compositions
US3033865A (en) * 1959-04-09 1962-05-08 Augustus S Wittnebel Solubilizing copper-8-quinolinolate
US3307970A (en) * 1961-11-30 1967-03-07 Merck & Co Inc Preparations for the production of metal 8-hydroxy quinolinates and process for utilizing same

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8747909B2 (en) 2003-04-09 2014-06-10 Osmose, Inc. Micronized wood preservative formulations
US8747908B2 (en) 2003-04-09 2014-06-10 Osmose, Inc. Micronized wood preservative formulations
US8460759B2 (en) 2003-04-09 2013-06-11 Osmose, Inc. Micronized wood preservative formulations
US20080260841A1 (en) * 2003-04-09 2008-10-23 Leach Robert M Micronized wood preservative formulations
US20090035564A1 (en) * 2003-04-09 2009-02-05 Leach Robert M Micronized Wood Preservative Formulations
US20090092683A1 (en) * 2003-04-09 2009-04-09 Leach Robert M Micronized Wood Preservative Formulations
US7674481B2 (en) 2003-04-09 2010-03-09 Osmose, Inc. Micronized wood preservative formulations
US9079328B2 (en) 2003-04-09 2015-07-14 Koppers Performance Chemicals Inc. Micronized wood preservative formulations
US8778407B2 (en) 2003-04-09 2014-07-15 Osmose, Inc. Micronized wood preservative formulations
US20050118280A1 (en) * 2003-04-09 2005-06-02 Leach Robert M. Micronized wood preservative formulations
US20040258767A1 (en) * 2003-04-09 2004-12-23 Leach Robert M. Micronized wood preservative formulations
US8637089B2 (en) 2003-04-09 2014-01-28 Osmose, Inc. Micronized wood preservative formulations
US8871277B2 (en) 2003-06-17 2014-10-28 Osmose, Inc. Particulate wood preservative and method for producing the same
US8409627B2 (en) 2003-06-17 2013-04-02 Osmose, Inc. Particulate wood preservative and method for producing the same
US8722198B2 (en) 2004-05-17 2014-05-13 Osmose, Inc. Method of preserving wood by injecting particulate wood preservative slurry
US8158208B2 (en) 2004-05-17 2012-04-17 Osmose, Inc. Method of preserving wood by injecting particulate wood preservative slurry
US9314030B2 (en) 2004-05-17 2016-04-19 Koppers Performance Chemicals Inc. Particulate wood preservative and method for producing same
US9775350B2 (en) 2004-10-14 2017-10-03 Koppers Performance Chemicals Inc. Micronized wood preservative formulations in organic carriers
US20060112850A1 (en) * 2004-10-14 2006-06-01 Jun Zhang Micronized wood preservative formulations in organic carriers

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