CA1257835A - Solid biocide dry blend - Google Patents
Solid biocide dry blendInfo
- Publication number
- CA1257835A CA1257835A CA000502823A CA502823A CA1257835A CA 1257835 A CA1257835 A CA 1257835A CA 000502823 A CA000502823 A CA 000502823A CA 502823 A CA502823 A CA 502823A CA 1257835 A CA1257835 A CA 1257835A
- Authority
- CA
- Canada
- Prior art keywords
- microbiocide
- resin
- composition
- powder
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F1/00—Details not covered by groups G06F3/00 - G06F13/00 and G06F21/00
- G06F1/26—Power supply means, e.g. regulation thereof
- G06F1/28—Supervision thereof, e.g. detecting power-supply failure by out of limits supervision
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0058—Biocides
Abstract
ABSTRACT OF THE DISCLOSURE
A composition comprising a dry blend mixture of a porous thermoplastic resin powder and from 1 to 80 wt. % of a microbiocide based upon the weight of the composition. The microbiocide is present in the mixture at a concentration of at least about 20 times greater than the normal upper usage concentration of the microbiocide, and is held within the pores of the thermoplastic powder.
The resulting concentrate is a substantially non-dusting, free-flowing powder which is readily incorporated into a second thermoplastic resin to produce a resulting article having the appropriate level of microbiocide.
A composition comprising a dry blend mixture of a porous thermoplastic resin powder and from 1 to 80 wt. % of a microbiocide based upon the weight of the composition. The microbiocide is present in the mixture at a concentration of at least about 20 times greater than the normal upper usage concentration of the microbiocide, and is held within the pores of the thermoplastic powder.
The resulting concentrate is a substantially non-dusting, free-flowing powder which is readily incorporated into a second thermoplastic resin to produce a resulting article having the appropriate level of microbiocide.
Description
~257t335 8AC~GROUND OF THE INVENTION
The present invention relates to solid biocide dry blend concentrates and methods of making such concentrates.
Resin compositions are protected against fungal or bacterial attack by incorporating a microbiocide therein to prevent the deterioration of articles formed from the resin composition due to microbiological attack on the susceptible portion of the components of the resin system. In order for the microbiocide to be effective in the resin composition, it is necessary that it be compatible therewith and uniformly dispersible in the resin composition to avoid forming resin composition portions free of the microbiocide ~hich would be susceptible to attack.
In the past, microbiocide compositions have been added to resins either as a powder or as a liquid composition. To assure compatibility and adequate dispersibility of the microbiocide, it was believed necessary to add the microbiocide with a liquid carrier, such as a plasticizer for the resin. The presently employed procedures usually involve first mixing the microbiocide in a liquid carrier which solubilizes or disperses the microbiocide uniformly, followed by mixing the liquid composition with the final resin composi~ion. The liquid solvents or dispersants employed are those such as plasticizers which do not degrade the properties of the final resin product when employed at moderate concentrations. Unfortunately, the solubility of many of the commonly used microbiocides in common liquid resin additives is quite low. Therefore, it is difficult to incorporate a sufficiently high concentration of the ~Z57835 microbiocide with the resin while avoiding an undesirably high concentration of the liquid carrier. Also, this-procedure imposes restrictions on the choice of plasticizer to be used in the final resin composition. In addition, it is desirable to avoid using plasticizers with some thermoplastic resins such as polyurethanes and polyolefins.
Alternatively, it has been proposed to add the micro-biocide directly to a formable resin composition at the low effective concentration which prevents microbiological attack.
However, this procedure has proven to be unsatisfactory since the needed concentration of microbiocide is quite low, generally less than about one wt. % and usually between about 200 and lO00 parts per million. If the microbiocide were to be employed in the resin at higher concentrations, the toxicity of the final product made therefrom may be dangerously increased. Therefore, if this ptocedure is employed, the processor must continuously carefully weigh small amounts of microbiocides to be added to the final product. Since most microbiocides available for protecting resins are powders, continuous handling of a fine-powdered solid which can easily be dispersed in air presents a major toxico-logical problem to the personnel working in the immediate area.
To eliminate these toxicological problems, major changes would be required in presently employed commercial plastic processing techniques which would render them expensive and commercially unfeasible. For this reason, the commercial processor utilizes the microbiocide in a liquid carrier which is somewhat less innocuous than the microbiocide per se. In addition, in order to attain homogeneous dispersion of these low concentrations of microbiocide into the resin, it is necessary to extend the mixing
The present invention relates to solid biocide dry blend concentrates and methods of making such concentrates.
Resin compositions are protected against fungal or bacterial attack by incorporating a microbiocide therein to prevent the deterioration of articles formed from the resin composition due to microbiological attack on the susceptible portion of the components of the resin system. In order for the microbiocide to be effective in the resin composition, it is necessary that it be compatible therewith and uniformly dispersible in the resin composition to avoid forming resin composition portions free of the microbiocide ~hich would be susceptible to attack.
In the past, microbiocide compositions have been added to resins either as a powder or as a liquid composition. To assure compatibility and adequate dispersibility of the microbiocide, it was believed necessary to add the microbiocide with a liquid carrier, such as a plasticizer for the resin. The presently employed procedures usually involve first mixing the microbiocide in a liquid carrier which solubilizes or disperses the microbiocide uniformly, followed by mixing the liquid composition with the final resin composi~ion. The liquid solvents or dispersants employed are those such as plasticizers which do not degrade the properties of the final resin product when employed at moderate concentrations. Unfortunately, the solubility of many of the commonly used microbiocides in common liquid resin additives is quite low. Therefore, it is difficult to incorporate a sufficiently high concentration of the ~Z57835 microbiocide with the resin while avoiding an undesirably high concentration of the liquid carrier. Also, this-procedure imposes restrictions on the choice of plasticizer to be used in the final resin composition. In addition, it is desirable to avoid using plasticizers with some thermoplastic resins such as polyurethanes and polyolefins.
Alternatively, it has been proposed to add the micro-biocide directly to a formable resin composition at the low effective concentration which prevents microbiological attack.
However, this procedure has proven to be unsatisfactory since the needed concentration of microbiocide is quite low, generally less than about one wt. % and usually between about 200 and lO00 parts per million. If the microbiocide were to be employed in the resin at higher concentrations, the toxicity of the final product made therefrom may be dangerously increased. Therefore, if this ptocedure is employed, the processor must continuously carefully weigh small amounts of microbiocides to be added to the final product. Since most microbiocides available for protecting resins are powders, continuous handling of a fine-powdered solid which can easily be dispersed in air presents a major toxico-logical problem to the personnel working in the immediate area.
To eliminate these toxicological problems, major changes would be required in presently employed commercial plastic processing techniques which would render them expensive and commercially unfeasible. For this reason, the commercial processor utilizes the microbiocide in a liquid carrier which is somewhat less innocuous than the microbiocide per se. In addition, in order to attain homogeneous dispersion of these low concentrations of microbiocide into the resin, it is necessary to extend the mixing
-2-~257835 time of the resultant composition. Furthermore, mixing of these resin compositions containing low concentrations of microbiocides results in a substantial portion of the microbiocide being coated on the surface of the mixing apparatus rather than being homo-geneously dispersed throughout the resin.
One solution to many of these problems is described in U.S. Patent 4,086,297. The '297 patent describes a solid microbiocide concentrate composition comprising a homogeneous mixture of a solid thermoplastic resin and from 1 to 80 wt. ~ of at least one microbiocide which is insoluble in water. The microbiocide is readily dispersible or soluble in the resin at temperatures sufficiently high to permit plastic manipulation of the resin and the dispersion or solution of the microbiocide is sustained indefinitely upon cooling to ambient temperature while the diffusivity of the microbiocide in the resin under such conditions becomes vanishingly small. The microbiocide retains its microbiocidal activity in the resin and does not degrade or react with the resin in which it is dispersed. The composition described therein provides a convenient non-toxic dosage form of the microbiocide which is subsequently mixed with a second thermoplastic resin at a concentration of about 0.5 to 15 wt. ~
to obtain a homogeneous resin composition containing an effective amount of the microbiocide.
Although the '297 patent describes compositions acceptable in most instances, certain disadvantages remain. The process used to prepare the compositions of the '297 patent includes heating the microbiocide and resin to melt and soften the resin and to form a homogeneous mixture. ~he homogeneous mixture is subjected to shear forces and heat in a suitable ~.257~335 apparatus and then formed, such as by extrusion, milling or calendering. After cooling, the formed composition is broken up into small particles, e.g., pellets, thereby permitting its incorporation into other thermoplastic compositions to provide an appropriate concentration of microbiocide.
The particles resulting from the above process are not suitable for incorporation into plastisols. Nor are such particles usable when screening to filter out impurities such as paper, etc. is performed in preparing a dry blend prior to extrusion. In addition, the heating, mixing and cooling steps of the process of the '297 patent are relatively high in terms of energy costs. Finally, the heating step of the process of the '297 patent means that microbiocides which are heat sensitive cannot be used therein.
Another attempt at solving the problem of handling dusty additives which may be toxic is set forth in U.S. Patent 4,025,690. The '690 patent describes a process for preparing pigment additives for plastic materials in which the dusty addi-tives are absorbed by a polymer or copolymer of vinyl chloride in granular form. The process consists of treating the additives and polymer or copolymer in a mixer while raising the temperature to obtain absorption of the additive by the particles of the polymer or copolymer. ~he mass is then cooled to ambient temper-ature. While appropriate for some additives, powdery additives, such as microbiocides, continue to be dusty even after absorp-tion, and much of the biocide remains on the surface of the resin where it can flake off and cause excessive dusting during hand-ling. The biocide can be readily seen on the surface of the resin particles by microscopic examination.
~257~335 Accordingly, a need exists for a microbiocide concentrate which is useful in plastisol formulations, is more slmply prepared than prior art concentrates, and allows a broader range of micro-biocides to be employed, while retaining the reduced toxicity and ease of handling of the compositions of the '297 patent.
SUMMARY OF THE INVENTION
The present invention is a composition comprising a dry blend mixture of a porous non-foamed thermoplastic resin powder which has tiny "channels" or interstices criss-crossing through the powder particles and from 1 to 80 wt. ~ of a microbiocide based on the weight of the compositlon. The microbiocide is present in the mixture at a concentration of at least about 20 times greater than the normal upper usage concentration of the microbiocide, and is held within the pores of the thermoplastic powder.
The resulting concentrate is a substantially non-dusting, free-flowing powder which is readily incorporated into a second thermoplastic resin to produce a resulting article having the appropriate level of microbiocide.
According to the present invention, in one aspect, therefore, there is provided a composition comprising a dry blend mixture of:
a) a porous thermoplastic resin powder having a porosity of at least about 0.10 cc/g as measured by the mercury intrusion method or about 30% as measured on a void volume basis, wherein the particle size of the resin powder is between about 40 and about 300 mesh, said resin being selected from the group consisting of polyvinyl chloride, polyethylene, ~, ,, ~L257~335 pol y8 tyrene, polypropylene, nylon, styrene-butadiene copolymer, polycarbonate, polystyrene-polyphenylene oxide blend, polyphenylene oxide and an ethylene/acrylic acid salt ionomer; and b) from 1 to 80 weight percent, based on the weight of the composition, of a microbiocide selected from the group consisting of 10,10'-oxybisphenoxarsine; N-(tri-chloromethylthio)-4-cyclohexene-1,2-dicarboximide; 2,3,5-trichloro-4-propylsulfonyl pyridine; 2,3,4,5-tetrachloro-4-(methylsulfonyl)pyridine; zinc salt of l-hydroxypyridine-2-thione; N-(trichloromethylthio)phthalimide; N-(2-methyl-naphthyl)maleimide; cis-N-(1,1,2,2-tetrachlorethyl)-thio-4-cyclohexene-l~2-dicarboximide;l-isopropyl-3-methyl pyrazolyl-5-dimethyl carbamate; 3-methyl pyrazolyl dimethyl-carbamate; manganese ethylene bisdithiocarbamate; zinc ethylene bisdithiocarbamate; disodium ethylene bisdithio-carbamate; ferric dimethyl dithiocarbamate; zinc dimethyl dithiocarbamate; 2,4-dinitro-6-capryl phenol crotonate; p-chlorophenyl-p-chlorobenzene sulphonate; 2-N-octyl-4-isothiazolin-3-one; methyl~butyl carbamoyl)-2-benzimidazole carbamate; 2-(4-thiazolyl)benzimidazole; copper 8-hydroxyl-quinolinate; a-diethoxyphosphinodithioacetylurea; a-dimethoxylphosphinodithioacetylurea;diethoxyphosphinodi-thioacetamide; dimethoxyphosphinodithioacetamide;
bis(dimethylamido)phosphoryl fluoride; 2-cyclohexyl-3-isothiazolone; 4~5-dichloro-2-cyclohexyl-3-isothiazolone~
and tributyl tin fluoride, -5a-~.2~i7~35 the microbiocide being present in the mixture at a concentration of at least about 20 times greater than the normal upper usage concentration of the microbiocide, and the microbiocide being within the pores of the thermoplastic resin ~owder, said composition being substantially non-dusting.
The present in~ention, in another aspect, resides in a method of making a substantially non-dusting, free-flowing dry blend mixture comprising mixing:
a) a porous thermoplastic resin powder having a porosity of at least about 0.10 cc/g as measured by the mercury intrusion method or about 30% as measured on a void volume basis having a particle size between about 40 and about 300 mesh, said resin being selected from the group consisting of polyvinyl chloride, polyethylene, polystyrene, polypropylene, nylon, styrene-butadiene copolymer, polycarbonate, polystyrene-polyphenylene oxide blend, polyphenylene oxide and an ethylene/acrylic acid salt ionomer; and b) from 1 to 80 weight percent, based on the weight of the composition, of a microbiocide selected from the group consisting of 10, 10' -oxybisphenoxarsine; N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboximide;
2,3,5-trichloro-4-propylsulfonyl pyridine; 2,3,4,5-tetrachloro-4-(methylsulfonyl) pyridine; zinc salt of 1-hydroxypyridine-2-thione; N-(trichloromethylthio) phthalimide; N-(2-methyl-naphthyl)maleimide; cis-N-(1,1,2,2--5b-~25q83~
tetrachlorethyl)-thio-4-cyclohexene-1,2-dicarboximide; 1-iso-propyl-3-methyl pyrazolyl-5-dimethyl carbamate; 3-methyl pyrazolyl dimethyl-carbamate; manganese ethylene bisdithiocarbamate; zinc ethylene bisdithiocarbamate;
disodium ethylene bisthiocarbamate; ferric dimethyl dithiocarbamate; zinc dimethyl dithiocarbamate; 2,4-dinitro-6-capryl phenol crotonate; p-chlorophenyl-p-chlorobenzene sulphonate; 2-N-octyl-4-isothia7olin-3-one; methyl(butyl carbamoyl)-2-benzimidazole; carbamate; 2-(4-thiazolyl) benzimidazole; copper 8-hydroxyl-quinolinate; a-d i e t h o x y p h o s p h i n o d i t h i o a c e t yl u r e a; a -d i m e t h o x y 1 p h o s p h i n o d i t h i o a c e t y 1 u r e a;
diethoxyphosphinodithioacetamide; dimethoxy-phosphinodithioacetamide; bis(dimethylamido)phosphoryl fluoride; 2-cyclohexyl-3-isothiazolone; 4,5-dichloro-2-cyclohexyl-3-isothiazolone, and tributyl tin fluoride, in a high intensity high shear mixing apparatus at a temperature sufficient to open the pores of the powder, and then cooling the mixture to obtain a free-flowing powder which contains the microbiocide at a concentration of at least about 20 times greater than the normal upper usage concentration of the microbiocide, the microbiocide being held within the pores of the thermoplastic resin powder.
DETAILED DESCRIPTION OF THE INVENTION
The compositions of this invention contain the micro-biocide at a concentration which permits the subsequent incorporation of the resultant composition into a second thermoplastic resin cQmposition at a concentration between about -5c-~.z5~7~335 0.5 and 15 wt. % based upon the total weight of the resultant composition. When less than about 0.5 wt. ~ of the composition of this invention is incorporated into the second thermoplastic resin composition, less than homogeneous dispersion ma~ be ~ 5d-, ,, ~, "~
~.257~335 obtained which causes the resultant composition to have under-protected areas. When more than about 15 wt. % of the compositions of this invention is incorporated into a second thermoplastic resin which is different than the first thermo-plastic resin, the two resins may become incompatible. Inaddition, when more than about 15 wt. % of the composition of this invention is incorporated into a second thermoplastic resin, undesirable changes in the physical characteristics of the second thermoplastic resin occur in that they approach those of the first thermoplastic resin.
The concentration of microbiocide in the composition of this invention is between about 1 and 80 wt. ~, preferably from about 5 to about 55 wt. %, based upon the total weight of the thermoplastic composition. The microbiocide concentration depends upon the particular microbiocide and composition and its relative compatibility in the resin. In each instance, the microbiocide concentration is at least about 20 times greater than its normal upper usage concentration in the final resin composition. For example, 10,10'-oxybisphenoxarsine is used normally in a concentration up to 0.05 wt. ~;
N-(trichloromethylthio)-4-cyclo-hexene-1,2-dicarboximide is used normally in a concentration up to 0.5 wt. %; 2,3,4,6-tetrachloro-4-methylsulfonyl)pyridine is used normally in a concentration up to 0.75 wt. %; and'N-(trichloromethylthio)-phthalamide is used normally in a concentration up to 0.2 wt. %. In any event, the microbiocide concentration is controlled so it is present in an effective concentration in a second thermoplastic resin composition when added thereto at between about 0.5 and 15 wt. %
~z57~335 based upon the weight of the second thermoplastic resin composition.
In order to form the compositions of the present invention, the microbiocide must be a liquid at the temperature at which the pores of the porous resin open, or be readily soluble in a carrier which is readily absorbable by the porous resin. In addition, the microbiocide must be substantially retained within the porous resin powder until such time as the microbiocide containing powder is processed into the final article. The microbiocide must also retain its activity and not itself become degraded or degrade the resin either during mixing to produce the dry blend or after being incorporated into the resin. Stability of the microbiocide-resin concentrate is determined readily by visual observation wherein irreversible discoloration of the concentrate represents degradation of the composition so that it is not useful in the present invention.
For example, the microbiocide, ortho-benzyl parachlorophenol is miscible in resins, particularly vinyl resins but the resultant resin-microbiocide composition turns irreversibly black and therefore is not useful herein.
The degree of retention of microbiocidal activity in the resin-microbiocide concentrate is determined in any conventional manner wherein the concentrate is incorporated into a plasticized second resin to obtain a composition containing the normal upper range concentration of the microbiocide. This composition then is placed in a petri dish, innoculated with a microorganism against which the microbiocide is normally effective and the zone of inhibition is observed in a conventional manner.
~257835 Since the microbiocide in the concentrate is retained within the resin, the potential for human exposure is reduced relative to the microbiocide per se or the microbiocide in solution, even though present at higher concentrations than its effective concentration as a microbiocide. Accordingly, it can be incorporated subsequently in a second thermoplastic resin composition with reduced hazard to working personnel since the dusting problem associated with the powdered microbiocides is eliminated. Furthermore, the composition of this invention reduces contamination of processing and weighing equipment and facilitates clean-up of this equipment.
The compositions of this invention are not meant to have useful end use mechanical properties. Therefore, they must be incorporated into another thermoplastic resin to produce useful fsbricated thermoplastic products. However, due to their less toxic nature, the composition of this invention provides a significant advantage over the prior art compositions which do not use concentrates in that they can be processed safely by conventional thermoplastic resin fabrication techniques without requiring costly safety equipment and without the need for a liquid carrier for the microbiocide. Moreover, as compared to pellets, the dry blended powders of the present invention are easier to disperse, do not get caught in screens, and can be measured out more accurately.
2~ The compositions of the present invention are prepared by mixing a porous thermoplastic resin powder with a high concentration of microbiocide. A high intensity-high shear mixer is used to perform the mixing, e.g. a"Henschel"mixer. Any of those mixers well known in the art may be used including, for * Trademark ~ ,.~.
,.~, ~.257~335 example, a centrifugal impact mixer, high speed dispersion mixer, - ribbon blender, conical dry blender, double arm mixer, vortical action mixer, and other such mixers, such as those described in ~The Encyclopedia of Plastic Equipments" by Herbert R. Simons, Reinhold Pub. Corp., New York, N.Y. (1964).
When the powder and microbiocide are initially com-bined, very little absorption occurs. As mixing is performed, the mixture continues to heat up due to an external heàt source and/or friction and collisions between the particles until the pores of the resin open and absorb the microbiocide. At this temperature, commonly referred to as the "drop temperature~, the liquid has been completely absorbed by the resin and the mixture is cooled down to obtain a dry, free-flowing powder containing the microbiocide. The drop temperature will vary depending on the resin, the microbiocide, whether a carrier has been employed to dissolve the microbiocide, and the concentration of microbio-cide. The drop temperature will typically vary between about 160F and 220F.
The porosity of the porous resin is particularly important in the practice of the present invention. Various resins are known in the art which would be suitable for use in the present examples. The porosity should typically be between about 30-70% when measured on a void volume basis, or about 0.10-0.60 cc/g when measured by the mercury intrusion method (ASTM
D2873). Using this latter method, the measurement is made by forcing mercury under pressure into the pores of the resin. The volume of mercury forced into the resin is measured and recorded as cc/g. The particle size of the powder is typically between about 40 and about 300 mesh. Typical porous resins powders for _g _ ~.257835 use in the present invention include porous polyvinyl chloride res-ins available from B.F. Goodrich Chemical Co. under the trademark "GEON" and from General Tire & Rubber Co. under the trademark nVYGEN"; porous polyethylene, polypropylene and nylon resins available from Armak under the trademark "ACCUREL"; porous styrene-butadiene, polycarbonate, polyolefin, polystyrene, polyphenylene oxide, polystyrene-polyphenylene oxide blends: and ethylene/acrylic acid salts (ionomers). However, any such suitable porous resin powder having the appropriate porosity may be used in the practice of the present invention.
Suitable microbiocides include:
OBPA -- 10,10'-oxybisphenoxarsine '~ancide 89"-- N-(trichloromethylthio3-4-cyclohexene-1,2-dicarboximide "Dowcil A-40"2_ 2,3,5-trichloro-4-propylsulfonyl pyridine Zinc Omadine -- zinc salt of l-hydroxypyridine-2-thione "Fungitrol 11"3- N-(trichloromethylthio)phthalimide N-(2-methylnaphthyl) maleimide ~Difolatan~-4- cis-N-(1,1,2,2-tetrachloroethyl)-thio-4-cyclohexene-1,2-dicarboximide Isolan -- l-isopropyl-3-methyl pyrazolyl-5-dimethyl carbamate
One solution to many of these problems is described in U.S. Patent 4,086,297. The '297 patent describes a solid microbiocide concentrate composition comprising a homogeneous mixture of a solid thermoplastic resin and from 1 to 80 wt. ~ of at least one microbiocide which is insoluble in water. The microbiocide is readily dispersible or soluble in the resin at temperatures sufficiently high to permit plastic manipulation of the resin and the dispersion or solution of the microbiocide is sustained indefinitely upon cooling to ambient temperature while the diffusivity of the microbiocide in the resin under such conditions becomes vanishingly small. The microbiocide retains its microbiocidal activity in the resin and does not degrade or react with the resin in which it is dispersed. The composition described therein provides a convenient non-toxic dosage form of the microbiocide which is subsequently mixed with a second thermoplastic resin at a concentration of about 0.5 to 15 wt. ~
to obtain a homogeneous resin composition containing an effective amount of the microbiocide.
Although the '297 patent describes compositions acceptable in most instances, certain disadvantages remain. The process used to prepare the compositions of the '297 patent includes heating the microbiocide and resin to melt and soften the resin and to form a homogeneous mixture. ~he homogeneous mixture is subjected to shear forces and heat in a suitable ~.257~335 apparatus and then formed, such as by extrusion, milling or calendering. After cooling, the formed composition is broken up into small particles, e.g., pellets, thereby permitting its incorporation into other thermoplastic compositions to provide an appropriate concentration of microbiocide.
The particles resulting from the above process are not suitable for incorporation into plastisols. Nor are such particles usable when screening to filter out impurities such as paper, etc. is performed in preparing a dry blend prior to extrusion. In addition, the heating, mixing and cooling steps of the process of the '297 patent are relatively high in terms of energy costs. Finally, the heating step of the process of the '297 patent means that microbiocides which are heat sensitive cannot be used therein.
Another attempt at solving the problem of handling dusty additives which may be toxic is set forth in U.S. Patent 4,025,690. The '690 patent describes a process for preparing pigment additives for plastic materials in which the dusty addi-tives are absorbed by a polymer or copolymer of vinyl chloride in granular form. The process consists of treating the additives and polymer or copolymer in a mixer while raising the temperature to obtain absorption of the additive by the particles of the polymer or copolymer. ~he mass is then cooled to ambient temper-ature. While appropriate for some additives, powdery additives, such as microbiocides, continue to be dusty even after absorp-tion, and much of the biocide remains on the surface of the resin where it can flake off and cause excessive dusting during hand-ling. The biocide can be readily seen on the surface of the resin particles by microscopic examination.
~257~335 Accordingly, a need exists for a microbiocide concentrate which is useful in plastisol formulations, is more slmply prepared than prior art concentrates, and allows a broader range of micro-biocides to be employed, while retaining the reduced toxicity and ease of handling of the compositions of the '297 patent.
SUMMARY OF THE INVENTION
The present invention is a composition comprising a dry blend mixture of a porous non-foamed thermoplastic resin powder which has tiny "channels" or interstices criss-crossing through the powder particles and from 1 to 80 wt. ~ of a microbiocide based on the weight of the compositlon. The microbiocide is present in the mixture at a concentration of at least about 20 times greater than the normal upper usage concentration of the microbiocide, and is held within the pores of the thermoplastic powder.
The resulting concentrate is a substantially non-dusting, free-flowing powder which is readily incorporated into a second thermoplastic resin to produce a resulting article having the appropriate level of microbiocide.
According to the present invention, in one aspect, therefore, there is provided a composition comprising a dry blend mixture of:
a) a porous thermoplastic resin powder having a porosity of at least about 0.10 cc/g as measured by the mercury intrusion method or about 30% as measured on a void volume basis, wherein the particle size of the resin powder is between about 40 and about 300 mesh, said resin being selected from the group consisting of polyvinyl chloride, polyethylene, ~, ,, ~L257~335 pol y8 tyrene, polypropylene, nylon, styrene-butadiene copolymer, polycarbonate, polystyrene-polyphenylene oxide blend, polyphenylene oxide and an ethylene/acrylic acid salt ionomer; and b) from 1 to 80 weight percent, based on the weight of the composition, of a microbiocide selected from the group consisting of 10,10'-oxybisphenoxarsine; N-(tri-chloromethylthio)-4-cyclohexene-1,2-dicarboximide; 2,3,5-trichloro-4-propylsulfonyl pyridine; 2,3,4,5-tetrachloro-4-(methylsulfonyl)pyridine; zinc salt of l-hydroxypyridine-2-thione; N-(trichloromethylthio)phthalimide; N-(2-methyl-naphthyl)maleimide; cis-N-(1,1,2,2-tetrachlorethyl)-thio-4-cyclohexene-l~2-dicarboximide;l-isopropyl-3-methyl pyrazolyl-5-dimethyl carbamate; 3-methyl pyrazolyl dimethyl-carbamate; manganese ethylene bisdithiocarbamate; zinc ethylene bisdithiocarbamate; disodium ethylene bisdithio-carbamate; ferric dimethyl dithiocarbamate; zinc dimethyl dithiocarbamate; 2,4-dinitro-6-capryl phenol crotonate; p-chlorophenyl-p-chlorobenzene sulphonate; 2-N-octyl-4-isothiazolin-3-one; methyl~butyl carbamoyl)-2-benzimidazole carbamate; 2-(4-thiazolyl)benzimidazole; copper 8-hydroxyl-quinolinate; a-diethoxyphosphinodithioacetylurea; a-dimethoxylphosphinodithioacetylurea;diethoxyphosphinodi-thioacetamide; dimethoxyphosphinodithioacetamide;
bis(dimethylamido)phosphoryl fluoride; 2-cyclohexyl-3-isothiazolone; 4~5-dichloro-2-cyclohexyl-3-isothiazolone~
and tributyl tin fluoride, -5a-~.2~i7~35 the microbiocide being present in the mixture at a concentration of at least about 20 times greater than the normal upper usage concentration of the microbiocide, and the microbiocide being within the pores of the thermoplastic resin ~owder, said composition being substantially non-dusting.
The present in~ention, in another aspect, resides in a method of making a substantially non-dusting, free-flowing dry blend mixture comprising mixing:
a) a porous thermoplastic resin powder having a porosity of at least about 0.10 cc/g as measured by the mercury intrusion method or about 30% as measured on a void volume basis having a particle size between about 40 and about 300 mesh, said resin being selected from the group consisting of polyvinyl chloride, polyethylene, polystyrene, polypropylene, nylon, styrene-butadiene copolymer, polycarbonate, polystyrene-polyphenylene oxide blend, polyphenylene oxide and an ethylene/acrylic acid salt ionomer; and b) from 1 to 80 weight percent, based on the weight of the composition, of a microbiocide selected from the group consisting of 10, 10' -oxybisphenoxarsine; N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboximide;
2,3,5-trichloro-4-propylsulfonyl pyridine; 2,3,4,5-tetrachloro-4-(methylsulfonyl) pyridine; zinc salt of 1-hydroxypyridine-2-thione; N-(trichloromethylthio) phthalimide; N-(2-methyl-naphthyl)maleimide; cis-N-(1,1,2,2--5b-~25q83~
tetrachlorethyl)-thio-4-cyclohexene-1,2-dicarboximide; 1-iso-propyl-3-methyl pyrazolyl-5-dimethyl carbamate; 3-methyl pyrazolyl dimethyl-carbamate; manganese ethylene bisdithiocarbamate; zinc ethylene bisdithiocarbamate;
disodium ethylene bisthiocarbamate; ferric dimethyl dithiocarbamate; zinc dimethyl dithiocarbamate; 2,4-dinitro-6-capryl phenol crotonate; p-chlorophenyl-p-chlorobenzene sulphonate; 2-N-octyl-4-isothia7olin-3-one; methyl(butyl carbamoyl)-2-benzimidazole; carbamate; 2-(4-thiazolyl) benzimidazole; copper 8-hydroxyl-quinolinate; a-d i e t h o x y p h o s p h i n o d i t h i o a c e t yl u r e a; a -d i m e t h o x y 1 p h o s p h i n o d i t h i o a c e t y 1 u r e a;
diethoxyphosphinodithioacetamide; dimethoxy-phosphinodithioacetamide; bis(dimethylamido)phosphoryl fluoride; 2-cyclohexyl-3-isothiazolone; 4,5-dichloro-2-cyclohexyl-3-isothiazolone, and tributyl tin fluoride, in a high intensity high shear mixing apparatus at a temperature sufficient to open the pores of the powder, and then cooling the mixture to obtain a free-flowing powder which contains the microbiocide at a concentration of at least about 20 times greater than the normal upper usage concentration of the microbiocide, the microbiocide being held within the pores of the thermoplastic resin powder.
DETAILED DESCRIPTION OF THE INVENTION
The compositions of this invention contain the micro-biocide at a concentration which permits the subsequent incorporation of the resultant composition into a second thermoplastic resin cQmposition at a concentration between about -5c-~.z5~7~335 0.5 and 15 wt. % based upon the total weight of the resultant composition. When less than about 0.5 wt. ~ of the composition of this invention is incorporated into the second thermoplastic resin composition, less than homogeneous dispersion ma~ be ~ 5d-, ,, ~, "~
~.257~335 obtained which causes the resultant composition to have under-protected areas. When more than about 15 wt. % of the compositions of this invention is incorporated into a second thermoplastic resin which is different than the first thermo-plastic resin, the two resins may become incompatible. Inaddition, when more than about 15 wt. % of the composition of this invention is incorporated into a second thermoplastic resin, undesirable changes in the physical characteristics of the second thermoplastic resin occur in that they approach those of the first thermoplastic resin.
The concentration of microbiocide in the composition of this invention is between about 1 and 80 wt. ~, preferably from about 5 to about 55 wt. %, based upon the total weight of the thermoplastic composition. The microbiocide concentration depends upon the particular microbiocide and composition and its relative compatibility in the resin. In each instance, the microbiocide concentration is at least about 20 times greater than its normal upper usage concentration in the final resin composition. For example, 10,10'-oxybisphenoxarsine is used normally in a concentration up to 0.05 wt. ~;
N-(trichloromethylthio)-4-cyclo-hexene-1,2-dicarboximide is used normally in a concentration up to 0.5 wt. %; 2,3,4,6-tetrachloro-4-methylsulfonyl)pyridine is used normally in a concentration up to 0.75 wt. %; and'N-(trichloromethylthio)-phthalamide is used normally in a concentration up to 0.2 wt. %. In any event, the microbiocide concentration is controlled so it is present in an effective concentration in a second thermoplastic resin composition when added thereto at between about 0.5 and 15 wt. %
~z57~335 based upon the weight of the second thermoplastic resin composition.
In order to form the compositions of the present invention, the microbiocide must be a liquid at the temperature at which the pores of the porous resin open, or be readily soluble in a carrier which is readily absorbable by the porous resin. In addition, the microbiocide must be substantially retained within the porous resin powder until such time as the microbiocide containing powder is processed into the final article. The microbiocide must also retain its activity and not itself become degraded or degrade the resin either during mixing to produce the dry blend or after being incorporated into the resin. Stability of the microbiocide-resin concentrate is determined readily by visual observation wherein irreversible discoloration of the concentrate represents degradation of the composition so that it is not useful in the present invention.
For example, the microbiocide, ortho-benzyl parachlorophenol is miscible in resins, particularly vinyl resins but the resultant resin-microbiocide composition turns irreversibly black and therefore is not useful herein.
The degree of retention of microbiocidal activity in the resin-microbiocide concentrate is determined in any conventional manner wherein the concentrate is incorporated into a plasticized second resin to obtain a composition containing the normal upper range concentration of the microbiocide. This composition then is placed in a petri dish, innoculated with a microorganism against which the microbiocide is normally effective and the zone of inhibition is observed in a conventional manner.
~257835 Since the microbiocide in the concentrate is retained within the resin, the potential for human exposure is reduced relative to the microbiocide per se or the microbiocide in solution, even though present at higher concentrations than its effective concentration as a microbiocide. Accordingly, it can be incorporated subsequently in a second thermoplastic resin composition with reduced hazard to working personnel since the dusting problem associated with the powdered microbiocides is eliminated. Furthermore, the composition of this invention reduces contamination of processing and weighing equipment and facilitates clean-up of this equipment.
The compositions of this invention are not meant to have useful end use mechanical properties. Therefore, they must be incorporated into another thermoplastic resin to produce useful fsbricated thermoplastic products. However, due to their less toxic nature, the composition of this invention provides a significant advantage over the prior art compositions which do not use concentrates in that they can be processed safely by conventional thermoplastic resin fabrication techniques without requiring costly safety equipment and without the need for a liquid carrier for the microbiocide. Moreover, as compared to pellets, the dry blended powders of the present invention are easier to disperse, do not get caught in screens, and can be measured out more accurately.
2~ The compositions of the present invention are prepared by mixing a porous thermoplastic resin powder with a high concentration of microbiocide. A high intensity-high shear mixer is used to perform the mixing, e.g. a"Henschel"mixer. Any of those mixers well known in the art may be used including, for * Trademark ~ ,.~.
,.~, ~.257~335 example, a centrifugal impact mixer, high speed dispersion mixer, - ribbon blender, conical dry blender, double arm mixer, vortical action mixer, and other such mixers, such as those described in ~The Encyclopedia of Plastic Equipments" by Herbert R. Simons, Reinhold Pub. Corp., New York, N.Y. (1964).
When the powder and microbiocide are initially com-bined, very little absorption occurs. As mixing is performed, the mixture continues to heat up due to an external heàt source and/or friction and collisions between the particles until the pores of the resin open and absorb the microbiocide. At this temperature, commonly referred to as the "drop temperature~, the liquid has been completely absorbed by the resin and the mixture is cooled down to obtain a dry, free-flowing powder containing the microbiocide. The drop temperature will vary depending on the resin, the microbiocide, whether a carrier has been employed to dissolve the microbiocide, and the concentration of microbio-cide. The drop temperature will typically vary between about 160F and 220F.
The porosity of the porous resin is particularly important in the practice of the present invention. Various resins are known in the art which would be suitable for use in the present examples. The porosity should typically be between about 30-70% when measured on a void volume basis, or about 0.10-0.60 cc/g when measured by the mercury intrusion method (ASTM
D2873). Using this latter method, the measurement is made by forcing mercury under pressure into the pores of the resin. The volume of mercury forced into the resin is measured and recorded as cc/g. The particle size of the powder is typically between about 40 and about 300 mesh. Typical porous resins powders for _g _ ~.257835 use in the present invention include porous polyvinyl chloride res-ins available from B.F. Goodrich Chemical Co. under the trademark "GEON" and from General Tire & Rubber Co. under the trademark nVYGEN"; porous polyethylene, polypropylene and nylon resins available from Armak under the trademark "ACCUREL"; porous styrene-butadiene, polycarbonate, polyolefin, polystyrene, polyphenylene oxide, polystyrene-polyphenylene oxide blends: and ethylene/acrylic acid salts (ionomers). However, any such suitable porous resin powder having the appropriate porosity may be used in the practice of the present invention.
Suitable microbiocides include:
OBPA -- 10,10'-oxybisphenoxarsine '~ancide 89"-- N-(trichloromethylthio3-4-cyclohexene-1,2-dicarboximide "Dowcil A-40"2_ 2,3,5-trichloro-4-propylsulfonyl pyridine Zinc Omadine -- zinc salt of l-hydroxypyridine-2-thione "Fungitrol 11"3- N-(trichloromethylthio)phthalimide N-(2-methylnaphthyl) maleimide ~Difolatan~-4- cis-N-(1,1,2,2-tetrachloroethyl)-thio-4-cyclohexene-1,2-dicarboximide Isolan -- l-isopropyl-3-methyl pyrazolyl-5-dimethyl carbamate
3-methyl-pyrazolyl dimethylcarbamate Maneb -- manganese ethylene bisdithiocarbamate Zineb -- zinc analog of Maneb Nabam -- disodium analog of Maneb Ferbam -- ferric dimethyl dithiocarbamate Ziram -- zinc analog of Ferbam Karathane -- 2,4-dinitro-6-capryl phenol crotonate Ovotran -- p-chlorophenyl-p-chlorobenzenesulphonate 'rademark
4.
r ~2578~s ~kane M-8 -~ 2-N-octyl-4-isothiazolin-3-one Benomyl -- methyl-l(butylcarbamoyl)-2-benzimidazole carbamate ~etasol TK-10~'-- 2-(4-thiazolyl) benzimidazole '~opper-~ "-- copper 8-hydroxy-quinolinate -diethoxyphosphinodithioacetylurea ~ -dimethoxyphosphinodithioacetylurea Diethoxyphosphinodithioacetamide Dimethoxyphosphinodithioacetamide 8is(dimethylamido) phosphoryl fluoride Tributyl tin fluoride and mixtures thereof.
The preferred microbiocides are 10,10'-oxybisphenoxarsine; N-~trichloromethylthio)-4-cyclohexene-1,2-dicarboximide; 2,3,5,6-tetrachloro-4-(methylsulfonyl) pyridine;
N-(2-methylnaphthyl) maleimide; and N-(trichloromethyl-thio)phthalimide since they are relatively easy to incorporate into a wide variety of resins at high concentration without significant loss of microbiological activity and without significant degradation of the resin.
- If the microbiocide is a solid at ambient temperatures, it must be dissolved in a suitable carrier prior to mixing with the porous resin powder or melted during the mixing stage. The carrier must be inert to the microbiocide, the resin powder, the resin of the ultimate product, and any other ingredients of any of the above. Suitable carriers include commonly used plasticizers such as the phthalates, azelates, adipates, sebacat~s and epoxidized soybean oil. The carrier is used in amounts sufficient to dissolve the microbiocide, and preferably in the minimum amount necessary to do so since excess amounts may . ~rradel[ ark 6.
7.
~,2S~835 adversely affect the properties of the concentrate and the ultimate article.
A carrier substantially improves the transport of biocide into the resin particle matrix during the dry blending cycle. On cooling, the biocide is trapped in the resin particle. If a carrier is not used and the biocide does not melt during mixing, much of the biocide remains on the surface of the resin where it can flake off and cause excessive dusting during handling. Such unabsorbed biocide can be readily seen on the surface of the resin particles by microscopic examination.
The compositions of this invention are blended with a second thermoplastic composition by conventional means. The concentrated microbiocide-resin composition can be added during compounding of the second thermoplastic composition or can be incorporated therein after it has been compounded but prior to fabrication of the second thermoplastic composition in any conventional manner such as extrusion, melting or calendering.
~ All that is required is that the microbiocide-containing composition and the second thermoplastic composition be com-patible so that a homogeneous final composition results. The microbiocide-containing composition should have a softening temperature below or within the range of temperatures encountered during conventional processing of the second thermoplastic composition. These temperatures are within the range of between about 250F and about 600F. It is preferred that the resin-microbiocide concentrates have a softening temperature within the range of about 200F to 500F.
In forming the microbiocide-containing composition of this invention, the usual resin additives optionally can be 1257~33~
included. If desired, a plasticizer for the resin can be incorporated with the composition. However, it has been found that when higher concentrations of microbiocide are employed, a reduced concentration of plasticizer must be employed to avoid S incompatibility of the microbiocide and resin. The concentration of plasticizer that can be tolerated in the compositions of this invention also is dependent upon the chemical compositions of the resin, the plasticizer and the microbiocide. Generally, moderate plasticizer concentrations can be tolerated within the range of between about 5 and 20 wt. % when the microbiocides are employed at concentrations of 50 wt. % or above. Higher plasticizer concentrations can be employed with lower concentrations of microbiocide. Thus, while the compositions of this invention can be made without plasticizers, it should be noted that it is not intended that this invention be limited by their exclusion.
To determine suitable plasticizers of a particular resin-microbiocide system, all that is necessary is the addition of the plasticizer, within the range noted above, to the resin-microbiocide composition, mixing of the resultant composition, and a visual determination for homogeneity. Any of the conventional resin plasticizers can be employed including dialkyl phthalates, epoxy plasticizers, polyester plasticizers, dialkyl phosphites and the like. In addition, the usual resin additives can be included such as ultraviolet stabilizers, heat stabilizers, fillers, dyes, pigments, lubricants and the like.
Representative suitable thermoplastic resins which can be compounded with the microbiocide-resin compositions of the present invention include polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyurethanes, polyamides, polyolefins, ~.2~7~35 polystyrene, vinyl chloride-acrylonitrile copolymers, polyesters and the like.
The concentrates of the present invention are more readily and less expensively made than the concentrates of the S prior art. Moreover, the compositions of the present invention are more rapidly dispersed in the resin than the concentrates of the prior art. It is also possible to use a wider range of biocides since lower processing temperatures are involved in making the concentrate. Another advantage is more accurate measuring or metering.
In order to further illustrate the present invention and the advantages thereof, the following specific examples are given, it being understood that these examples are intended only to be illustrative without serving as a limitation on the scope of the present invention.
These examples illustrate the production of a typical concentrate according to the present invention.
The following ingredients are mixed in a~enschel~mixer at the wt. ~ indicated:
Ex . 1 Ex . 2 Porous polyvinyl chlo~de resin '~Diamond 450"PVC) 65.00 55.50 Dioctyl phthalate plasticizer 20.00 17.23 N-(2-methylnaphthyl) maleimide 12.50 25.00 Ca, Zn stabilizer ~Mark 538)"*** 0.50 0.50 Epoxidized soybean oil plasticizer 1.83 1.60 Stearic acid 0.17 0.17 TotallQ0.00 100.00 * Trademark ** -*** -$2~q835 The average particle size of the resin is 40-140 mesh, and the average porosity is 0.21-0.30 cc/g (ASTM D2873).
The mixture is mixed until a drop temperature of 180F
is obtained, at which time the microbiocide is absorbed resulting in a free-flowing non-dusting powder which is cooled.
These examples illustra~e that the dry blend concentrate of the present invention can be extruded and pelletized.
10The dry blend of Example 1 is extruded at temperatures of 150 and 160C and at 125 rpm, and the dry blend of Example 2 is extruded at temperatures of 140 and 150C. The dry blends are extruded alone or in combination with 0.1 wt.% of color tracer (Carmine Red HF-3C). After extrusion and cooling, the extruded rod is pelletized.
Each of the dry blends extrudes and pelletizes well.
The pellets not containing color tracer are a clear yellow color, and the pellets containing the color tracer are a clear and uniform red color.
and COMPARATIVE EXAMPLES A AND B
The dispersion characteristics of the microbiocide-dry blend formulations of Examples 1 and 2 in a typical low plasticizer level base are compared by the gel-count method to the same base without added microbiocide-dry blend (Comparative Example A) and the same base to which is added the same amount of raw polyvinyl chloride resin (Comparative Example B).
~Z57~335 - The formulation of the base is as follows:
ComPonent Wei~ht(q) Polyvinyl chloride resin 100.00 Di-2-ethylhexyl phthalate 40.00 Epoxidized soybean oil 7.70 W Stabilizer"(Mark 202A)" 1.00 Heat Stabilizer"(Mark RCB)"* 3.50 ~eat Stabilizer"(Mark C)"* 1.50 Stearic Acid 0.25 Films are prepared by milling the components of the base until a uniform dispersion is obtained, at which time about 9.05~ by weight of carbon black is added to each of the four samples and 1~ by weight of the dry blend of Example 1 (Example
r ~2578~s ~kane M-8 -~ 2-N-octyl-4-isothiazolin-3-one Benomyl -- methyl-l(butylcarbamoyl)-2-benzimidazole carbamate ~etasol TK-10~'-- 2-(4-thiazolyl) benzimidazole '~opper-~ "-- copper 8-hydroxy-quinolinate -diethoxyphosphinodithioacetylurea ~ -dimethoxyphosphinodithioacetylurea Diethoxyphosphinodithioacetamide Dimethoxyphosphinodithioacetamide 8is(dimethylamido) phosphoryl fluoride Tributyl tin fluoride and mixtures thereof.
The preferred microbiocides are 10,10'-oxybisphenoxarsine; N-~trichloromethylthio)-4-cyclohexene-1,2-dicarboximide; 2,3,5,6-tetrachloro-4-(methylsulfonyl) pyridine;
N-(2-methylnaphthyl) maleimide; and N-(trichloromethyl-thio)phthalimide since they are relatively easy to incorporate into a wide variety of resins at high concentration without significant loss of microbiological activity and without significant degradation of the resin.
- If the microbiocide is a solid at ambient temperatures, it must be dissolved in a suitable carrier prior to mixing with the porous resin powder or melted during the mixing stage. The carrier must be inert to the microbiocide, the resin powder, the resin of the ultimate product, and any other ingredients of any of the above. Suitable carriers include commonly used plasticizers such as the phthalates, azelates, adipates, sebacat~s and epoxidized soybean oil. The carrier is used in amounts sufficient to dissolve the microbiocide, and preferably in the minimum amount necessary to do so since excess amounts may . ~rradel[ ark 6.
7.
~,2S~835 adversely affect the properties of the concentrate and the ultimate article.
A carrier substantially improves the transport of biocide into the resin particle matrix during the dry blending cycle. On cooling, the biocide is trapped in the resin particle. If a carrier is not used and the biocide does not melt during mixing, much of the biocide remains on the surface of the resin where it can flake off and cause excessive dusting during handling. Such unabsorbed biocide can be readily seen on the surface of the resin particles by microscopic examination.
The compositions of this invention are blended with a second thermoplastic composition by conventional means. The concentrated microbiocide-resin composition can be added during compounding of the second thermoplastic composition or can be incorporated therein after it has been compounded but prior to fabrication of the second thermoplastic composition in any conventional manner such as extrusion, melting or calendering.
~ All that is required is that the microbiocide-containing composition and the second thermoplastic composition be com-patible so that a homogeneous final composition results. The microbiocide-containing composition should have a softening temperature below or within the range of temperatures encountered during conventional processing of the second thermoplastic composition. These temperatures are within the range of between about 250F and about 600F. It is preferred that the resin-microbiocide concentrates have a softening temperature within the range of about 200F to 500F.
In forming the microbiocide-containing composition of this invention, the usual resin additives optionally can be 1257~33~
included. If desired, a plasticizer for the resin can be incorporated with the composition. However, it has been found that when higher concentrations of microbiocide are employed, a reduced concentration of plasticizer must be employed to avoid S incompatibility of the microbiocide and resin. The concentration of plasticizer that can be tolerated in the compositions of this invention also is dependent upon the chemical compositions of the resin, the plasticizer and the microbiocide. Generally, moderate plasticizer concentrations can be tolerated within the range of between about 5 and 20 wt. % when the microbiocides are employed at concentrations of 50 wt. % or above. Higher plasticizer concentrations can be employed with lower concentrations of microbiocide. Thus, while the compositions of this invention can be made without plasticizers, it should be noted that it is not intended that this invention be limited by their exclusion.
To determine suitable plasticizers of a particular resin-microbiocide system, all that is necessary is the addition of the plasticizer, within the range noted above, to the resin-microbiocide composition, mixing of the resultant composition, and a visual determination for homogeneity. Any of the conventional resin plasticizers can be employed including dialkyl phthalates, epoxy plasticizers, polyester plasticizers, dialkyl phosphites and the like. In addition, the usual resin additives can be included such as ultraviolet stabilizers, heat stabilizers, fillers, dyes, pigments, lubricants and the like.
Representative suitable thermoplastic resins which can be compounded with the microbiocide-resin compositions of the present invention include polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyurethanes, polyamides, polyolefins, ~.2~7~35 polystyrene, vinyl chloride-acrylonitrile copolymers, polyesters and the like.
The concentrates of the present invention are more readily and less expensively made than the concentrates of the S prior art. Moreover, the compositions of the present invention are more rapidly dispersed in the resin than the concentrates of the prior art. It is also possible to use a wider range of biocides since lower processing temperatures are involved in making the concentrate. Another advantage is more accurate measuring or metering.
In order to further illustrate the present invention and the advantages thereof, the following specific examples are given, it being understood that these examples are intended only to be illustrative without serving as a limitation on the scope of the present invention.
These examples illustrate the production of a typical concentrate according to the present invention.
The following ingredients are mixed in a~enschel~mixer at the wt. ~ indicated:
Ex . 1 Ex . 2 Porous polyvinyl chlo~de resin '~Diamond 450"PVC) 65.00 55.50 Dioctyl phthalate plasticizer 20.00 17.23 N-(2-methylnaphthyl) maleimide 12.50 25.00 Ca, Zn stabilizer ~Mark 538)"*** 0.50 0.50 Epoxidized soybean oil plasticizer 1.83 1.60 Stearic acid 0.17 0.17 TotallQ0.00 100.00 * Trademark ** -*** -$2~q835 The average particle size of the resin is 40-140 mesh, and the average porosity is 0.21-0.30 cc/g (ASTM D2873).
The mixture is mixed until a drop temperature of 180F
is obtained, at which time the microbiocide is absorbed resulting in a free-flowing non-dusting powder which is cooled.
These examples illustra~e that the dry blend concentrate of the present invention can be extruded and pelletized.
10The dry blend of Example 1 is extruded at temperatures of 150 and 160C and at 125 rpm, and the dry blend of Example 2 is extruded at temperatures of 140 and 150C. The dry blends are extruded alone or in combination with 0.1 wt.% of color tracer (Carmine Red HF-3C). After extrusion and cooling, the extruded rod is pelletized.
Each of the dry blends extrudes and pelletizes well.
The pellets not containing color tracer are a clear yellow color, and the pellets containing the color tracer are a clear and uniform red color.
and COMPARATIVE EXAMPLES A AND B
The dispersion characteristics of the microbiocide-dry blend formulations of Examples 1 and 2 in a typical low plasticizer level base are compared by the gel-count method to the same base without added microbiocide-dry blend (Comparative Example A) and the same base to which is added the same amount of raw polyvinyl chloride resin (Comparative Example B).
~Z57~335 - The formulation of the base is as follows:
ComPonent Wei~ht(q) Polyvinyl chloride resin 100.00 Di-2-ethylhexyl phthalate 40.00 Epoxidized soybean oil 7.70 W Stabilizer"(Mark 202A)" 1.00 Heat Stabilizer"(Mark RCB)"* 3.50 ~eat Stabilizer"(Mark C)"* 1.50 Stearic Acid 0.25 Films are prepared by milling the components of the base until a uniform dispersion is obtained, at which time about 9.05~ by weight of carbon black is added to each of the four samples and 1~ by weight of the dry blend of Example 1 (Example
5), Example 2 (Example 6) or raw PVC resin (Comparative Example B) is added. Milling is continued for five additional minutes and then each sample is drawn out into a thin film approximately 2 to 3 mils in thickness.
The number of gels per square inch are counted with the following results:
ExamPle Observation Averaqe 5 7 6 6.0
The number of gels per square inch are counted with the following results:
ExamPle Observation Averaqe 5 7 6 6.0
6 5 6 ~ 6.3 A 4 8 6 6.0 B 8 9 10 8.3 From these results, it can be seen that the dry blends of Examples 1 and 2 readily disperse in the base formulation, wherea~ the sample containing raw PVC tcomparative Example B) contains areas which are not homogeneous.
* Trademark 3LZ5q~335 The dry blends of Examples 1 and 2 can also be tested for dispersion by the color tracer method. Pellets of dry blend from Example 3 tExample 7) and Example 4 (Example 8), each containing color tracer, are blended with the following highly plasticized formulation:
ComPOnent Weiqht(g) PVC Resin 100 ~Santicizer 711~* 32 Diisodecyl phthalate40 Epoxidized soybean oil 6 ~Mark RCB~(Ba, Cd, Zn) 3 ~Mark 446~(U.V. stabilizer) 0.5 ~IThermolite 49"(Tin) Calcium Stearate 0.29 Stearic Acid 0~29 TiO2 29 ~Atomite~l(calcium carbonate) 10 The resulting blends are extruded at temperatures of 150 and 160C at 75 rpm using a ribbon die. There is no trace of uneven color distribution in either of the extruded ribbons indicating uniform dispersion of the dry blend and microbiocide throughout the ribbon.
The following example illustrates that stratification and separation do not occur in the dry blend during shipping and handling.
* Trademark for a dialkyl adipate plasticizer.
** Trademark for an organotin stabllizer for PvC resins.
*** Trademark.
~ZS7835 The following sample is prepared, the ingredients being present in the indicated wt.~:
Inqredients ~olyvinyl chloride resin73.0 (Diamond PVC 450) N-(2-methylnaphthyl) maleimide 12.5 Calcium-zinc stabilizer 0.5 Diisodecyl phthalate 14.0 Total lO0.0 The sample is prepared by blending in a ~enschel mixer to a drop temperature of 220F, and then cooling.
A sample is placed in a container which is placed in the trunk of an automobile and removed after the automobile has traveled 1200 miles.
Representative portions from the top, middle and bottom of the container are analyzed for microbiocide [N-(2-methylnaphthyl maleimide] with the following results:
wt.~
ToP Middle Bottom 13.4 14.1 13.4 From these results, it can be concluded that no significant migration or stratification of the microbiocide occurs during transportation and handling.
~257~335 The following examples illustrate the production of a typical concentrate according to the present invention using a different microbiocide than used in the preceding examples.
The following ingredients are mixed in a"~enschel"mixer at the wt. ~ indicated:
Ex.ll Ex.12 Porous polyvinyl chloride"
resin"(Diamond 450 PVC) 78.5 Porous polyvinyl chloride resin "(Pantasote XTR-3) * - 79.5 Diisodecyl phthalate (DIDP) plasticizer 15.0 15.0 10,10'-oxybisphenoxarsine (OBPA) 5.0 5.0 Ca, Zn stabilizer ~(Mark 538)" 0.5 0-5 Stearic acid 1.0 In each example, the resin is heated in the ~enschel mixer at 200F, followed by the addition of a solution of the OBPA and DIDP which has been heated to 320F. The temperature of the mixtures is then raised to 210F. Next, the stabilizer and stearic acid are added. Mixing is continued until a drop temperature of 220F is obtained, at which time the microbiocide is absorbed, resulting in a free-flowing non-dusting powder which is cooled.
The following examples illustrate the importance of the microbiocide either being a liquid at the drop temperature or being dissolved in a carrier prior to mixing with the porous resin.
* Trademark ~ ~J _ _ ~257835 Dry blends are prepared in a"Henschel ~ixer"by blending all of the ingredients until the temperature reaches 220F. The blend of Comparative Example C is prepared by an addition of biocide directly to the resin. The blend of Example 12 is prepared by first dissolving the biocide in dioctyl phthalate plasticizer by heating to 250F. The hot solution is added directly to the resin during the mixing cycle. During preparation and during discharge from the"~enschel Mixer', both blends are observed to determine whether dusting occurs. The biocide dry blend particles are also examined under a 20X
magnification microscope for signs of neat biocide which has not been forced into the interstices of the resin particle.
The ingredients are present in the following wt. %:
Inqredients ExamPle 12comParatiVe ExamPle C
Polyvinyl Chloride *62.0 87.0 resin ~Diamond 450)~
N-(2-methylnaphthyl) 12.5 12.5 maleimide Dioctyl phthalate 25.0 20 Calcium stearate 0.5 0 5 Total 100.0 100.0 - Substantial dusting during both discharge and blending i5 observed from the blend of Comparative Example C. Excessive biocide is seen on the particle surface and in the dry blend upon microscopic examination of the blend of Comparative Example C.
In contrast, no dusting during discharge or blending is observed from the blend of Example 12. Moreover, no biocide is seen on the surface of the resin particles nor in the dry blend.
* Trademark -20-~257~35 While the invention has been described in terms of various preferred embodiments, one skilled in the art will appreciate that various modifications, substitutions, omissions, and changes may be made without departing from the spirit thereof. Accordingly, it is intended that the scope of the present invention be limited solely by the scope of the following claims.
* Trademark 3LZ5q~335 The dry blends of Examples 1 and 2 can also be tested for dispersion by the color tracer method. Pellets of dry blend from Example 3 tExample 7) and Example 4 (Example 8), each containing color tracer, are blended with the following highly plasticized formulation:
ComPOnent Weiqht(g) PVC Resin 100 ~Santicizer 711~* 32 Diisodecyl phthalate40 Epoxidized soybean oil 6 ~Mark RCB~(Ba, Cd, Zn) 3 ~Mark 446~(U.V. stabilizer) 0.5 ~IThermolite 49"(Tin) Calcium Stearate 0.29 Stearic Acid 0~29 TiO2 29 ~Atomite~l(calcium carbonate) 10 The resulting blends are extruded at temperatures of 150 and 160C at 75 rpm using a ribbon die. There is no trace of uneven color distribution in either of the extruded ribbons indicating uniform dispersion of the dry blend and microbiocide throughout the ribbon.
The following example illustrates that stratification and separation do not occur in the dry blend during shipping and handling.
* Trademark for a dialkyl adipate plasticizer.
** Trademark for an organotin stabllizer for PvC resins.
*** Trademark.
~ZS7835 The following sample is prepared, the ingredients being present in the indicated wt.~:
Inqredients ~olyvinyl chloride resin73.0 (Diamond PVC 450) N-(2-methylnaphthyl) maleimide 12.5 Calcium-zinc stabilizer 0.5 Diisodecyl phthalate 14.0 Total lO0.0 The sample is prepared by blending in a ~enschel mixer to a drop temperature of 220F, and then cooling.
A sample is placed in a container which is placed in the trunk of an automobile and removed after the automobile has traveled 1200 miles.
Representative portions from the top, middle and bottom of the container are analyzed for microbiocide [N-(2-methylnaphthyl maleimide] with the following results:
wt.~
ToP Middle Bottom 13.4 14.1 13.4 From these results, it can be concluded that no significant migration or stratification of the microbiocide occurs during transportation and handling.
~257~335 The following examples illustrate the production of a typical concentrate according to the present invention using a different microbiocide than used in the preceding examples.
The following ingredients are mixed in a"~enschel"mixer at the wt. ~ indicated:
Ex.ll Ex.12 Porous polyvinyl chloride"
resin"(Diamond 450 PVC) 78.5 Porous polyvinyl chloride resin "(Pantasote XTR-3) * - 79.5 Diisodecyl phthalate (DIDP) plasticizer 15.0 15.0 10,10'-oxybisphenoxarsine (OBPA) 5.0 5.0 Ca, Zn stabilizer ~(Mark 538)" 0.5 0-5 Stearic acid 1.0 In each example, the resin is heated in the ~enschel mixer at 200F, followed by the addition of a solution of the OBPA and DIDP which has been heated to 320F. The temperature of the mixtures is then raised to 210F. Next, the stabilizer and stearic acid are added. Mixing is continued until a drop temperature of 220F is obtained, at which time the microbiocide is absorbed, resulting in a free-flowing non-dusting powder which is cooled.
The following examples illustrate the importance of the microbiocide either being a liquid at the drop temperature or being dissolved in a carrier prior to mixing with the porous resin.
* Trademark ~ ~J _ _ ~257835 Dry blends are prepared in a"Henschel ~ixer"by blending all of the ingredients until the temperature reaches 220F. The blend of Comparative Example C is prepared by an addition of biocide directly to the resin. The blend of Example 12 is prepared by first dissolving the biocide in dioctyl phthalate plasticizer by heating to 250F. The hot solution is added directly to the resin during the mixing cycle. During preparation and during discharge from the"~enschel Mixer', both blends are observed to determine whether dusting occurs. The biocide dry blend particles are also examined under a 20X
magnification microscope for signs of neat biocide which has not been forced into the interstices of the resin particle.
The ingredients are present in the following wt. %:
Inqredients ExamPle 12comParatiVe ExamPle C
Polyvinyl Chloride *62.0 87.0 resin ~Diamond 450)~
N-(2-methylnaphthyl) 12.5 12.5 maleimide Dioctyl phthalate 25.0 20 Calcium stearate 0.5 0 5 Total 100.0 100.0 - Substantial dusting during both discharge and blending i5 observed from the blend of Comparative Example C. Excessive biocide is seen on the particle surface and in the dry blend upon microscopic examination of the blend of Comparative Example C.
In contrast, no dusting during discharge or blending is observed from the blend of Example 12. Moreover, no biocide is seen on the surface of the resin particles nor in the dry blend.
* Trademark -20-~257~35 While the invention has been described in terms of various preferred embodiments, one skilled in the art will appreciate that various modifications, substitutions, omissions, and changes may be made without departing from the spirit thereof. Accordingly, it is intended that the scope of the present invention be limited solely by the scope of the following claims.
Claims (10)
1. A composition comprising a dry blend mixture of:
a) a porous thermoplastic resin powder having a porosity of at least about 0.10 cc/g as measured by the mercury intrusion method or about 30% as measured on a void volume basis, wherein the particle size of the resin powder is between about 40 and about 300 mesh, said resin being selected from the group consisting of polyvinyl chloride, polyethylene, polystyrene, polypropylene, nylon, styrene-butadiene copolymer, polycarbonate, polystyrene-polyphenylene oxide blend, polyphenylene oxide and an ethylene/acrylic acid salt ionomer; and b) from 1 to 80 weight percent, based on the weight of the composition, of a microbiocide selected from the group consisting of 10,10'-oxybisphenoxarsine; N-(tri-chloromethylthio)-4-cyclohexene-1,2-dicarboximide; 2,3,5-trichloro-4-propylsulfonyl pyridine; 2,3,4,5-tetrachloro-4-(methylsulfonyl)pyridine; zinc salt of 1-hydroxypyridine-2-thione; N-(trichloromethylthio)phthalimide; N-(2-methyl-naphthyl)maleimide; cis-N-(1,1,2,2-tetrachlorethyl)-thio-4-cyclohexene-1,2-dicarboximide;1-isopropyl-3-methyl pyrazolyl-5-dimethyl carbamate; 3-methyl pyrazolyl dimethyl-carbamate; manganese ethylene bisdithiocarbamate; zinc ethylene bisdithiocarbamate; disodium ethylene bisdithio-carbamate; ferric dimethyl dithiocarbamate; zinc dimethyl dithiocarbamate; 2,4-dinitro-6-capryl phenol crotonate; p-chlorophenyl-p-chlorobenzene sulphonate; 2-N-octyl-4-isothiazolin-3-one; methyl(butyl carbamoyl)-2-benzimidazole carbamate; 2-(4-thiazolyl)benzimidazole; copper 8-hydroxyl-quinolinate; .alpha.-diethoxyphosphinodithioacetylurea; .alpha.-dimethoxylphosphinodithioacetylurea;diethoxyphosphinodi-thioacetamide; dimethoxyphosphinodithioacetamide;
bis(dimethylamido)phosphoryl fluoride; 2-cyclohexyl-3-isothiazolone; 4,5-dichloro-2-cyclohexyl-3-isothiazolone, and tributyl tin fluoride, the microbiocide being present in the mixture at a concentration of at least about 20 times greater than the normal upper usage concentration of the microbiocide, and the microbiocide being within the pores of the thermoplastic resin powder, said composition being substantially non-dusting.
a) a porous thermoplastic resin powder having a porosity of at least about 0.10 cc/g as measured by the mercury intrusion method or about 30% as measured on a void volume basis, wherein the particle size of the resin powder is between about 40 and about 300 mesh, said resin being selected from the group consisting of polyvinyl chloride, polyethylene, polystyrene, polypropylene, nylon, styrene-butadiene copolymer, polycarbonate, polystyrene-polyphenylene oxide blend, polyphenylene oxide and an ethylene/acrylic acid salt ionomer; and b) from 1 to 80 weight percent, based on the weight of the composition, of a microbiocide selected from the group consisting of 10,10'-oxybisphenoxarsine; N-(tri-chloromethylthio)-4-cyclohexene-1,2-dicarboximide; 2,3,5-trichloro-4-propylsulfonyl pyridine; 2,3,4,5-tetrachloro-4-(methylsulfonyl)pyridine; zinc salt of 1-hydroxypyridine-2-thione; N-(trichloromethylthio)phthalimide; N-(2-methyl-naphthyl)maleimide; cis-N-(1,1,2,2-tetrachlorethyl)-thio-4-cyclohexene-1,2-dicarboximide;1-isopropyl-3-methyl pyrazolyl-5-dimethyl carbamate; 3-methyl pyrazolyl dimethyl-carbamate; manganese ethylene bisdithiocarbamate; zinc ethylene bisdithiocarbamate; disodium ethylene bisdithio-carbamate; ferric dimethyl dithiocarbamate; zinc dimethyl dithiocarbamate; 2,4-dinitro-6-capryl phenol crotonate; p-chlorophenyl-p-chlorobenzene sulphonate; 2-N-octyl-4-isothiazolin-3-one; methyl(butyl carbamoyl)-2-benzimidazole carbamate; 2-(4-thiazolyl)benzimidazole; copper 8-hydroxyl-quinolinate; .alpha.-diethoxyphosphinodithioacetylurea; .alpha.-dimethoxylphosphinodithioacetylurea;diethoxyphosphinodi-thioacetamide; dimethoxyphosphinodithioacetamide;
bis(dimethylamido)phosphoryl fluoride; 2-cyclohexyl-3-isothiazolone; 4,5-dichloro-2-cyclohexyl-3-isothiazolone, and tributyl tin fluoride, the microbiocide being present in the mixture at a concentration of at least about 20 times greater than the normal upper usage concentration of the microbiocide, and the microbiocide being within the pores of the thermoplastic resin powder, said composition being substantially non-dusting.
2. The composition of claim 1 wherein the porosity of the powder is between about 0.10 and 0.60 cc/g as measured by the mercury intrusion method, or between about 30 and 70% as measured on a void volume basis.
3. The composition of claim 1 wherein the composition also contains a plasticizer for the resin.
4. The composition of claim 1 wherein the microbiocide is 10,10'-oxybisphenoxarsine; N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboxamide; 2,3,4,6-tetrachloro-4(methylsulfonyl) pyridine; N-(trichloromethylthio)phthalimide; tributyl tin fluoride; or N-(2-methyl-naphthyl)maleimide.
5. The composition of claim 1 wherein the resin is polyvinyl chloride and the microbiocide is N-(2-methylnaphthyl)maleimide or 10,10'-oxybisphenoxarsine.
6. A method of making a substantially non-dusting, free-flowing dry blend mixture comprising mixing:
a) a porous thermoplastic resin powder having a porosity of at least about 0.10 cc/g as measured by the mercury intrusion method or about 30% as measured on a void volume basis having a particle size between about 40 and about 300 mesh, said resin being selected from the group consisting of polyvinyl chloride, polyethylene, polystyrene, polypropylene, nylon, styrene-butadiene copolymer, polycarbonate, polystyrene-polyphenylene oxide blend, polyphenylene oxide and an ethylene/acrylic acid salt ionomer; and b) from 1 to 80 weight percent, based on the weight of the composition, of a microbiocide selected from the group consisting of 10, 10' -oxybisphenoxarsine; N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboximide;
2,3,5-trichloro-4-propylsulfonyl pyridine; 2,3,4,5-tetrachloro-4-(methylsulfonyl) pyridine; zinc salt of 1-hydroxypyridine-2-thione; N-(trichloromethylthio) phthalimide; N-(2-methyl-naphthyl)maleimide; cis-N-(1,1,2,2-tetrachlorethyl)-thio-4-cyclohexene-1,2-dicarboximide; 1-iso-propyl-3-methyl pyrazolyl-5-dimethyl carbamate; 3-methyl pyrazolyl dimethyl-carbamate; manganese ethylene bisdithiocarbamate; zinc ethylene bisdithiocarbamate;
disodium ethylene bisthiocarbamate; ferric dimethyl dithiocarbamate; zinc dimethyl dithiocarbamate; 2,4-dinitro-6-capryl phenol crotonate; p-chlorophenyl-p-chlorobenzene sulphonate; 2-N-octyl-4-isothiazolin-3-one; methyl(butyl carbamoyl)-2-benzimidazole; carbamate; 2-(4-thiazolyl) benzimidazole; copper 8-hydroxyl-guinolinate; .alpha.-d i e t h o x y p h o s p h i n o d i t h i o a c e t y l u r e a; .alpha. -d i m e t h o x y l p h o s p h i n o d i t h i o a c e t y l u r e a; .alpha. -diethoxyphosphinodithioacetamide; dimethoxy-phosphinodithioacetamide; bis(dimethylamido)phosphoryl fluoride; 2-cyclohexyl-3-isothiazolone; 4,5-dichloro-2-cyclohexyl-3-isothiazolone, and tributyl tin fluoride, in a high intensity high shear mixing apparatus at a temperature sufficient to open the pores of the powder, and then cooling the mixture to obtain a free-flowing powder which contains the microbiocide at a concentration of at least about 20 times greater than the normal upper usage concentration of the microbiocide, the microbiocide being held within the pores of the thermoplastic resin powder.
a) a porous thermoplastic resin powder having a porosity of at least about 0.10 cc/g as measured by the mercury intrusion method or about 30% as measured on a void volume basis having a particle size between about 40 and about 300 mesh, said resin being selected from the group consisting of polyvinyl chloride, polyethylene, polystyrene, polypropylene, nylon, styrene-butadiene copolymer, polycarbonate, polystyrene-polyphenylene oxide blend, polyphenylene oxide and an ethylene/acrylic acid salt ionomer; and b) from 1 to 80 weight percent, based on the weight of the composition, of a microbiocide selected from the group consisting of 10, 10' -oxybisphenoxarsine; N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboximide;
2,3,5-trichloro-4-propylsulfonyl pyridine; 2,3,4,5-tetrachloro-4-(methylsulfonyl) pyridine; zinc salt of 1-hydroxypyridine-2-thione; N-(trichloromethylthio) phthalimide; N-(2-methyl-naphthyl)maleimide; cis-N-(1,1,2,2-tetrachlorethyl)-thio-4-cyclohexene-1,2-dicarboximide; 1-iso-propyl-3-methyl pyrazolyl-5-dimethyl carbamate; 3-methyl pyrazolyl dimethyl-carbamate; manganese ethylene bisdithiocarbamate; zinc ethylene bisdithiocarbamate;
disodium ethylene bisthiocarbamate; ferric dimethyl dithiocarbamate; zinc dimethyl dithiocarbamate; 2,4-dinitro-6-capryl phenol crotonate; p-chlorophenyl-p-chlorobenzene sulphonate; 2-N-octyl-4-isothiazolin-3-one; methyl(butyl carbamoyl)-2-benzimidazole; carbamate; 2-(4-thiazolyl) benzimidazole; copper 8-hydroxyl-guinolinate; .alpha.-d i e t h o x y p h o s p h i n o d i t h i o a c e t y l u r e a; .alpha. -d i m e t h o x y l p h o s p h i n o d i t h i o a c e t y l u r e a; .alpha. -diethoxyphosphinodithioacetamide; dimethoxy-phosphinodithioacetamide; bis(dimethylamido)phosphoryl fluoride; 2-cyclohexyl-3-isothiazolone; 4,5-dichloro-2-cyclohexyl-3-isothiazolone, and tributyl tin fluoride, in a high intensity high shear mixing apparatus at a temperature sufficient to open the pores of the powder, and then cooling the mixture to obtain a free-flowing powder which contains the microbiocide at a concentration of at least about 20 times greater than the normal upper usage concentration of the microbiocide, the microbiocide being held within the pores of the thermoplastic resin powder.
7. The method of claim 6 wherein the microbiocide is a liquid at the temperature used to open the pores of the powder.
8. The method of claim 6 wherein the microbiocide is dissolved in a carrier prior to mixing with the resin powder.
9. The method of claim 8 wherein the carrier is a plasticizer for the resin.
10. The method of claim 6 wherein the resin is polyvinyl chloride and the microbiocide is N-(2-methylnaphthyl)maleimide or 10,10'-oxybisphenoxarsine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US70762885A | 1985-03-04 | 1985-03-04 | |
| US707,628 | 1985-03-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1257835A true CA1257835A (en) | 1989-07-25 |
Family
ID=24842467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000502823A Expired CA1257835A (en) | 1985-03-04 | 1986-02-27 | Solid biocide dry blend |
Country Status (16)
| Country | Link |
|---|---|
| US (2) | US4663359A (en) |
| EP (1) | EP0197631B2 (en) |
| JP (1) | JPS61205201A (en) |
| KR (1) | KR900008466B1 (en) |
| AT (1) | ATE72257T1 (en) |
| AU (1) | AU576941B2 (en) |
| BR (1) | BR8600820A (en) |
| CA (1) | CA1257835A (en) |
| DE (1) | DE3683667D1 (en) |
| DK (1) | DK166793B1 (en) |
| ES (1) | ES8708179A1 (en) |
| GR (1) | GR860593B (en) |
| MX (1) | MX162270A (en) |
| NO (1) | NO170311C (en) |
| NZ (1) | NZ215076A (en) |
| ZA (1) | ZA861046B (en) |
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| US4895877A (en) * | 1984-06-11 | 1990-01-23 | Morton Thiokol, Inc. | Microbiocidal compositions comprising an aryl alkanol and a microbiocidal compound dissolved therein |
| US4711914A (en) * | 1985-04-22 | 1987-12-08 | Morton Thiokol, Inc. | Microbiocidal compositions comprising an aryl alkanol and a microbiocidal compound dissolved therein |
| JPS62175401A (en) * | 1986-01-28 | 1987-08-01 | Kurita Water Ind Ltd | Slow-releasing antibacterial agent |
| US4789692A (en) * | 1986-08-12 | 1988-12-06 | Morton Thiokol, Inc. | Resin-immobilized biocides |
| US4830883A (en) * | 1986-09-09 | 1989-05-16 | Hexcel Corporation | Polyimide foam precursor and its use in reinforcing open-cell materials |
| EP0281918A3 (en) * | 1987-03-11 | 1990-10-17 | BASF Aktiengesellschaft | Plant protecting agent containing an active ingredient |
| US4869905A (en) * | 1987-05-12 | 1989-09-26 | The B. F. Goodrich Company | Method of making and a slow release composition for abating acid water formation |
| JPH0688885B2 (en) * | 1987-12-26 | 1994-11-09 | 品川燃料株式会社 | Method for producing dispersion containing antibacterial powder |
| EP0403657B1 (en) * | 1988-12-27 | 1998-01-28 | Asahi Kasei Kogyo Kabushiki Kaisha | A porous, crystallized, aromatic polycarbonate prepolymer, a porous, crystallized aromatic polycarbonate, and production methods |
| DE3903247A1 (en) * | 1989-02-03 | 1990-08-09 | Shell Int Research | FUNGICIDIC COMPOSITION, METHOD FOR THEIR PRODUCTION AND THEIR USE, IN PARTICULAR FOR THE HEALING TREATMENT OF PLANTS Suffering from Fungus Diseases |
| US5214073A (en) * | 1989-10-17 | 1993-05-25 | Asahi Kasei Kogyo Kabushiki Kaisha | Porous, crystallized, aromatic polycarbonate prepolymer, a porous, crystallized aromatic polycarbonate, and production methods |
| GB2242433A (en) * | 1990-03-01 | 1991-10-02 | Grace W R & Co | Packaging film containing an additive |
| US5229124A (en) * | 1990-04-02 | 1993-07-20 | Morton International, Inc. | Microbicides immobilized in water soluble thermoplastic resins and aqueous dispersions of microbicides prepared therefrom |
| IT1240647B (en) * | 1990-05-14 | 1993-12-17 | Himont Inc | NON-EXTRUDED CONCENTRATES OF ADDITIVES, CHARGES OR PIGMENTS |
| US5639803A (en) * | 1990-10-19 | 1997-06-17 | Olin Corporation | Process for incorporating biocides into a liquid dispersion |
| JPH06503079A (en) * | 1990-12-13 | 1994-04-07 | アクゾ ナムローゼ フェンノートシャップ | Primarily solid concentrates containing biocides |
| DE4142578A1 (en) * | 1991-12-21 | 1993-06-24 | Basf Ag | METHOD FOR PRODUCING THERMOPLASTIC MOLDING MATERIALS BASED ON POWDER-SHAPED POLYPHENYLENE ETHERS AND VINYLAROMATIC POLYMERS |
| US5319000A (en) * | 1992-05-08 | 1994-06-07 | Olin Corporation | Process for stable biocide dispersion |
| US5929132A (en) * | 1992-11-19 | 1999-07-27 | Arch Chemicals, Inc. | Process for incorporating biocides into a liquid dispersion |
| US5554373A (en) * | 1993-11-05 | 1996-09-10 | Seabrook; Samuel G. | Compositions containing anti-microbial agents and methods for making and using same |
| CH685878A5 (en) * | 1993-12-08 | 1995-10-31 | Brugg Ag Kabelwerke | Process for the preparation of an additive-loaded porous Traegermaterials |
| US6093407A (en) | 1997-10-03 | 2000-07-25 | Dupont Powder Coatings Usa, Inc. | Anti-microbial powder coatings |
| US5906825A (en) * | 1997-10-20 | 1999-05-25 | Magellan Companies, Inc. | Polymers containing antimicrobial agents and methods for making and using same |
| JP2002521497A (en) * | 1998-08-05 | 2002-07-16 | ビーエーエスエフ アクチェンゲゼルシャフト | Granules for soil with controlled release of active ingredient (CR granules for soil) |
| US6475505B1 (en) | 1999-12-20 | 2002-11-05 | Ciba Specialty Chemicals Corporation | Biocide-polyester concentrates and biocidal compositions prepared therefrom |
| DE10010072A1 (en) * | 2000-03-02 | 2001-09-06 | Rheinchemie Rheinau Gmbh | Biocidal batches based on crosslinked oils, process for their preparation and their use in thermoplastic molding compositions |
| US8063116B2 (en) * | 2006-08-25 | 2011-11-22 | Sciessent Llc | Antimicrobial powder coatings and method |
| US8518449B2 (en) * | 2006-08-25 | 2013-08-27 | Sciessent Llc | Polymer particle coating method |
| EP1925201A1 (en) * | 2006-11-09 | 2008-05-28 | Werner Zapletal | Method for antimicrobial treatment of powder |
| DE102007028923A1 (en) * | 2007-06-22 | 2008-12-24 | Lanxess Deutschland Gmbh | Biozodwirkstoff containing particulate polymers |
| WO2009046172A1 (en) * | 2007-10-03 | 2009-04-09 | Isp Investments Inc. | Stabilizer concentrate for matrix compositions processed at elevated temperatures |
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| BE666601A (en) * | 1964-07-09 | |||
| US3371053A (en) * | 1965-08-09 | 1968-02-27 | Raskin Betty Lou | Multicellular plastic particles and dispersions thereof |
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| JPS5218827A (en) * | 1975-08-04 | 1977-02-12 | Katayama Chem Works Co Ltd | Soil-treating agents for the control of white ants and method of apply ing the same |
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| DE3026688C2 (en) * | 1980-07-15 | 1986-02-20 | Akzo Gmbh, 5600 Wuppertal | Process for the production of powdery, porous polymer particles |
| US4435524A (en) * | 1981-09-08 | 1984-03-06 | The B. F. Goodrich Company | Process for preparing spherical and porous vinyl resin particles |
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| US4458057A (en) * | 1982-10-27 | 1984-07-03 | The Bf Goodrich Company | Process for producing spherical and porous vinyl resin particles |
-
1986
- 1986-02-10 NZ NZ215076A patent/NZ215076A/en unknown
- 1986-02-12 DE DE8686300954T patent/DE3683667D1/en not_active Expired - Lifetime
- 1986-02-12 AT AT86300954T patent/ATE72257T1/en not_active IP Right Cessation
- 1986-02-12 EP EP86300954A patent/EP0197631B2/en not_active Expired - Lifetime
- 1986-02-12 ZA ZA861046A patent/ZA861046B/en unknown
- 1986-02-19 AU AU53753/86A patent/AU576941B2/en not_active Ceased
- 1986-02-19 MX MX1599A patent/MX162270A/en unknown
- 1986-02-26 BR BR8600820A patent/BR8600820A/en not_active IP Right Cessation
- 1986-02-27 CA CA000502823A patent/CA1257835A/en not_active Expired
- 1986-03-01 JP JP61042842A patent/JPS61205201A/en active Granted
- 1986-03-03 DK DK096386A patent/DK166793B1/en not_active IP Right Cessation
- 1986-03-03 NO NO860778A patent/NO170311C/en not_active IP Right Cessation
- 1986-03-03 ES ES552591A patent/ES8708179A1/en not_active Expired
- 1986-03-03 GR GR860593A patent/GR860593B/en unknown
- 1986-03-04 KR KR1019860001492A patent/KR900008466B1/en not_active IP Right Cessation
- 1986-04-17 US US06/853,083 patent/US4663359A/en not_active Expired - Lifetime
- 1986-10-16 US US06/919,403 patent/US4661528A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AU576941B2 (en) | 1988-09-08 |
| NO860778L (en) | 1986-09-05 |
| MX162270A (en) | 1991-04-19 |
| DK96386D0 (en) | 1986-03-03 |
| EP0197631A3 (en) | 1987-10-07 |
| NO170311C (en) | 1992-10-07 |
| ATE72257T1 (en) | 1992-02-15 |
| KR900008466B1 (en) | 1990-11-22 |
| EP0197631B1 (en) | 1992-01-29 |
| JPS61205201A (en) | 1986-09-11 |
| NO170311B (en) | 1992-06-29 |
| ZA861046B (en) | 1987-01-28 |
| US4663359A (en) | 1987-05-05 |
| ES552591A0 (en) | 1987-10-01 |
| US4661528A (en) | 1987-04-28 |
| NZ215076A (en) | 1988-09-29 |
| KR860007332A (en) | 1986-10-10 |
| DE3683667D1 (en) | 1992-03-12 |
| AU5375386A (en) | 1986-09-11 |
| EP0197631A2 (en) | 1986-10-15 |
| BR8600820A (en) | 1986-11-11 |
| DK166793B1 (en) | 1993-07-19 |
| GR860593B (en) | 1986-06-26 |
| EP0197631B2 (en) | 1999-12-15 |
| JPH0257043B2 (en) | 1990-12-03 |
| DK96386A (en) | 1986-09-05 |
| ES8708179A1 (en) | 1987-10-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |