WO2012064894A1

WO2012064894A1 - Antimicrobial compositions for incorporation into polymers

Info

Publication number: WO2012064894A1
Application number: PCT/US2011/060059
Authority: WO
Inventors: Lok Yuen Lo; Neal G. Stewart
Original assignee: Filligent (Hk) Limited; Filligent Usa, Inc.
Priority date: 2010-11-09
Filing date: 2011-11-09
Publication date: 2012-05-18

Abstract

The present invention describes compositions comprising a complex of a metallic salt or metal ion reacted with a metal phthalocyanine, which can be incorporated into polymeric materials to impart an antimicrobial, antibacterial, antiviral, and/or spermicidal property to the polymeric material. In one embodiment, the antimicrobial compositions comprise particles containing copper and/or zinc complexed with a phthalocyanine dye under conditions of heat in aqueous medium. The biocidal metal-containing particles of the invention can be incorporated into moldable polymers including but not limited to latex or polyurethane prior to casting or molding. The incorporated particles impart antimicrobial or antiviral properties to the material, but do not interfere with the casting or molding of the polymeric material, and are more compatible than salts of divalent metal ions alone.

Description

ANTIMICROBIAL COMPOSITIONS FOR INCORPORATION INTO

POLYMERS

CROSS-REFERENCE TO RELATED APPLICATION

The present Application claims the benefit of priority from United States

Provisional Patent Application No. 61/411,850 filed November 9, 2010 and titled "Antimicrobial Compositions For Incorporation Into Polymers"; the contents of which are incorporated in this disclosure by reference in their entirety. TECHNICAL FIELD

This invention relates to antimicrobial compositions, in particular antimicrobial compositions suitable for incorporation into polymeric materials and a method of making the antimicrobial compositions and polymeric materials. BACKGROUND ART

Some metal ions such as copper, zinc or silver have strong antimicrobial activity and are also relatively safe at active antimicrobial concentrations if they come into contact with the skin of animals or humans. However, some biocidal metal ions are problematic for incorporation into polymeric materials, such as latex or polyurethane, prior to molding or casting into products such as insoles, condoms, gloves, tubing, sponges or other products where antimicrobial activity is desirable. Copper ions, for example, discolor latex and promote its degradation by reacting with its constituent proteins.

What are needed are particles that impart antimicrobial or antiviral properties to polymeric materials, but do not interfere with the casting or molding of the polymeric material, and are more compatible than salts of divalent metal ions. With these goals in mind, the inventor created biocidal metal-containing particles that can be incorporated into moldable polymers including but not limited to latex or polyurethane prior to casting or molding to result in polymeric materials having antimicrobial, antiviral and spermicidal properties.

DISCLOSURE OF INVENTION

The present invention comprises a composition for incorporation into a polymeric material comprising a free metal ion and metal phthalocyanine complex. The complex comprises a precipitate formed from a reacted mixture of one or more than one metal phthalocyanine and one or more metallic salt or metal ion. The composition imparts one or more bioactivity property to a polymeric material, including an antimicrobial activity, antibacterial activity, antiviral activity and/or a spermicidal activity.

In particular, the metal phthalocyanine can be a reactive phthalocyanine dye or a metal phthalocyanine sulfonate. The one or more metallic salt or metal ion utilized to react with the metal phthalocyanine can be copper acetate, copper dithionate, copper fluorosilicate, copper formate, copper gluconate, copper glycerophosphate, copper halides, copper iodide, copper lactate, copper nitrate, copper phenolsulfonate, copper salicylate, copper stearate, copper succinate, copper sulfate, copper tartrate, zinc acetate, zinc ammonium sulfate, zinc chromate, zinc citrate, zinc formate, zinc gluconate, zinc glycerophosphate, zinc halides, zinc iodide, zinc lactate, zinc nitrate, zinc phenolsulfonate, zinc salicylate, zinc stearate, zinc succinate, zinc sulfate, zinc tartrate, a silver ion, a copper ion, a zinc ion, an aluminum ion, ferric iron, and ferrous iron.

The polymeric material in which the composition can be incorporated includes one of latex, polyurethane, polyvinyl alcohol, neoprene, nitrile rubber, nylon, polyvinyl choride (PVC), polystyrene, polyethylene, polypropylene, polyacrylonitrile, and silicone. One to five percent of the polymeric material can be comprised of the composition.

Also disclosed is a polymeric material comprising one or more than one metal phthalocyanine and one or more metallic salt or metal ion, wherein the polymeric material has antimicrobial activity, antibacterial activity, antiviral activity and/or spermicidal activity. The polymeric material can be latex, polyurethane, polyvinyl alcohol, neoprene, nitrile rubber, nylon, polyvinyl choride (PVC), polystyrene, polyethylene, polypropylene, polyacrylonitrile, or silicone. The metal phthalocyanine can be a reactive phthalocyanine dye or a metal phthalocyanine sulfonate. In one embodiment, the reactive phthalocyanine dye comprises C.I. Reactive Blue 21 dye. In another embodiment, the metal phthalocyanine sulfonate can be any one of copper phthalocyanine, copper phthalocyanine tetrasulfonate, zinc phthalocyanine, zinc phthalocyanine tetrasulfonate, iron phthalocyanine tetrasulfonate, copper phthalocyanine disulfonate, zinc phthalocyanine disulfonate, iron phthalocyanine disulfonate, copper phthalocyanine trisulfonate, zinc phthalocyanine trisulfonate, and iron phthalocyanine trisulfonate.

The one or more metallic salt or metal ion can be a monovalent metallic salt or metal ion, a divalent metallic salt or metal ion, and a trivalent metallic salt or metal ion. Such divalent metallic salt can be one of copper acetate, copper dithionate, copper fluorosilicate, copper formate, copper gluconate, copper glycerophosphate, copper halides, copper iodide, copper lactate, copper nitrate, copper phenolsulfonate, copper salicylate, copper stearate, copper succinate, copper sulfate, copper tartrate, zinc acetate, zinc ammonium sulfate, zinc chromate, zinc citrate, zinc formate, zinc gluconate, zinc glycerophosphate, zinc halides, zinc iodide, zinc lactate, zinc nitrate, zinc phenolsulfonate, zinc salicylate, zinc stearate, zinc succinate, zinc sulfate, and zinc tartrate. Alternatively, the polymeric material can include a monovalent metal ion such as silver, a divalent metal ion such as copper, zinc, and/or ferric iron, or a trivalent metal ion such as aluminum and/or ferrous iron.

In addition, a method of making the composition and a biocidal polymeric material that incorporates the composition is disclosed. The method comprises the steps of preparing a metal ion phthalocyanine complex comprising one or more metal phthalocyanine and one or more metallic salt or metallic ion, and mixing the metal ion phthalocyanine complex into the polymeric material. Approximately one to five percent resulting polymeric material can be comprised of the composition. The polymeric material can then be molded or formed into a device that has antibacterial, antimicrobial, antiviral, and/or spermicidal activity.

A method of preparing a metal ion phthalocyanine complex can comprise: heating an aqueous medium; adding a metal phthalocyanine to said heated aqueous medium; and adding one or more metallic salt to the heated aqueous medium. The metal phthalocyanine and metallic salt react to form a precipitate, and the precipitate is isolated, washed, and dried. This precipitate can be added to a polymeric material to impart biocidal properties to the material.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a graph depicting the percent in reduction of bacterial counts vs. the percent of a copper and zinc ion phthalocyanine complex, for one hour and eight hour periods of contact time, according to the present invention.

MODES FOR CARRYING OUT THE INVENTION

The detailed description set forth below in connection with the appended drawings is intended to provide example embodiments of the present invention and is not intended to represent the only forms in which the invention may be constructed or utilized. The description sets forth the functions and the sequences of steps for constructing and operating the invention. However, it is to be understood that the same or equivalent functions and sequences may be accomplished by different embodiments that are also intended to be encompassed within the spirit and scope of the invention. Additional embodiments, features, and/or advantages of the invention will become apparent from the description or may be learned by practicing the invention.

The present invention pertains to a metal phthalocyanine reacted with a metallic salt or metal ion to form a complex that can be utilized in polymeric materials to impart antimicrobial, antiviral, and/or spermicidal properties to the materials. In one embodiment of the present invention, a vinyl- sulphone reactive metal phthalocyanine dye, including but not limited to C.I. Reactive Blue 21 dye or another reactive phthalocyanine dye known to one of ordinary skill in the art, is heated in aqueous medium in the presence of a salt of a divalent metal ion, followed by washing and isolation of the resultant particulate matter. The resultant particulate matter is then mixed into a polymeric material prior to molding, casting or extruding into a product. Polymeric materials suitable for incorporation of the particles of the invention include latex, polyurethane, polyvinyl alcohol, neoprene, nitrile rubber (butadiene acrylonitrile copolymer), nylon, PVC, polystyrene, polyethylene, polypropylene, polyacrylonitrile, silicone, and other similar substances.

In another embodiment of the invention, the antimicrobial compositions can be formed from divalent metal ions reacted with a metal phthalocyanine sulfonate, including but not limited to copper phthalocyanine, copper phthalocyanine tetrasulfonate, zinc phthalocyanine, zinc phthalocyanine tetrasulfonate, iron phthalocyanine tetrasulfonate, copper phthalocyanine disulfonate, zinc phthalocyanine disulfonate, iron phthalocyanine disulfonate, copper phthalocyanine trisulfonate, zinc phthalocyanine trisulfonate, and iron phthalocyanine trisulfonate.

In addition to antimicrobial and antiviral activity, divalent metal ions, especially copper, have spermicidal properties. Therefore, compositions of the invention provide for enhanced spermicidal activity of barrier contraceptives including condoms and diaphragms, in addition to imparting antimicrobial and antiviral properties.

In other embodiments of the invention, monovalent metal ions such as silver ions or trivalent metal ions such as aluminum can be reacted with a metal phthalocyanine dye or with a metal phthalocyanine sulfonate to form the antimicrobial compositions for incorporation into polymeric materials. Example 1: Preparation of Free Copper Ion Phthalocyanine Complex

According to one embodiment of the present invention, free copper ion phthalocyanine complex was prepared according to the present invention as follows. First, 200 ml distilled water was heated to 80°C. 10 g of CI Reactive Blue 21 (Novacron® Turquoise H-GN) was added to the distilled water and temperature was maintained at 80°C. Next, 14 g of copper acetate was added in 2 g intervals with continuous magnetic stirring. The mixture was allowed to react for thirty minutes. A precipitate formed and was filtered and washed with distilled water three times in order to remove the unreacted CI Reactive Blue 21 and copper acetate. The washed precipitate was dried in oven at 60°C for 4 hours. The metal content of the complex was analyzed by Niton XRF analyzer XL3t. The copper content of the complex obtained was 68%, which is 17 times higher than the raw CI Reactive Blue 21 (Novacron® Turquoise H-GN).

Example 2: Preparation of Free Copper and Zinc Ion Phthalocyanine Complex

According to another embodiment of the present invention, free copper and zinc ions phthalocyanine complex was prepared according to the present invention as follows. First, 200 ml distilled water was heated to 80°C. 10 g of CI Reactive Blue 21 (Novacron® Turquoise H-GN) was added to the distilled water and temperature was maintained at 80°C. Next, 14 g of copper acetate and zinc acetate were added in 2 g intervals with continuous magnetic stirring. The mixture was allowed to react for thirty minutes. A precipitate formed and was filtered and washed with distilled water three times in order to remove the unreacted CI Reactive Blue 21, copper acetate, and zinc acetate. The washed precipitate was dried in an oven at 60°C for 4 hours. It was followed by analysis of copper and zinc content of the obtained sample. The copper and zinc content were 48.3% and 11.8% respectively. Though the above example utilizes copper acetate and zinc acetate, functionally equivalent copper salts known to those of ordinary skill in the art include copper acetate, copper dithionate, copper fluorosilicate, copper formate, copper gluconate, copper glycerophosphate, copper halides, copper iodide, copper lactate, copper nitrate, copper phenolsulfonate, copper salicylate, copper stearate, copper succinate, copper sulfate, and copper tartrate. Likewise, functionally equivalent zinc salts known to those of ordinary skill in the art include zinc acetate, zinc ammonium sulfate, zinc chromate, zinc citrate, zinc formate, zinc gluconate, zinc glycerophosphate, zinc halides, zinc iodide, zinc lactate, zinc nitrate, zinc phenolsulfonate, zinc salicylate, zinc stearate, zinc succinate, zinc sulfate, zinc tartrate.

In another alternative embodiment of the present invention, free copper and zinc ion phthalocyanme complex are prepared according to the present invention as follows. First, 200 ml aliquots of distilled water of water are heated to 80°C in a set of beakers. 10 g each of copper phthalocyanme, copper phthalocyanme tetrasulfonate, zinc phthalocyanme, zinc phthalocyanme tetrasulfonate and iron phthalocyanme tetrasulfonate are separately added to the heated water in individual beakers (one metal phthalocyanme compound per beaker) and temperature is maintained at 80°C. Next, 14 g of copper acetate and zinc acetate are added into each beaker by 2 g intervals with continuous magnetic stirring. The mixture was allowed to react for thirty minutes. A precipitate formed and was filtered and washed with distilled water three times in order to remove the unreacted metal phthalocyanme and copper and zinc ions. The washed precipitate is dried in an oven at 60°C for 4 hours, followed by analysis of copper and zinc content of the obtained sample.

Example 3: Application of Free Copper and Zinc Ion Phthalocyanine Complex into Polyurethane Sponge Material According to one embodiment of the present invention, 1% of phthalocyanine Complex comprising 48.3% of free copper ion and 1 1.8% of free zinc ion prepared according to Example 2, was mixed with 49.5% polypropylene glycol, 49.5% toluene diisocyanate from which polyurethane flexible sponge material was foamed and molded.

Example 4: Application of Free Copper and Zinc Ion Phthalocyanine Complex into Polyurethane Sponge Material

According to one embodiment of the present invention, 3% of phthalocyanine Complex comprising 48.3% of free copper ion and 1 1.8% of free zinc ion prepared according to Example 2, was mixed with 48.5% polypropylene glycol, 48.5%) toluene diisocyanate, from which polyurethane flexible sponge was foamed and molded. Example 5: Application of Free Copper and Zinc Ion Phthalocyanine Complex into Polyurethane Sponge Material

According to one embodiment of the present invention, 5% of phthalocyanine Complex comprising 48.3% of free copper ion and 1 1.8% of free zinc ion prepared according to Example 2, was mixed with 47.5% polypropylene glycol, 47.5%) toluene diisocyanate, from which polyurethane flexible sponge was foamed and molded.

Example 6: Assessment of Antibacterial Property of Polyurethane Sponge Material Containing Free Copper and Zinc Ion Phthalocyanine Complex

The antibacterial and antimicrobial properties of the treated sponge were assessed in a direct inoculation study. Staphylococcus aureus ATCC 6538 was selected as the challenge organism. A 0.06 mL aliquot of inoculum was applied on the surface of sponge and colony forming unit recovered was counted after 1 and 8 hours. Percent reduction was calculated according to the following equation: Average Control Results - Average Test Results ._nn „ _r, , ..

- - x 100 = Percent Reduction

Average Control Results

Table 1

As shown in Table 1 and Fig. 1, the assessment showed 1% Copper and Zinc Ion Phthalocyanine Complex reduced bacterial counts by 66% and 74% in 1 and 8 hours respectively. When the concentration of complex was increased to 3%, the percent of reduction was increased to 89% in 1 hour and 98% in 8 hours respectively. When the concentration was further increased to 5%, the percent reduction was as high as 96% in 1 hour and 98% in 8 hours. The foregoing results are relative to a control of unmodified polyurethane sponge material.

Example 7: Application of Free Copper and Zinc Ion Phthalocyanine Complex into Latex Material

According to one embodiment of the present invention, 3% of phthalocyanine Complex comprising 48.3% of free copper ion and 11.8% of free zinc ion prepared according to Example 2, is mixed with liquid latex, which is then formed into condoms, contraceptive diaphragms, gloves or other protective barrier products by standard latex molding methods known in the art, such as dipping molds into liquid latex and removing the mold, allowing the latex to dry and cure. In addition to antimicrobial properties, the free copper and zinc phthalocyanine complex imparts spermicidal activity to latex materials or devices, in part due to the known spermicidal activity of copper ions.

Example 8: Application of Free Copper and Zinc Ion Phthalocyanine Complex into Polyvinylalcohol Material

According to one embodiment of the present invention, 3% of phthalocyanine Complex comprising 48.3% of free copper ion and 11.8% of free zinc ion prepared according to Example 2, is mixed with a 4% aqueous solution of polyvinylalcohol, which is applied to textiles or fabrics and dried, imparting antimicrobial properties to the textiles.

Example 9: Application of Free Copper and Zinc Ion Phthalocyanine Complex into Polyethylene Material

According to one embodiment of the present invention, 3% of phthalocyanine Complex comprising 48.3% of free copper ion and 11.8% of free zinc ion prepared according to Example 2, is mixed with molten polyethylene, which is molded, extruded, spun, or drawn by standard methods known in the art to form objects or textile fibers with antimicrobial activity.

Example 10: Application of Free Copper and Zinc Ion Phthalocyanine Complex into Polypropylene Material

According to one embodiment of the present invention, 3% of phthalocyanine Complex comprising 48.3% of free copper ion and 11.8% of free zinc ion prepared according to Example 2, is mixed with molten polypropylene, which is molded, extruded, spun, or drawn by standard methods known in the art to form objects or textile fibers with antimicrobial activity. Example 11: Application of Free Copper and Zinc Ion Phthalocyanine Complex into Nitrile Rubber (butadiene acrylonitrile copolymer) Material

According to one embodiment of the present invention, 3% of phthalocyanine Complex comprising 48.3% of free copper ion and 11.8% of free zinc ion prepared according to Example 2, is mixed with an aqueous nitrile rubber (butadiene acrylonitrile copolymer) dispersion (nitrile rubber latex), which is formed or molded into gloves, textiles footwear or other objects by standard methods known in the art.

Example 12: Preparation of Free Silver Ion Phthalocyanine Complex

According to another embodiment of the present invention, a monovalent metallic salt or metal ion can be used to react with a metal phthalocyanine to create the compositions for incorporation into polymeric materials. For example, in one embodiment, free silver ion phthalocyanine complex is prepared according to the present invention as follows. First, 200 ml distilled water is heated to 80°C. 10 g of CI Reactive Blue 21 (Novacron® Turquoise H-GN) is added to the water and temperature is maintained at 80°C. Next, 14 g of silver acetate is added in 2 g intervals with continuous magnetic stirring. The mixture was allowed to react for thirty minutes. A precipitate formed and was filtered and washed with distilled water three times in order to remove the unreacted CI Reactive Blue 21 and silver acetate. The washed precipitate is dried in an oven at 60°C for 4 hours. The metal content of the complex is analyzed by Niton XRF analyzer XL3t. The resulting composition can be incorporated into polymeric materials in a manner similar to those described herein.

Example 13: Preparation of Free Aluminum Ion Phthalocyanine Complex

According to another embodiment of the present invention, a trivalent metallic salt or metal ion can be used to react with a metal phthalocyanine to create the compositions for incorporation into polymeric materials. For example, in one embodiment, free aluminum ion phthalocyanine complex is prepared according to the present invention as follows. First, 200 ml distilled water is heated to 80°C. 10 g of CI Reactive Blue 21 (Novacron® Turquoise H-GN) is added to the water and temperature is maintained at 80°C. Next, 14 g of aluminum acetate is added in 2 g intervals with continuous magnetic stirring. The mixture was allowed to react for thirty minutes. A precipitate formed and was filtered and washed with distilled water three times in order to remove the unreacted CI Reactive Blue 21 and aluminum acetate. The washed precipitate is dried in an oven at 60°C for 4 hours. The metal content of the complex is analyzed by Niton XRF analyzer XL3t. The resulting composition can be incorporated into polymeric materials in a manner similar to those described herein.

INDUSTRIAL APPLICABILITY

The foregoing compositions comprising a complex of a metallic salt or metal ion reacted with a metal phthalocyanine described herein can be incorporated into the polymeric materials at different percentages to impart antibacterial, antiviral and spermicidal properties to the materials. Such polymeric materials can be formed into products such as insoles, condoms, gloves, tubing, sponges or other products where antimicrobial activity is desirable.

While the present invention has been described with regards to particular embodiments, it is recognized that additional variations of the present invention may be devised without departing from the inventive concept. A person skilled in the art would appreciate that exemplary embodiments described hereinabove are merely illustrative of the general principles of the present invention. Other variations may be employed that are within the scope of the invention. Accordingly, the drawings and description are illustrative and not meant to be a limitation thereof.

Claims

CLAIMS What is claimed is:

1. A polymeric material comprising:

one or more than one metal phthalocyanme; and

one or more metallic salt or metal ion;

whereby said polymeric material has one or more bioactivity property selected from the group consisting of antimicrobial activity, antibacterial activity, antiviral activity and spermicidal activity.

2. The polymeric material of claim 1, said one or more than one metal phthalocyanme is selected from the group consisting of a reactive phthalocyanme dye and a metal phthalocyanine sulfonate.

3. The polymeric material of claim 2, said reactive phthalocyanine dye comprises C.I. Reactive Blue 21 dye.

4. The polymeric material of claim 2, said metal phthalocyanine sulfonate is selected from the group consisting of copper phthalocyanine, copper phthalocyanine tetrasulfonate, zinc phthalocyanine, zinc phthalocyanine tetrasulfonate, iron phthalocyanine tetrasulfonate, copper phthalocyanine disulfonate, zinc phthalocyanine disulfonate, iron phthalocyanine disulfonate, copper phthalocyanine trisulfonate, zinc phthalocyanine trisulfonate, and iron phthalocyanine trisulfonate.

5. The polymeric material of claim 1, said one or more metallic salt or metal ion is selected from the group comprising a monovalent metallic salt or metal ion, a divalent metallic salt or metal ion, and a trivalent metallic salt or metal ion.

6. The polymeric material of claim 5, said divalent metallic salt is selected from the group consisting of copper acetate, copper dithionate, copper fluorosilicate, copper formate, copper gluconate, copper glycerophosphate, copper halides, copper iodide, copper lactate, copper nitrate, copper phenolsulfonate, copper salicylate, copper stearate, copper succinate, copper sulfate, copper tartrate, zinc acetate, zinc ammonium sulfate, zinc chromate, zinc citrate, zinc formate, zinc gluconate, zinc glycerophosphate, zinc halides, zinc iodide, zinc lactate, zinc nitrate, zinc phenolsulfonate, zinc salicylate, zinc stearate, zinc succinate, zinc sulfate, and zinc tartrate.

7. The polymeric material of claim 5, said monovalent metal ion comprises a silver ion.

8. The polymeric material of claim 5, said divalent metal ion is selected from the group comprising copper, zinc, and ferric iron.

9. The polymeric material of claim 5, said trivalent metal ion is selected from the group comprising aluminum and ferrous iron.

10. The polymeric material of claim 1, said polymeric material is selected from the group consisting of latex, polyurethane, polyvinyl alcohol, neoprene, nitrile rubber, nylon, polyvinyl choride (PVC), polystyrene, polyethylene, polypropylene, polyacrylonitrile, and silicone.

11. A method of making a polymeric material having one or more bioactivity property selected from the group consisting of antimicrobial activity, antiviral activity and spermicidal activity, said method comprising the steps of:

preparing a metal ion phthalocyanine complex comprising one or more metal phthalocyanine and one or more metallic salt or metallic ion; and

mixing said metal ion phthalocyanine complex into said polymeric material.

12. The method of claim 11, said polymeric material is selected from the group consisting of latex, polyurethane, polyvinyl alcohol, neoprene, nitrile rubber, nylon, polyvinyl choride (PVC), polystyrene, polyethylene, polypropylene, polyacrylonitrile, and silicone.

13. The method of claim 11, wherein said polymeric material further comprises one to five percent of said metal ion phthalocyanine complex.

14. The method of claim 11 , said step of preparing a metal ion phthalocyanine complex further comprises:

heating an aqueous medium;

adding said metal phthalocyanine to said heated aqueous medium; adding said one or more metallic salt to said heated aqueous medium, wherein said metal phthalocyanine and said metallic salt react to form said complex as a precipitate; and

isolating, washing, and drying said precipitate.

15. The method of claim 11 , said metal phthalocyanine comprises C.I. Reactive Blue 21 dye and said one or more metallic salt or metallic ion comprises copper acetate and zinc acetate.

16. A composition comprising a free metal ion and metal phthalocyanine complex, said complex comprising:

a precipitate formed from a reacted mixture of at least one metal phthalocyanine and at least one metallic salt or metal ion;

whereby said composition is capable of imparting one or more bioactivity property to a polymeric material, said one or more bioactivity property is selected from the group consisting of antimicrobial activity, antibacterial activity, antiviral activity and spermicidal activity.

17. The composition of claim 16, said at least one metal phthalocyanine is selected from the group consisting of a reactive phthalocyanine dye and a metal phthalocyanine sulfonate.

18. The composition of claim 16, said at least one metallic salt or metal ion is selected from the group consisting of copper acetate, copper dithionate, copper fluorosilicate, copper formate, copper gluconate, copper glycerophosphate, copper halides, copper iodide, copper lactate, copper nitrate, copper phenolsulfonate, copper salicylate, copper stearate, copper succinate, copper sulfate, copper tartrate, zinc acetate, zinc ammonium sulfate, zinc chromate, zinc citrate, zinc formate, zinc gluconate, zinc glycerophosphate, zinc halides, zinc iodide, zinc lactate, zinc nitrate, zinc phenolsulfonate, zinc salicylate, zinc stearate, zinc succinate, zinc sulfate, zinc tartrate, a silver ion, a copper ion, a zinc ion, an aluminum ion, ferric iron, and ferrous iron.

19. The composition of claim 16, said at least one metal phthalocyanine comprises C.I. Reactive Blue 21 dye and said at least one metallic salt or metallic ion comprises copper acetate and zinc acetate.

20. A method of making the composition of claim 16 comprising the steps of: heating an aqueous medium;

adding said at least one metal phthalocyanine to said heated aqueous medium;

adding said at least one metallic salt or metal ion to said heated aqueous medium, wherein said at least one metal phthalocyanine and said at least one metallic salt react to form said complex as a precipitate; and

isolating, washing, and drying said precipitate.