CA1071799A - Method of making biocide compositions and compositions therefor - Google Patents
Method of making biocide compositions and compositions thereforInfo
- Publication number
- CA1071799A CA1071799A CA266,657A CA266657A CA1071799A CA 1071799 A CA1071799 A CA 1071799A CA 266657 A CA266657 A CA 266657A CA 1071799 A CA1071799 A CA 1071799A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- microbiocide
- solid
- resin
- thermoplastic resin
- 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
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Classifications
-
- 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
-
- 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
-
- 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 solid composition comprising a homogeneous mixture of a solid thermoplastic resin and from 1 to 80 weight % of at least one microbiocide which is insoluble in water, 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, retains its micro-biocidal activity in the resin and does not degrade or react with the resin in which it is dispersed. This composition provides a convenient non-toxic dosage form of the micro-biocide which is subsequently mixed with a second thermo-plastic resin at a concentration of about 0.5 to 15 weight %
to obtain a homogeneous resin composition containing an effective amount of the microbiocide.
A solid composition comprising a homogeneous mixture of a solid thermoplastic resin and from 1 to 80 weight % of at least one microbiocide which is insoluble in water, 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, retains its micro-biocidal activity in the resin and does not degrade or react with the resin in which it is dispersed. This composition provides a convenient non-toxic dosage form of the micro-biocide which is subsequently mixed with a second thermo-plastic resin at a concentration of about 0.5 to 15 weight %
to obtain a homogeneous resin composition containing an effective amount of the microbiocide.
Description
~ i 107179~
\
This invention relates to solid resin-microbiocide compositions and to a method for forming resin products there-with. ~ore particularly, the present invention relates to solid polymeric compositions containing a high concentration of a microbiocide for the purpose of providing an easily handleable, predispersed and a relatively non-toxic form of the biocide and a method for forming resin products therefrom.
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 which would be susceptible to attack. Heretofore, 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 thereby providing a vehicle for the microbiocide to promote its migration throughout the resin, particularly to its surface. The presently employed procedures usually involve first mixing the microbiocide in a liquid carrier which solubilizes of disperses the microbiocide uniformly followed r by mixing the liquid composition with the final resin composition.
The liquid solvents or dispersants employed are those which do not degrade the properties of the final resin product such `~
1~71799 `'`
1 as plasticizers 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 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.
Alternatively, it has been proposed to add the microbiocide directly to a formable resin composition at the low effective concentrations which prevent microbiological attack. However this procedure has proven to be unsatisfactory since the needed concentrations of microbiocide is quite low, generally less than about 1 weight % and usually between about 200 and 1000 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 procedure 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 toxicological 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 process or utilizes the 1 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 necessar~ to extend the mixing time of the resultant composition. Furthermore, mixing -of these resin compositions containing low concentrations of microbiocides results in the microbiocide being coated on the surface of the mixing apparatus rather than being homogeneously dispersed throughout the resin.
It ~ould be highly desirable to provide solid micro-biocidal compositions having high concentrations of a micro-biocide, above its usually employed effective concentrations, which eliminates the need for a liquid carrier. This would permit incorporating the microbiocide at the desired con-centration subsequently into a resin composition while avoiding toxicological hazards and while providing improved control of the concentration of liquid additives in the final resin product. Furthermore, it would be desirable to ~ provide such compositions wherëin the microbiocide does not degrade the resin and is not itself degraded when incorporated ;1 in the resin so that the compositions can be incorporated sub- -sequently into a resin wherein the microbiocide is present :.
at effective concentrations.
- SUMMARY OF THE INVENTION
:''' - :
This invention provides solid compositions comprising a thermoplastic resin containing between about 1 and 80 weight :j % of at least one microbiocide which is insoluble in water, 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 .~ .
:. 3 10717~9 1 indefinitely upon cooling to ambient temperature while the diffusivity of the microbiocide in the resin under such con-ditions becomes vanishingly small, retains its microbiocidal activity in the resin and does not degrade or react with the resin in which it is dispersed. Representative suitable microbiocides include 10, 10'-oxybisphenoxarsine, N-(tri-chloromethylthio)-4-cyclo-hexene-1,2-dicarboxamide, 2,3,5,6-tetrachloro-4-(methylsulfonyl) pyridine and N-(trichloro-methylthio) phthalimide which is dispersed and/or solubilized in the resin. The solid compositions are both compatible and homogeneously dispersible in a second thermoplastic resin composition to provide effective resistance against microbiocidal attack on the secona thermoplastic resin composition. The solid microbiocidal compositions are prepared by mixing the microbiocide and resin under conditions such that the micro-biocide is rendered substantially nonmigratory to form a homogeneous composition. These microbiocides also function as processing aids for the resin in that they reduce the `
processing temperatures needed to form homogeneous compositions.
Even ~hough the concentration of the microbiocide is above that which would normally present a toxicological hazard, the homo-geneous microbiocide-resin composition is far less toxic than - either the microbiocide itself or liquid compositions con-taining the microbiocide. These compositions can be made without employing a liquid carrier for the microbiocide so that unwanted liquid additives in the second resin composition to be fabricated can be avoided. The concentrated micro-biocide-resin composition is incorporated into the second resin composition in amounts such that the two compositions are compatible and such that the final resin composition con-tains the microbiocide at an effective concentration and below 1(~7~799 1 the concentration that presents a toxicologiCal hazard.
DESCRIPTION OF SPECIFIC EMBODIME2~TS
The compositions of this invention contain the micro-biocide at a concentration which permits the subsequent in-corporation of the resultant composition into a second thermoplastic resin composition as a concentration between about 0.5 and 15 weight ~ based upon the total weight of the resultant composition. When less than about 0.5 weight % of 1 the composition of this invention is incorporated into the second thermoplastic resin composition, less than homogeneous dispersion may be obtained which causes the resultant com-position to ha~e underprotected areas. When more than about 15 weight % of the composition of this invention is incorporated into a second thermoplastic resin which is different than the first thermoplastic resin, the two resins may beco~e incompatible. In addition, when more than about 15 weight of the composition of this invention is incorporated into a second thermoplastic resin different from the first thermo-plastic resin,undesirable changes in the physical characteristicsof the second-thermoplastic resin occurs in that they approach those of the first thermoplastic resin.
f .
' The concentration of microbiocide in the composition of this invention is between about 1 and 80 weight %, preferably from about 5 to about 55 weight %, based upon the total weight of the thermoplastic composition. The micro-biocide 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, ln, lo ~ -oxybis-1 phenoxarsine is used normally in a concentration up to 0.05weight ~; N-(trichloromethylthio)-4-cyclo-hexene-1,2-dicarboximide is used normally in a concentration up to 0.5 weight ~; 2,3,4,6-tetrachloro-4-(methylsulfonyl)pyridine is used normally in a concentration up to 0.75 weight ~; N-(trichloromethylthio) phthalamide is used normally in a con-centration up to 0.75 weight % or Zinc Omadine or tributyl tin fluoride which are used normally in a concentration up to 0.2 weigh.t %. In any event, the microbiocide concentration is controlled so i~ is present in an effective concentration in a second thermoplastic resin composition when added thereto between about 0.5 and 15 weight % based upon the weight of the second thermoplastic resin composition.
In order to form homogeneous resin-microbiocide compositions, 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 solutiorl 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 at the high microbiocidal concentrations utilized herein. In addition, the microbiocide must retain :.~ its activity and not itself becomP degraded or does not degrade .: the resin either during mixing with the resin or after being incorporated into the resin. Stability of the microbiocide-resin concentrate is determined readily by visual observation wherein irreversible dark coloring of the concentrate represents degradation of the composition so that it is not useful in the present invention. For example, the micro-biocide, ortho-benzyl parachlorophenol is miscible in resins, iO7~L799 1 particularly vinyl resins but the resultant resin-microbiocide composition turns irreversibly black and therefore is not useful herein. Tributyl tin oxide is another common micro-biocide not useful herein since it is essentially immiscible with vinyl resins. It is also essential that the microbiocide be substantially insoluble in water so that it is not easily leached from the resin-microbiocide composition either during normal storage or normal use.
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 con-taining the normal upper range concentration of th~ micro-biocide. 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.
~ince the microbiocide is far less migratory within ;,' - the resin than the microbiocide per se or the microbiocide - 20 in solution, it is far less toxic than the microbiocide per ;
se or liquid solutions of the microbiocide even though present ,; at higher concentrations than its effective concentration.
, 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 com-; position of this invention reduces contamination of processing and weighing equipment and facilitates clean~up of this equipment.
The compositions of this invention normally have 1 poor end use physical properties. Therefore, they must be incorporated into another thermoplastic resin to produce useful fabricated thermoplastic products. However, due to their less toxic nature, the compo5ition of this invention provides a significant advantage over the prior art compositions in that they can be processed safely in conventional thermoplastic resin fabrication techni~ues without requiring costly safety equipment and without the need for a liquid carrier for the microbiocide.
In another aspect of this invention, it has been found that the microbiocides employed herein, when employed in high concentrations, function as processing aids in that they ; reduce the melt viscosity and softening point of the thermo-; plastic resin to such a degree that the resin and microbiocide composition can be processed to form a homogeneous composition ` without the need for plasticizers for the resin. That is, the microbiocide has the effect of reducing the viscosity of the thermoplastic resin so that when the two are mixed,such as by milling, the resultant composition can be heated to tem-peratures normally employed in resin-forming processes without the need for adding processing aids that reduce the viscosity of the resin or which provide heat stability to the resin.
This is surprising since this effect on the resin is not ` observed when the microbiocide is incorporated at the normally low concentrations at which the microbiocide is effective to prevent or to inhibit microbiological attack without presenting a toxicological hazard to humans. The degree of this effect is dependent upon the type of thermoplastic resin employed, the type of microbiocide employed and the concentration of microbiocide employed.
10~1~99 :`~
1 The compositions of this invention are prepared by mixing a particulate thermoplastic resin with a high concentration of microbiocide such that a homogeneous composition can be obtained without the need for additional processing aids such as a plasticizer, a heat stabilizer or a lubricant for the resin to obtain the advantages set forth above. However, they can be added if desired for special effect. The micro-biocide and resin are mixed to obtain a dry homogeneous particulate composition. Thereafter, the composition is heated and mixed so that the resin is melted to a homogeneous composition to obtain solution or dispersion of the microbiocide in the resin. ~hen heating and mixing the composition, the melting point and viscosity of the resin composition is reduced as compared to the resin per se. It has been found that homogeneous resin-microbiocide compositions containing high ~' concentrations of the microbiocide ~an be formed in this manner.
. In addition, it has been found that 10,10'-oxybisphenoxarsine and 2,3,5,6-tetrachloro-4-~methylsulfonyl) pyridine function as-a heat stabilizer for polyvinyl chloride-polyvinyl .:.
~-- 20 acetate copolymers and homopolymer.
` Representative suitable thermoplastic resins that can be employed to form the microbiocide-resin composition or which can be compounded with the microbiocide-resin com-position include polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyurethanes, polyamides, polyolefins, polystyrene, vinyl chloride-acrylonitrile copolymers, poly-esters and ~he like.
~uitable microbiocides include:
B OBPA - 10,10'-oxybisphenoxarsine Vancide 89 - N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboximide ::
1~71799 i Dowcil S-13 - 2,3,5,6-tetrachloro-4-(methylsulfonyl) pyridine Dowcil A-40*- 2,3,5-trichloro-4-propylsulfonyl pyridine Zinc Omadine*- zinc salt of l-hydroxypyridine-2-thione Fungitrol 11*- N-(trichloromethylthio) phthalimide Difolatan*- 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 bixdithiocarbamate Zineb - zinc analog of ~laneb ~: Nabam - disodium analog or Maneb . Ferbam - ferric dimethyl dithiocarbamate Ziram - zinc analog of Ferbam ~ Karathane*- 2,4-dinitro-6-capryl phenol crotonate ;~ Ovotran*- p-chlorophenyl-p-chlorobenzenesulphonate ;. Skane M-8*- 2-N-octyl-4-isothiazolin-3-one Benomyl - methyl-l(butylcarbamoyl)-2-benzimidazole carbamate Metasol TK-100*- 2-(4-thiazolyl) benzimidazole ` Copper-8 - copper 8-hydroxy-quinolinate :~ a-diethoxyphosphinodithioacetylurea a-dimethoxyphosphinodithioacetylurea Diethoxyphosphinodithioacetamide : Dimethoxyphosphinodithioacetamide Bis(dimethylamido) phosphoryl fluoride Tributyl tin fluoride and mixtures thereof. The preferred microbiocides are 10,10'-oxybisphenoxarsine, N-(trichloromethylthio)-4-cyclohexene-1,2-30 dicarboximide,2,3,5,6-tetrachloro-4-(methylsulfonyl) pyridine *Trade Mark ~ .
1~71799 1 and N-(trichloro~ethylthio) phthalimide since they are relatively easy to incorporate into a wide variety of resins at high concentration without significant loss of micro-biological activity and without significant degradation to the resin.
The microbiocide and resin are mixed under conditions of heating to melt and to soften the resin and to form a homo-geneous mixture wherein upon cooling the microbiocide is rendered far less migratory by the resin matrix. The mixture ~ 1~ is subjected to shear forces and heat in any suitable apparatus ;i' such as a two-roll mill or a Banbury mixer or extruder and ,.
' the resultant softened composition is formed such as by extrusion, milling or calendering. The formed composition is cooled so that it can be broken up into small particles thereby permitting its subsequent incorporation into other ` thermoplastic compositions having an effective low concentration of the microbiocides.
The compositions of this invention are blended with a second thermoplastic composition by conven~ional 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 compatible so that a homogeneous final composition results.
The microbiocide-containing composition should have a softening temperature below or within the range of temperatures en-countered during conventional processing of the second thermo-1 plastic composition. These temperatures are within the range of between about 250~ and about 500F. It is preferred that the resin-microbiocide concentrates have a softening temperature within a range of about 150F to 300F.
In forming the microbiocide-containing composition of this invention, the usual resin additives optionally can be 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, ; lO reduced concentration of plasticizer must be employed to avoid 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 comp~sitions -~ of the resin, the plasticizer and the microbiocide. Generally, - moderate plasticizer concentrations can be tolerated within the range of between about 5 and 2~ weight % when the micro-biocides are employed at concentrations of 50 weight % 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 is limited by their exclusion. To determine suitable plasticizers for a particular resin-microbiocide system, all that is necessary is that one add the plasticizer, within the range noted above, to the resin-microbiocide composition, mix the resultant composition and visually determine whether the microbiocide has been immobilized by the resin to form a homogeneous composition. Any of the conventional resin plasticizers can be employed including dialkyl phthalates, epoxy plasticizers, polyester plasticizers, dialkyl phosphites , ..
1~71799 and the like. In addition, the usual resin additives can be included such as ultraviolet stabilizer, heat stabilizer, fillers, dyes, pigments, lubricants and the like.
In a preferred aspect of this invention, the con-; centrated microbiocide-resin composition is formed with a vinyl chloride-vinyl acetate copolymer and the microbiocide, preferably 10,10'-oxybisphenoxarsine ~OBPA), and is incorporated into a second thermoplastic resin having a composition different than the chloride-vinyl acetate copolymer employed to form the concentrate. It has been found that the final composition produced thereby contains the microbiocide , ,.- ~, ~ , homogeneously distributed therein in effective concentrations while minimizing or eliminating the need for a plasticizer ; :;
during compounding o~ the final composition. This is desirable since some thermoplastic resins such as polyurethanes can ~ ;
tolerate only very small concentrations of a plasticizer, if ` any, to avoid physical degradation of the thermoplastic resins r In addition, as noted above, the presence of a plasticizer may cause undesirable blooming of the microbiocide in the resin and so that minimizing or eliminating the use of a plasticizer is desirable in forming a final product having desirable physical characteristics and which is protected against microbiological attack. Particularly desirable products are obtained when the second thermoplastic resin is polyurethane, polyvinyl chloride or polyethylene. Although any of the microbiocides set forth above are useful in forming these final products, OBPA is preferred since it has high microbiocidal activity and so that only small concentrations of the concentrate are required to obtain homogeneous dispersion of OBPA at effective concentrations. In this embodiment, the 1~7~7~39 1 PVC/PVA based concentrate is employed in amounts of between about 0.5 and 5.0 weight percent based upon the total com-position. In a specific embodiment, the concentrate is formed from about 95 parts vinyl chloride-vinyl acetate copolymer and about 5 parts OBPA which optionally can contain about 0.1 parts of a lubricant such as stearic acid or zinc stearate.
About 1 part of this concentrate then is compounded into about 99 parts of a second thermoplastic resin composition such as polyvinyl chloride, polyurethane or polyethylene which optionally can contain the usual resin additives set forth above.
The following examples illustrate the present in-vention and are not intended to limit the same.
EXAMPLE I
This example illustrates that Dowcil S-13 can be incorporated into thermoplastic resins either in the absence or in the presence of a plasticizer.
Each of the formulations set forth below in Table I
were blended in a Henschel mixer at temperature ranging from about 70 F to 220 F for a period of 1 to 10 minutes to form a homogeneous powder blend. In each instance, the thermoplastic resin, in particulate form, was added to the Henschel mixer together with the other plastic additive, if any, and micro-biocide. After the thermoplastic resin composition had been mixed, it was extruded at a temperature between 150F
and 300F into a rod form which then was cooled to room temperature. The rod then was pelletized. Compatibility was determined by sheeting a portion of the pellets and visually observing whether blooming had occurred over a period of up to two months at one week intervals. Extrusion properties 1C~71799 1 were determined by the ability of the composition to retain its rod from for subsequent pelletization.
TABLE I
Sample No. 1 2 3 4 5 6 7 (parts by weight) PVC (low MW)100.0100.0100.0 47 .
.~ Copolymer VYHH
~:: PVC/VA (86:14) 46.75 100 100 Ba, Cd, Zn Stabilizer-(Mark KCs) 3.0 3.0 1.0 Stearic Acid 0.5 0.5 1.0 0.25 : Dioctyl Phthalate15.0 15 . .
: Dipropylene Glycol Dibenzoate 15.0 -Dowcil S-13 17.8 17.8 306.0 53.0 53.0 25 20 _ Compatibility I C C C C C C
Extrusion properties NG G G NG G G G
. ~
~0 Milling properties G G G G G G G
.. ..
I = Incompatible or Surface Blooming --C = Compatible NG = Not Good G = Good As shown in Table I, Dowcil S-13 is compatible in vinyl chloride-vinyl acetate copolymers or vinyl chloride homopolymers at high levels without a plasticizer. However, surface blooming results when 15 parts of dioctyl phthalate plasticizer and 0.5 parts of stearic acid lubricant are included in the composition while compatibility and no blooming result 1 when employing 15 parts of the sarne plasticizer without the stearic acid lubricant. In each instance, the resin-microbiocide composition can be formed by extrusion and~or milling.
Samples 1 through 7 are compatible with thermoplastic polymers to ~orm compositions containing an ef~ective con-centration of ~owcil S-13 including vinyl chloride homopolymers, polyethylene polyvinyl acetate, polyurethane, vinyl chloride-vinyl acetate copolymers and thermoplastic rubbers such as chlorinated polyethylene and nitrile rubbers.
To determine microbiological activity of the Dowcil S-13- resin concentrate of this invention, 1.5 weight percent of sa~ple 5, based on total weight was blended with the resin composition employéd for such testing in Example III by the blending process described in Example III. The testing procedures and the bacteria and fungi tested were those set forth in Example III including a 500 hour weather test. The results are set forth in Table Ia.
TABLE Ia Antimicrobiocidal Activity Zone of Inhibition (mm)/Stain or Growth .
Samp~e 5 + PVC Staph. K. Pink Mixed Aureus pneumonial Stain Spore Unleached 7/NGCAl/NGCA 8/NS 3/NG
Leached 7/NGCAl/NGCA 8/NS 3/NG
Weathered 100 Hours 5/NGCA 0~5/NGCA 5/NS 2jNG
Weathered 200 Hours 6/NGCA 0.5/NGCA 5/NS 0/NG
Weathered 300 Hours 0/LS 0/LG 0/HS 0/LG
Weathered 500 Hours 0/HS 0/LG
NGCA = No Growth Contact Area LG = Low Growth NS = No Stain HS = Heavy Stain NG = No Growth LS = Light Stain ~ 16 -1(~71799 1 As shown in Table Ia, the film showed good antifungal activity both before and after weathering and no evidence of stain up to 200 hours of weathering.
EXAMPLE II
This example illustrates that Vancide-89 can be incorporated into thermoplastic resins either in the absence ~`~ or in the presence of a plasticizer.
Each of the formulations set forth below in Table II
were blended in a Henschel mixer, except Sample 9, which was blended in a two roll mill at about 250F. Temperatures in the Henschel mixer ranged from 70F to 220F. Mixing times ranged from l to lO minutes. In each instance, the thermo-plastic polymer in particulate form was added to the` Henschel mixer or the two roll mill, together with the microbiocide and other plastic additives set forth, if any. After the composition had been mixed, it was extruded at a temperature between 150F and 300F and extruded into a 2.5 mil thick sheet. Compatibility was determined by visually observing whether blooming had occurred over a period of up to two months at one week intervals. Extrusion properties were determined by the ability of the composition to retain its sheet form for subsequent pelletization.
107179~
TABLE I I
Sample No. 8 9 10 11 12 . _ . ... . ...
(Parts by Weight) 100.0 100.0 100.0 PVC (Low MW) :: . .. .. . _ .
- CvcP/lYm8e6r V14HH 49~75 1~)0 . . .
Ba, Cd, Zn, Stabilizer - (Mark KCB) 3.0 3.0 3.0 -- . . .
Stearic Acid 0.5 0.5 0.5 0.25 Dioctyl Phthalate 15.0 15.0 15 1 0 - - --_- _ __ _ _ Vancide-89 17.8 17.8 118.5 50.0 25 ... . . . .................. . ~ _ Mark 275 Tin Stabilizer 0 5 . . . _ . _ . . . _ _ _ . . . _ _ . . . _ _ Compatibility I C C C C
.. .. _ _ .
Extrusion Properties NG NG NG G G
. _ ... _ . .. .. _ Milling Properties G G G G G
.
I = Incompatible C = Compatible NG = Not Good G = Good As shown in Table II, ~ancide-89 is compatible in vinyl chloride-vinyl acetate copolymer or polyvinyl chloride at high levels with or without a plasticizer. In compatibility results when 15 parts of dioctyl phthalate plasticizer is included in the composition.
In each instance, the resin-microbiocide composition can be formed by extrusion and/or milling. Samples 8 through 12 are compatible with thermoplastic polymers to form compositions containing an effective concentration of Vancide 89 including polyvinyl chloride, polyethylene,polyvinyl acetate, poly~
urethane, vinyl chloride-vinyl acetate copolymers and thermo--- 18 --~. '' 1(~71799 1 plastic rubbers such as chlorinated polyethylene and nitrile rubbers.
To determine microbiological activity of the Vancide-89-resin concentrate of this invention, 1 weight percent of Sample 11, based on total weight was blended with the resin composition employed for such testing in Example III by the blending process described in Example III. The testing pro-cedures and the bacteria and fungi tested were those set forth in Example III but omitting the 300 hour weather test.
The results are set forth in Table IIa.
TABLE IIa Antimicrobiocidal Activity Zone of Inhibi~tion (mm)/Stain or Growth Sample 11 + PVC Staph X. Pink Mixed Aureus pneumonial Stain Spore Unleached 4/NGCA 0/NGCA ~.5/NS 2/NG
Leached 4/NGCA 0/NGCA 0.5/NS, 2/NG
Weathered 100 Hours 4/NGCA 0/NGCA 0/NS l/NG
Weathered 200 Hours 3/NGCA 0/NGCA 0/TrS l/NG
NGCA = No Growth Contact Area NS = No Stain NG = No Growth TrS = Trace Stain As shown in Table IIa, the film showed good antifungal and antibacterial activity both before and after weathering.
EXAMPLE III
This example illustrates that OBPA can be incorporated into thermoplastic resins either in the absence or in the presence of a plasticizer.
Each of the formulations set forth below in Table III
were blended in a Henschel mixer at a temperature ranging from 1~179.~
about 70F to 210F for a period of 1 to l0 minutes. In each instance, the thermoplastic polymer in particulate form was added to the Henschel mixer together with microbiocide and the other plastic additives set forth, if any. After the composition had been mixed, it was extruded into a 25 mil thick sheet. Compatibility was determined by visually observing whether blooming had occurred over a period of up to two months at one week intervals. Extension properties were determined by the ability of the composition to retain its sheet form for subsequent pelletization.
TABLE III
Sample No. 13 14 15 16 16a 16b _, ____ . ............ . . ,. _ _ PVC (Low MW) 100.029.0 100 .
PVC/VA Copolymer 95 100 100 . _ _ ....
- Ba, Cd, Zn, Stabilizer 3.0 0.50 0.5 0.5 . . _ _ . . . _ Stearic Acid 0.25 0.5 . .
- 20 Dioct~l Phthalate 50.0 - 25 25 . _ . _ OBPA 11.177.7 5.5 50 6.6 6.6 . _ _ , . . _ . .
Compatibility I C C G G G
_ Extrusion Properties G G G G G
.
Milling Properties G G G G G G
.
I = Incompatible C = Compatible G = Good 1(~71799 :, `
1- As shown in Table III, ospA is compatible in vinyl -~ chloride-vinyl acetate copolymers or polyvin~l chloride at high levels with or without a plasticizer. However, incompatibility results when 50 parts of dioctyl phthalate plasticizer is included in the polyvinyl chloride composition. In each instance, the resin-microbiocide composition can be formed by extrusion and/or milling.
Samples 13 through 16 are compatibLe with thermo-plastic polymers to form compositions containing an effective concentration of OBPA including polyvinyl chloride, poly-ethylene, polyvinyl acetate, polyurethane, vinyl chloride-vinyl acetate copolymers and thermoplastic rubbers such as chlorinated polyethylene-and nitrile rubbers.
To determine microbiological activity of the OBPA-resin concentrate of this invention, 1 weight percent of a sample 15 based on total weight was blended with a resin composition comprising 100 parts by weight PVC, 3.5 parts Mark ~CV (barium-cadmium-zinc heat stabilizer), 1.5 parts Mark C (phosphite chelate)j 1.0 parts Mark 202A (V.V. Stabilizer), 0.25 stearic acid, 40 parts dioctyl phthalate and 7.7 parts expoxidized soybean oil to obtain a final composition containing 0.05% OBPA.
Blending was effected at about 72F (ambient temperature) and the resultant composition was calendered to form the resin film. The film was tested for microbiological activity both before and after weathering and leached or unleached against Staph. aureus, 209 ATCC 6538; K. pneumonial, ATCC-4352;
Pink stain, Str. recticulum ATCC 25607 and a mixed fungal spore of Aspergillus niger, ATCC 9642, Aspergillus flavus, ATCC 9643, pencillium, ATCC 9644 and Chaetomium globosum, ATCC
6205. The leached film was placed in a water resevoir with at . .
` 1071~99 1 least 5 changes of water for 24 hours wherein the water was 80-85F. The weathered samples were exposed to 100 or 200 or 300 hours of accelerated weathering in an Atlas-XW-W Xenon arc Weather-Ometer programmed (No. 7 cam per ASTM-G-26-70) for continuous light with 18 minutes of water spray every two hours.
Test specimens were placed on nutrient agar inoculated with the bacterial and fungal test organisms. After incubation lbacteria 24 hours at 37C, fungi - 14 days at 28C), anti-microbiocidal activity was evaluated by measuring the size ofthe clear zone of no growth around the sample and rating the degree of growth or stain visually. The results are shown in Table IIIa.
TABLE IIIa Antimicrobiocidal Activity 20ne of Inhibition tmm)/Stain or Growth _ _ . . . _ .
Sample 15 + PVC Staph K. Pink Mixed Aureus pneumonial Stain Spore .. .. _ _ _ . . . . . .. _ . _ Unleached 9/NGCA 5/NGCA 5/NS 6/NG
20 Leached 9/NGCA 4/NGCA 5/NS 6/NG
Weathered 100 Hours 8/NGCA l/NGCA 3/NS 2/NG
Weathered 200 Hours 6/NGCA l/NGCA l/NS 2/NG
Weathered 300 Hours O/TrS O/NG
NGCA = No Growth Contact Area NG = No Growth NS = No Stain TrS = Trace Stain As shown in Table IIIa, the film showed good anti-fungal and antibacterial activity both before and after weathering.
~C~717~9 1 EX~lPLE IV
This example illustrates the nontoxic nature of the compositions of this invention.
A solid composition was prepared by mixing 2,371 grams of a vinyl chloride - 16.8 wt. % vinyl acetate copolymer and 129 grams 10,10' osPA (containing 3 wt. % DOP). The resultant homogeneous composition was extruded into a rod and pelletized.
The pellets were tested for oral and dermal toxicity by the procedures described below.
Adult male rats of the Sprague-Dawley strain, weighing 150-250 grams were fasted for 24 hours, then given a single calculated dose of the above-described composition and placed in screen bottom cages with free access to water and laboratory food for a two week observation period. The solid composition was mixed with the laboratory food in a weight ratio of 1:4.
The results are shown in Table IV.
TABLE IV
Dosage Level of OBPA-Copolymer Mortality (gm/kg) - Number Day . .
As shown in Table IV, no mortality was observed in the test rats even at levels as high as 20 gm per kg of body weight. Thus, the solid composition has a surprisingly high Oral LD50 level in excess of 20 gm/kg. In contrast, OBPA has an Oral LD50 of 15 milligram/kg.
The test for dermal toxicity was conducted with male rabbits. The animals were housed in individual screen bottom ~071799 cages and supplied with water and laboratory food ad libitum and the OBPA-copolymer composition inserted under a sleeve of rubber snugly fastened about the clipped trunk of the test animal. The animals were immobilized for a 24 hour period immediately following the treatment. At the end of the exposure period, the sleeves were removed and the test animals returned to cagès for a two week observation period during which evidences of toxicity were noted and mortality data tabulated as shown in Table V.
TABLE V
Animal Dose Body ~eight (gms) Number ~gm/kg) Initial 1 Week 2 Weeks .
\
This invention relates to solid resin-microbiocide compositions and to a method for forming resin products there-with. ~ore particularly, the present invention relates to solid polymeric compositions containing a high concentration of a microbiocide for the purpose of providing an easily handleable, predispersed and a relatively non-toxic form of the biocide and a method for forming resin products therefrom.
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 which would be susceptible to attack. Heretofore, 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 thereby providing a vehicle for the microbiocide to promote its migration throughout the resin, particularly to its surface. The presently employed procedures usually involve first mixing the microbiocide in a liquid carrier which solubilizes of disperses the microbiocide uniformly followed r by mixing the liquid composition with the final resin composition.
The liquid solvents or dispersants employed are those which do not degrade the properties of the final resin product such `~
1~71799 `'`
1 as plasticizers 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 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.
Alternatively, it has been proposed to add the microbiocide directly to a formable resin composition at the low effective concentrations which prevent microbiological attack. However this procedure has proven to be unsatisfactory since the needed concentrations of microbiocide is quite low, generally less than about 1 weight % and usually between about 200 and 1000 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 procedure 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 toxicological 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 process or utilizes the 1 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 necessar~ to extend the mixing time of the resultant composition. Furthermore, mixing -of these resin compositions containing low concentrations of microbiocides results in the microbiocide being coated on the surface of the mixing apparatus rather than being homogeneously dispersed throughout the resin.
It ~ould be highly desirable to provide solid micro-biocidal compositions having high concentrations of a micro-biocide, above its usually employed effective concentrations, which eliminates the need for a liquid carrier. This would permit incorporating the microbiocide at the desired con-centration subsequently into a resin composition while avoiding toxicological hazards and while providing improved control of the concentration of liquid additives in the final resin product. Furthermore, it would be desirable to ~ provide such compositions wherëin the microbiocide does not degrade the resin and is not itself degraded when incorporated ;1 in the resin so that the compositions can be incorporated sub- -sequently into a resin wherein the microbiocide is present :.
at effective concentrations.
- SUMMARY OF THE INVENTION
:''' - :
This invention provides solid compositions comprising a thermoplastic resin containing between about 1 and 80 weight :j % of at least one microbiocide which is insoluble in water, 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 .~ .
:. 3 10717~9 1 indefinitely upon cooling to ambient temperature while the diffusivity of the microbiocide in the resin under such con-ditions becomes vanishingly small, retains its microbiocidal activity in the resin and does not degrade or react with the resin in which it is dispersed. Representative suitable microbiocides include 10, 10'-oxybisphenoxarsine, N-(tri-chloromethylthio)-4-cyclo-hexene-1,2-dicarboxamide, 2,3,5,6-tetrachloro-4-(methylsulfonyl) pyridine and N-(trichloro-methylthio) phthalimide which is dispersed and/or solubilized in the resin. The solid compositions are both compatible and homogeneously dispersible in a second thermoplastic resin composition to provide effective resistance against microbiocidal attack on the secona thermoplastic resin composition. The solid microbiocidal compositions are prepared by mixing the microbiocide and resin under conditions such that the micro-biocide is rendered substantially nonmigratory to form a homogeneous composition. These microbiocides also function as processing aids for the resin in that they reduce the `
processing temperatures needed to form homogeneous compositions.
Even ~hough the concentration of the microbiocide is above that which would normally present a toxicological hazard, the homo-geneous microbiocide-resin composition is far less toxic than - either the microbiocide itself or liquid compositions con-taining the microbiocide. These compositions can be made without employing a liquid carrier for the microbiocide so that unwanted liquid additives in the second resin composition to be fabricated can be avoided. The concentrated micro-biocide-resin composition is incorporated into the second resin composition in amounts such that the two compositions are compatible and such that the final resin composition con-tains the microbiocide at an effective concentration and below 1(~7~799 1 the concentration that presents a toxicologiCal hazard.
DESCRIPTION OF SPECIFIC EMBODIME2~TS
The compositions of this invention contain the micro-biocide at a concentration which permits the subsequent in-corporation of the resultant composition into a second thermoplastic resin composition as a concentration between about 0.5 and 15 weight ~ based upon the total weight of the resultant composition. When less than about 0.5 weight % of 1 the composition of this invention is incorporated into the second thermoplastic resin composition, less than homogeneous dispersion may be obtained which causes the resultant com-position to ha~e underprotected areas. When more than about 15 weight % of the composition of this invention is incorporated into a second thermoplastic resin which is different than the first thermoplastic resin, the two resins may beco~e incompatible. In addition, when more than about 15 weight of the composition of this invention is incorporated into a second thermoplastic resin different from the first thermo-plastic resin,undesirable changes in the physical characteristicsof the second-thermoplastic resin occurs in that they approach those of the first thermoplastic resin.
f .
' The concentration of microbiocide in the composition of this invention is between about 1 and 80 weight %, preferably from about 5 to about 55 weight %, based upon the total weight of the thermoplastic composition. The micro-biocide 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, ln, lo ~ -oxybis-1 phenoxarsine is used normally in a concentration up to 0.05weight ~; N-(trichloromethylthio)-4-cyclo-hexene-1,2-dicarboximide is used normally in a concentration up to 0.5 weight ~; 2,3,4,6-tetrachloro-4-(methylsulfonyl)pyridine is used normally in a concentration up to 0.75 weight ~; N-(trichloromethylthio) phthalamide is used normally in a con-centration up to 0.75 weight % or Zinc Omadine or tributyl tin fluoride which are used normally in a concentration up to 0.2 weigh.t %. In any event, the microbiocide concentration is controlled so i~ is present in an effective concentration in a second thermoplastic resin composition when added thereto between about 0.5 and 15 weight % based upon the weight of the second thermoplastic resin composition.
In order to form homogeneous resin-microbiocide compositions, 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 solutiorl 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 at the high microbiocidal concentrations utilized herein. In addition, the microbiocide must retain :.~ its activity and not itself becomP degraded or does not degrade .: the resin either during mixing with the resin or after being incorporated into the resin. Stability of the microbiocide-resin concentrate is determined readily by visual observation wherein irreversible dark coloring of the concentrate represents degradation of the composition so that it is not useful in the present invention. For example, the micro-biocide, ortho-benzyl parachlorophenol is miscible in resins, iO7~L799 1 particularly vinyl resins but the resultant resin-microbiocide composition turns irreversibly black and therefore is not useful herein. Tributyl tin oxide is another common micro-biocide not useful herein since it is essentially immiscible with vinyl resins. It is also essential that the microbiocide be substantially insoluble in water so that it is not easily leached from the resin-microbiocide composition either during normal storage or normal use.
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 con-taining the normal upper range concentration of th~ micro-biocide. 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.
~ince the microbiocide is far less migratory within ;,' - the resin than the microbiocide per se or the microbiocide - 20 in solution, it is far less toxic than the microbiocide per ;
se or liquid solutions of the microbiocide even though present ,; at higher concentrations than its effective concentration.
, 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 com-; position of this invention reduces contamination of processing and weighing equipment and facilitates clean~up of this equipment.
The compositions of this invention normally have 1 poor end use physical properties. Therefore, they must be incorporated into another thermoplastic resin to produce useful fabricated thermoplastic products. However, due to their less toxic nature, the compo5ition of this invention provides a significant advantage over the prior art compositions in that they can be processed safely in conventional thermoplastic resin fabrication techni~ues without requiring costly safety equipment and without the need for a liquid carrier for the microbiocide.
In another aspect of this invention, it has been found that the microbiocides employed herein, when employed in high concentrations, function as processing aids in that they ; reduce the melt viscosity and softening point of the thermo-; plastic resin to such a degree that the resin and microbiocide composition can be processed to form a homogeneous composition ` without the need for plasticizers for the resin. That is, the microbiocide has the effect of reducing the viscosity of the thermoplastic resin so that when the two are mixed,such as by milling, the resultant composition can be heated to tem-peratures normally employed in resin-forming processes without the need for adding processing aids that reduce the viscosity of the resin or which provide heat stability to the resin.
This is surprising since this effect on the resin is not ` observed when the microbiocide is incorporated at the normally low concentrations at which the microbiocide is effective to prevent or to inhibit microbiological attack without presenting a toxicological hazard to humans. The degree of this effect is dependent upon the type of thermoplastic resin employed, the type of microbiocide employed and the concentration of microbiocide employed.
10~1~99 :`~
1 The compositions of this invention are prepared by mixing a particulate thermoplastic resin with a high concentration of microbiocide such that a homogeneous composition can be obtained without the need for additional processing aids such as a plasticizer, a heat stabilizer or a lubricant for the resin to obtain the advantages set forth above. However, they can be added if desired for special effect. The micro-biocide and resin are mixed to obtain a dry homogeneous particulate composition. Thereafter, the composition is heated and mixed so that the resin is melted to a homogeneous composition to obtain solution or dispersion of the microbiocide in the resin. ~hen heating and mixing the composition, the melting point and viscosity of the resin composition is reduced as compared to the resin per se. It has been found that homogeneous resin-microbiocide compositions containing high ~' concentrations of the microbiocide ~an be formed in this manner.
. In addition, it has been found that 10,10'-oxybisphenoxarsine and 2,3,5,6-tetrachloro-4-~methylsulfonyl) pyridine function as-a heat stabilizer for polyvinyl chloride-polyvinyl .:.
~-- 20 acetate copolymers and homopolymer.
` Representative suitable thermoplastic resins that can be employed to form the microbiocide-resin composition or which can be compounded with the microbiocide-resin com-position include polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyurethanes, polyamides, polyolefins, polystyrene, vinyl chloride-acrylonitrile copolymers, poly-esters and ~he like.
~uitable microbiocides include:
B OBPA - 10,10'-oxybisphenoxarsine Vancide 89 - N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboximide ::
1~71799 i Dowcil S-13 - 2,3,5,6-tetrachloro-4-(methylsulfonyl) pyridine Dowcil A-40*- 2,3,5-trichloro-4-propylsulfonyl pyridine Zinc Omadine*- zinc salt of l-hydroxypyridine-2-thione Fungitrol 11*- N-(trichloromethylthio) phthalimide Difolatan*- 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 bixdithiocarbamate Zineb - zinc analog of ~laneb ~: Nabam - disodium analog or Maneb . Ferbam - ferric dimethyl dithiocarbamate Ziram - zinc analog of Ferbam ~ Karathane*- 2,4-dinitro-6-capryl phenol crotonate ;~ Ovotran*- p-chlorophenyl-p-chlorobenzenesulphonate ;. Skane M-8*- 2-N-octyl-4-isothiazolin-3-one Benomyl - methyl-l(butylcarbamoyl)-2-benzimidazole carbamate Metasol TK-100*- 2-(4-thiazolyl) benzimidazole ` Copper-8 - copper 8-hydroxy-quinolinate :~ a-diethoxyphosphinodithioacetylurea a-dimethoxyphosphinodithioacetylurea Diethoxyphosphinodithioacetamide : Dimethoxyphosphinodithioacetamide Bis(dimethylamido) phosphoryl fluoride Tributyl tin fluoride and mixtures thereof. The preferred microbiocides are 10,10'-oxybisphenoxarsine, N-(trichloromethylthio)-4-cyclohexene-1,2-30 dicarboximide,2,3,5,6-tetrachloro-4-(methylsulfonyl) pyridine *Trade Mark ~ .
1~71799 1 and N-(trichloro~ethylthio) phthalimide since they are relatively easy to incorporate into a wide variety of resins at high concentration without significant loss of micro-biological activity and without significant degradation to the resin.
The microbiocide and resin are mixed under conditions of heating to melt and to soften the resin and to form a homo-geneous mixture wherein upon cooling the microbiocide is rendered far less migratory by the resin matrix. The mixture ~ 1~ is subjected to shear forces and heat in any suitable apparatus ;i' such as a two-roll mill or a Banbury mixer or extruder and ,.
' the resultant softened composition is formed such as by extrusion, milling or calendering. The formed composition is cooled so that it can be broken up into small particles thereby permitting its subsequent incorporation into other ` thermoplastic compositions having an effective low concentration of the microbiocides.
The compositions of this invention are blended with a second thermoplastic composition by conven~ional 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 compatible so that a homogeneous final composition results.
The microbiocide-containing composition should have a softening temperature below or within the range of temperatures en-countered during conventional processing of the second thermo-1 plastic composition. These temperatures are within the range of between about 250~ and about 500F. It is preferred that the resin-microbiocide concentrates have a softening temperature within a range of about 150F to 300F.
In forming the microbiocide-containing composition of this invention, the usual resin additives optionally can be 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, ; lO reduced concentration of plasticizer must be employed to avoid 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 comp~sitions -~ of the resin, the plasticizer and the microbiocide. Generally, - moderate plasticizer concentrations can be tolerated within the range of between about 5 and 2~ weight % when the micro-biocides are employed at concentrations of 50 weight % 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 is limited by their exclusion. To determine suitable plasticizers for a particular resin-microbiocide system, all that is necessary is that one add the plasticizer, within the range noted above, to the resin-microbiocide composition, mix the resultant composition and visually determine whether the microbiocide has been immobilized by the resin to form a homogeneous composition. Any of the conventional resin plasticizers can be employed including dialkyl phthalates, epoxy plasticizers, polyester plasticizers, dialkyl phosphites , ..
1~71799 and the like. In addition, the usual resin additives can be included such as ultraviolet stabilizer, heat stabilizer, fillers, dyes, pigments, lubricants and the like.
In a preferred aspect of this invention, the con-; centrated microbiocide-resin composition is formed with a vinyl chloride-vinyl acetate copolymer and the microbiocide, preferably 10,10'-oxybisphenoxarsine ~OBPA), and is incorporated into a second thermoplastic resin having a composition different than the chloride-vinyl acetate copolymer employed to form the concentrate. It has been found that the final composition produced thereby contains the microbiocide , ,.- ~, ~ , homogeneously distributed therein in effective concentrations while minimizing or eliminating the need for a plasticizer ; :;
during compounding o~ the final composition. This is desirable since some thermoplastic resins such as polyurethanes can ~ ;
tolerate only very small concentrations of a plasticizer, if ` any, to avoid physical degradation of the thermoplastic resins r In addition, as noted above, the presence of a plasticizer may cause undesirable blooming of the microbiocide in the resin and so that minimizing or eliminating the use of a plasticizer is desirable in forming a final product having desirable physical characteristics and which is protected against microbiological attack. Particularly desirable products are obtained when the second thermoplastic resin is polyurethane, polyvinyl chloride or polyethylene. Although any of the microbiocides set forth above are useful in forming these final products, OBPA is preferred since it has high microbiocidal activity and so that only small concentrations of the concentrate are required to obtain homogeneous dispersion of OBPA at effective concentrations. In this embodiment, the 1~7~7~39 1 PVC/PVA based concentrate is employed in amounts of between about 0.5 and 5.0 weight percent based upon the total com-position. In a specific embodiment, the concentrate is formed from about 95 parts vinyl chloride-vinyl acetate copolymer and about 5 parts OBPA which optionally can contain about 0.1 parts of a lubricant such as stearic acid or zinc stearate.
About 1 part of this concentrate then is compounded into about 99 parts of a second thermoplastic resin composition such as polyvinyl chloride, polyurethane or polyethylene which optionally can contain the usual resin additives set forth above.
The following examples illustrate the present in-vention and are not intended to limit the same.
EXAMPLE I
This example illustrates that Dowcil S-13 can be incorporated into thermoplastic resins either in the absence or in the presence of a plasticizer.
Each of the formulations set forth below in Table I
were blended in a Henschel mixer at temperature ranging from about 70 F to 220 F for a period of 1 to 10 minutes to form a homogeneous powder blend. In each instance, the thermoplastic resin, in particulate form, was added to the Henschel mixer together with the other plastic additive, if any, and micro-biocide. After the thermoplastic resin composition had been mixed, it was extruded at a temperature between 150F
and 300F into a rod form which then was cooled to room temperature. The rod then was pelletized. Compatibility was determined by sheeting a portion of the pellets and visually observing whether blooming had occurred over a period of up to two months at one week intervals. Extrusion properties 1C~71799 1 were determined by the ability of the composition to retain its rod from for subsequent pelletization.
TABLE I
Sample No. 1 2 3 4 5 6 7 (parts by weight) PVC (low MW)100.0100.0100.0 47 .
.~ Copolymer VYHH
~:: PVC/VA (86:14) 46.75 100 100 Ba, Cd, Zn Stabilizer-(Mark KCs) 3.0 3.0 1.0 Stearic Acid 0.5 0.5 1.0 0.25 : Dioctyl Phthalate15.0 15 . .
: Dipropylene Glycol Dibenzoate 15.0 -Dowcil S-13 17.8 17.8 306.0 53.0 53.0 25 20 _ Compatibility I C C C C C C
Extrusion properties NG G G NG G G G
. ~
~0 Milling properties G G G G G G G
.. ..
I = Incompatible or Surface Blooming --C = Compatible NG = Not Good G = Good As shown in Table I, Dowcil S-13 is compatible in vinyl chloride-vinyl acetate copolymers or vinyl chloride homopolymers at high levels without a plasticizer. However, surface blooming results when 15 parts of dioctyl phthalate plasticizer and 0.5 parts of stearic acid lubricant are included in the composition while compatibility and no blooming result 1 when employing 15 parts of the sarne plasticizer without the stearic acid lubricant. In each instance, the resin-microbiocide composition can be formed by extrusion and~or milling.
Samples 1 through 7 are compatible with thermoplastic polymers to ~orm compositions containing an ef~ective con-centration of ~owcil S-13 including vinyl chloride homopolymers, polyethylene polyvinyl acetate, polyurethane, vinyl chloride-vinyl acetate copolymers and thermoplastic rubbers such as chlorinated polyethylene and nitrile rubbers.
To determine microbiological activity of the Dowcil S-13- resin concentrate of this invention, 1.5 weight percent of sa~ple 5, based on total weight was blended with the resin composition employéd for such testing in Example III by the blending process described in Example III. The testing procedures and the bacteria and fungi tested were those set forth in Example III including a 500 hour weather test. The results are set forth in Table Ia.
TABLE Ia Antimicrobiocidal Activity Zone of Inhibition (mm)/Stain or Growth .
Samp~e 5 + PVC Staph. K. Pink Mixed Aureus pneumonial Stain Spore Unleached 7/NGCAl/NGCA 8/NS 3/NG
Leached 7/NGCAl/NGCA 8/NS 3/NG
Weathered 100 Hours 5/NGCA 0~5/NGCA 5/NS 2jNG
Weathered 200 Hours 6/NGCA 0.5/NGCA 5/NS 0/NG
Weathered 300 Hours 0/LS 0/LG 0/HS 0/LG
Weathered 500 Hours 0/HS 0/LG
NGCA = No Growth Contact Area LG = Low Growth NS = No Stain HS = Heavy Stain NG = No Growth LS = Light Stain ~ 16 -1(~71799 1 As shown in Table Ia, the film showed good antifungal activity both before and after weathering and no evidence of stain up to 200 hours of weathering.
EXAMPLE II
This example illustrates that Vancide-89 can be incorporated into thermoplastic resins either in the absence ~`~ or in the presence of a plasticizer.
Each of the formulations set forth below in Table II
were blended in a Henschel mixer, except Sample 9, which was blended in a two roll mill at about 250F. Temperatures in the Henschel mixer ranged from 70F to 220F. Mixing times ranged from l to lO minutes. In each instance, the thermo-plastic polymer in particulate form was added to the` Henschel mixer or the two roll mill, together with the microbiocide and other plastic additives set forth, if any. After the composition had been mixed, it was extruded at a temperature between 150F and 300F and extruded into a 2.5 mil thick sheet. Compatibility was determined by visually observing whether blooming had occurred over a period of up to two months at one week intervals. Extrusion properties were determined by the ability of the composition to retain its sheet form for subsequent pelletization.
107179~
TABLE I I
Sample No. 8 9 10 11 12 . _ . ... . ...
(Parts by Weight) 100.0 100.0 100.0 PVC (Low MW) :: . .. .. . _ .
- CvcP/lYm8e6r V14HH 49~75 1~)0 . . .
Ba, Cd, Zn, Stabilizer - (Mark KCB) 3.0 3.0 3.0 -- . . .
Stearic Acid 0.5 0.5 0.5 0.25 Dioctyl Phthalate 15.0 15.0 15 1 0 - - --_- _ __ _ _ Vancide-89 17.8 17.8 118.5 50.0 25 ... . . . .................. . ~ _ Mark 275 Tin Stabilizer 0 5 . . . _ . _ . . . _ _ _ . . . _ _ . . . _ _ Compatibility I C C C C
.. .. _ _ .
Extrusion Properties NG NG NG G G
. _ ... _ . .. .. _ Milling Properties G G G G G
.
I = Incompatible C = Compatible NG = Not Good G = Good As shown in Table II, ~ancide-89 is compatible in vinyl chloride-vinyl acetate copolymer or polyvinyl chloride at high levels with or without a plasticizer. In compatibility results when 15 parts of dioctyl phthalate plasticizer is included in the composition.
In each instance, the resin-microbiocide composition can be formed by extrusion and/or milling. Samples 8 through 12 are compatible with thermoplastic polymers to form compositions containing an effective concentration of Vancide 89 including polyvinyl chloride, polyethylene,polyvinyl acetate, poly~
urethane, vinyl chloride-vinyl acetate copolymers and thermo--- 18 --~. '' 1(~71799 1 plastic rubbers such as chlorinated polyethylene and nitrile rubbers.
To determine microbiological activity of the Vancide-89-resin concentrate of this invention, 1 weight percent of Sample 11, based on total weight was blended with the resin composition employed for such testing in Example III by the blending process described in Example III. The testing pro-cedures and the bacteria and fungi tested were those set forth in Example III but omitting the 300 hour weather test.
The results are set forth in Table IIa.
TABLE IIa Antimicrobiocidal Activity Zone of Inhibi~tion (mm)/Stain or Growth Sample 11 + PVC Staph X. Pink Mixed Aureus pneumonial Stain Spore Unleached 4/NGCA 0/NGCA ~.5/NS 2/NG
Leached 4/NGCA 0/NGCA 0.5/NS, 2/NG
Weathered 100 Hours 4/NGCA 0/NGCA 0/NS l/NG
Weathered 200 Hours 3/NGCA 0/NGCA 0/TrS l/NG
NGCA = No Growth Contact Area NS = No Stain NG = No Growth TrS = Trace Stain As shown in Table IIa, the film showed good antifungal and antibacterial activity both before and after weathering.
EXAMPLE III
This example illustrates that OBPA can be incorporated into thermoplastic resins either in the absence or in the presence of a plasticizer.
Each of the formulations set forth below in Table III
were blended in a Henschel mixer at a temperature ranging from 1~179.~
about 70F to 210F for a period of 1 to l0 minutes. In each instance, the thermoplastic polymer in particulate form was added to the Henschel mixer together with microbiocide and the other plastic additives set forth, if any. After the composition had been mixed, it was extruded into a 25 mil thick sheet. Compatibility was determined by visually observing whether blooming had occurred over a period of up to two months at one week intervals. Extension properties were determined by the ability of the composition to retain its sheet form for subsequent pelletization.
TABLE III
Sample No. 13 14 15 16 16a 16b _, ____ . ............ . . ,. _ _ PVC (Low MW) 100.029.0 100 .
PVC/VA Copolymer 95 100 100 . _ _ ....
- Ba, Cd, Zn, Stabilizer 3.0 0.50 0.5 0.5 . . _ _ . . . _ Stearic Acid 0.25 0.5 . .
- 20 Dioct~l Phthalate 50.0 - 25 25 . _ . _ OBPA 11.177.7 5.5 50 6.6 6.6 . _ _ , . . _ . .
Compatibility I C C G G G
_ Extrusion Properties G G G G G
.
Milling Properties G G G G G G
.
I = Incompatible C = Compatible G = Good 1(~71799 :, `
1- As shown in Table III, ospA is compatible in vinyl -~ chloride-vinyl acetate copolymers or polyvin~l chloride at high levels with or without a plasticizer. However, incompatibility results when 50 parts of dioctyl phthalate plasticizer is included in the polyvinyl chloride composition. In each instance, the resin-microbiocide composition can be formed by extrusion and/or milling.
Samples 13 through 16 are compatibLe with thermo-plastic polymers to form compositions containing an effective concentration of OBPA including polyvinyl chloride, poly-ethylene, polyvinyl acetate, polyurethane, vinyl chloride-vinyl acetate copolymers and thermoplastic rubbers such as chlorinated polyethylene-and nitrile rubbers.
To determine microbiological activity of the OBPA-resin concentrate of this invention, 1 weight percent of a sample 15 based on total weight was blended with a resin composition comprising 100 parts by weight PVC, 3.5 parts Mark ~CV (barium-cadmium-zinc heat stabilizer), 1.5 parts Mark C (phosphite chelate)j 1.0 parts Mark 202A (V.V. Stabilizer), 0.25 stearic acid, 40 parts dioctyl phthalate and 7.7 parts expoxidized soybean oil to obtain a final composition containing 0.05% OBPA.
Blending was effected at about 72F (ambient temperature) and the resultant composition was calendered to form the resin film. The film was tested for microbiological activity both before and after weathering and leached or unleached against Staph. aureus, 209 ATCC 6538; K. pneumonial, ATCC-4352;
Pink stain, Str. recticulum ATCC 25607 and a mixed fungal spore of Aspergillus niger, ATCC 9642, Aspergillus flavus, ATCC 9643, pencillium, ATCC 9644 and Chaetomium globosum, ATCC
6205. The leached film was placed in a water resevoir with at . .
` 1071~99 1 least 5 changes of water for 24 hours wherein the water was 80-85F. The weathered samples were exposed to 100 or 200 or 300 hours of accelerated weathering in an Atlas-XW-W Xenon arc Weather-Ometer programmed (No. 7 cam per ASTM-G-26-70) for continuous light with 18 minutes of water spray every two hours.
Test specimens were placed on nutrient agar inoculated with the bacterial and fungal test organisms. After incubation lbacteria 24 hours at 37C, fungi - 14 days at 28C), anti-microbiocidal activity was evaluated by measuring the size ofthe clear zone of no growth around the sample and rating the degree of growth or stain visually. The results are shown in Table IIIa.
TABLE IIIa Antimicrobiocidal Activity 20ne of Inhibition tmm)/Stain or Growth _ _ . . . _ .
Sample 15 + PVC Staph K. Pink Mixed Aureus pneumonial Stain Spore .. .. _ _ _ . . . . . .. _ . _ Unleached 9/NGCA 5/NGCA 5/NS 6/NG
20 Leached 9/NGCA 4/NGCA 5/NS 6/NG
Weathered 100 Hours 8/NGCA l/NGCA 3/NS 2/NG
Weathered 200 Hours 6/NGCA l/NGCA l/NS 2/NG
Weathered 300 Hours O/TrS O/NG
NGCA = No Growth Contact Area NG = No Growth NS = No Stain TrS = Trace Stain As shown in Table IIIa, the film showed good anti-fungal and antibacterial activity both before and after weathering.
~C~717~9 1 EX~lPLE IV
This example illustrates the nontoxic nature of the compositions of this invention.
A solid composition was prepared by mixing 2,371 grams of a vinyl chloride - 16.8 wt. % vinyl acetate copolymer and 129 grams 10,10' osPA (containing 3 wt. % DOP). The resultant homogeneous composition was extruded into a rod and pelletized.
The pellets were tested for oral and dermal toxicity by the procedures described below.
Adult male rats of the Sprague-Dawley strain, weighing 150-250 grams were fasted for 24 hours, then given a single calculated dose of the above-described composition and placed in screen bottom cages with free access to water and laboratory food for a two week observation period. The solid composition was mixed with the laboratory food in a weight ratio of 1:4.
The results are shown in Table IV.
TABLE IV
Dosage Level of OBPA-Copolymer Mortality (gm/kg) - Number Day . .
As shown in Table IV, no mortality was observed in the test rats even at levels as high as 20 gm per kg of body weight. Thus, the solid composition has a surprisingly high Oral LD50 level in excess of 20 gm/kg. In contrast, OBPA has an Oral LD50 of 15 milligram/kg.
The test for dermal toxicity was conducted with male rabbits. The animals were housed in individual screen bottom ~071799 cages and supplied with water and laboratory food ad libitum and the OBPA-copolymer composition inserted under a sleeve of rubber snugly fastened about the clipped trunk of the test animal. The animals were immobilized for a 24 hour period immediately following the treatment. At the end of the exposure period, the sleeves were removed and the test animals returned to cagès for a two week observation period during which evidences of toxicity were noted and mortality data tabulated as shown in Table V.
TABLE V
Animal Dose Body ~eight (gms) Number ~gm/kg) Initial 1 Week 2 Weeks .
2 2 - 3650 3774 3846
3 4 2960 3329 3512
4 4 3140 3247 3510 6 ~ 3355 3557 3585 . . ._ ._ . ... --No mortalities were observed during the test period.
Thus, the dermal toxicity of the test composition is in excess of 8 gm/kg.
EXAMPLE V
This example illustrates that Fungitrol-ll and Zinc Omadine can be incorporated in high concentrations in polyvinyl chloride, homopolymer and polyvinyl chloride-polyvinyl acetate copolymer containing from about 10 to 18 weight polyvinyl acetate and provide antimicrobiocidal activity.
The compositions in Table VI were blended to form a microbiocide concentrate, subsequently blended with polyvinyl 1 chloride to form a film containing the microbiocide at its normal usage concentration and the film then was tested for microbiological activity. The initial concentrates were prepared by physically mixing the resin, microbiocide and 1%
Mark 275 tin stabilizer in a Hobart Blender for 5 minutes.
The dry blends were formed into strands on a Rheocard extruder at 50 RPm screw speed with a 1/8 inch diameter die. The strands were allowed to cool to room temperature and then were ground into small irregular particles. The compositions dry-blended and extruded are shown in Table VI.
TABLE VI
r - Microbiocide Weight %
Microbiocide Resin Extruction ~emperature,C
Fungitrol-ll 35 PVC/PVA 110, 115, 120, 125 Fungitrol-ll 50 PVC/PVA 110, 115, 125, 130 Fungitrol-ll 35 PVC 120, 120, 125, 135 .
Fungitrol-ll 50 PVC 120, 120, 125, 135 . .
Zinc Omadine 5 - PVC/PV~ 110, 120, 135, 135 ..
2inc Omadine 10 PVC/PVA 110, 120, 125, 125 . _ Zinc Omadine 20 PVC/PVA 110, 120, 125, 135 .
Zinc Omadine 10 PVC 110, 120, 125, 135 Zinc Omadine 20 PVC 110, 120, 125, 135 . . .
In each instance, a homogeneous composition was formed which could be incorporated subse~uently into a polyvinyl chloride composition to form a resin composition having micro-biocidal activity at the normal usage concentration of themicrobiocide.
The PVC resin composition with which the concentrates set forth above were blended comprises 100 parts PVC, 3.5 parts Mark KCB (borium-cadmium-zinc heat stabilizer), 1.5 parts phos-phite chelate, 1.0 parts Mark 202A (UV stabilizer), 0.25 parts stearic acid, 40 parts dioctyl phthalate and 7.7 parts epoxidized soybean oil. This composition was blended with 1.5 weight ~ of the Fungitrol-ll composition formed from PVC and containing 50% Fungitrol-ll to form a composition containing 0.75 weight % Fungitrol-ll or was blended with 1.0 weight ~ of the Zinc Omadine composition ~ormed from PVC and containing 20% Zinc Omadine to form a composition containing 0.20 weight % of Zinc Omadine. Blending was effected at about 72F (ambient temperature) and the resultant compositions were milled to form the resin film. These films were tested for microbiological activity both before and after weathering against Staph. aureus, 209 ATCC 6538; K. pneumonial, ATCC 4352; Pink stain, Str.
reticulum ATCC 25607 and a mixed fungal spore of Asper~illus niger, ATCC 9642, Aspergillus flavus, ATCC 9643, Penicilllum ` funiculosum, ATCC 9644 and Chaetomium globosum, ATCC 6205. The ._ 20 weathered samples were exposed to 100 hours of accelerated weathering in an Atlas 600-XW-W Xenon arc Weather Ometer, programmed (No. 7 cam per ATSM-G-2670) for continuous light with 18 minutes of water spray every 2 hours.
Test specimens were placed on nutrient agar inoculated with the bacterial and fungal test organisms. After incubation (bacteria - 24 hours at 37C, fungi - 14 days at 28C), anti-microbiocidal activity was evaluated by measuring the size of the clear zone of no growth around the sample and rating the degree of growth or stain visually. The results arç shown in Table VII.
10~1799 TABLE VII
Antimicrobiocidal Activity Zone of Inhibition (mm)/Stain or Growth Microbiocide Staph. K. Pink Mixed aureu~ pneumonial Stain Spore Fungitrol-ll Unweathered 2/NGCA0/NGCA 0/NS 3/NG
Weathered-100 hrs. l/NGCA 0/NGCA 0/NS 3/NG
1 0 - - -'~-~-- ' Zinc Omadine Unweathered 7/NGCA2.5/NGCA 5/NS 2/NG
Weathered-100 hrs. 0/GCA 0~GCA 0/HS 0/MG
NGCA = No Growth in Contact Area GCA = Growth in Contact Area NS = No Stain NG = No Growth-HS = Heavy Stain MG = Moderate Growth As shown in Table VII, the PVC film containing the Fungitrol-ll concentrate showed good antigungal activity to mixed fungi before and after weathering~and no evidence of stain. At the concentration used (0.75%), antibacterial activity was shown to Sta ~. aureus, but not to the gram negative K. pneumonial. The PVC film containing Zinc Omadine showed excellent antimicrobial activity before weathering to all of the bacterial and fungal test organisms. Activity was lost after 100 hours of weathering.
EXAMPLE VI
This example illustrates that tributyl tin fluoride can be incorporated into thermoplastic resins in high con-centrations.
~071799 .
1 Each of the formulations set forth in Table VIII
were mixed in a Hobart Blender for 5 minutes at about 72F
(ambient temperature). Each resin was added to the blender in particulate form with 1 weight % Mark 275 (tin stabilizer) and the tributyl tin fluoride. The resultant compositions were extruded on a Rheocard extruder at the temperatures shown in Table VIII to form strands. The extruder was operated at 50 RPM screw speed with a 1/8 inch diameter die. The strands were visually evaluated and then ground to small irregular particles, added to a polyvinyl chloride composition, processed into films and were found to impart microbiocidal activity to the films.
TABLE VIII
', ' .
. _ _ . .. . .
Weight %
Tributyl Tin Extrusion Resin Fluorlde Temperature, C Appearance PVC/PVA 10 120, 135, 140, 150 Homogeneous white Qpaque solid suspens- ~ -ion of tribut~l tin fluoride with resin;
- smooth surface PVC/PVA 20 125, 135, 135, 140 Homogeneous white opaque solid sus-pension of tributyl tin fluoride with resin;smooth surface PVC 10 140, 145, 155, 155 Homogeneous white - opaque solid sus-pension of tributyl tin fluoride with resin; rough surface It was found that tributyl tin fluoride was more easily homogeneously added to PVC/PVA than to PVC to form a homogeneous composition wherein the tributyl tin fluoride is dispersed into the resins. All of the composition formed were -- satisfactory as resin-microbiocidal concentrates.
Thus, the dermal toxicity of the test composition is in excess of 8 gm/kg.
EXAMPLE V
This example illustrates that Fungitrol-ll and Zinc Omadine can be incorporated in high concentrations in polyvinyl chloride, homopolymer and polyvinyl chloride-polyvinyl acetate copolymer containing from about 10 to 18 weight polyvinyl acetate and provide antimicrobiocidal activity.
The compositions in Table VI were blended to form a microbiocide concentrate, subsequently blended with polyvinyl 1 chloride to form a film containing the microbiocide at its normal usage concentration and the film then was tested for microbiological activity. The initial concentrates were prepared by physically mixing the resin, microbiocide and 1%
Mark 275 tin stabilizer in a Hobart Blender for 5 minutes.
The dry blends were formed into strands on a Rheocard extruder at 50 RPm screw speed with a 1/8 inch diameter die. The strands were allowed to cool to room temperature and then were ground into small irregular particles. The compositions dry-blended and extruded are shown in Table VI.
TABLE VI
r - Microbiocide Weight %
Microbiocide Resin Extruction ~emperature,C
Fungitrol-ll 35 PVC/PVA 110, 115, 120, 125 Fungitrol-ll 50 PVC/PVA 110, 115, 125, 130 Fungitrol-ll 35 PVC 120, 120, 125, 135 .
Fungitrol-ll 50 PVC 120, 120, 125, 135 . .
Zinc Omadine 5 - PVC/PV~ 110, 120, 135, 135 ..
2inc Omadine 10 PVC/PVA 110, 120, 125, 125 . _ Zinc Omadine 20 PVC/PVA 110, 120, 125, 135 .
Zinc Omadine 10 PVC 110, 120, 125, 135 Zinc Omadine 20 PVC 110, 120, 125, 135 . . .
In each instance, a homogeneous composition was formed which could be incorporated subse~uently into a polyvinyl chloride composition to form a resin composition having micro-biocidal activity at the normal usage concentration of themicrobiocide.
The PVC resin composition with which the concentrates set forth above were blended comprises 100 parts PVC, 3.5 parts Mark KCB (borium-cadmium-zinc heat stabilizer), 1.5 parts phos-phite chelate, 1.0 parts Mark 202A (UV stabilizer), 0.25 parts stearic acid, 40 parts dioctyl phthalate and 7.7 parts epoxidized soybean oil. This composition was blended with 1.5 weight ~ of the Fungitrol-ll composition formed from PVC and containing 50% Fungitrol-ll to form a composition containing 0.75 weight % Fungitrol-ll or was blended with 1.0 weight ~ of the Zinc Omadine composition ~ormed from PVC and containing 20% Zinc Omadine to form a composition containing 0.20 weight % of Zinc Omadine. Blending was effected at about 72F (ambient temperature) and the resultant compositions were milled to form the resin film. These films were tested for microbiological activity both before and after weathering against Staph. aureus, 209 ATCC 6538; K. pneumonial, ATCC 4352; Pink stain, Str.
reticulum ATCC 25607 and a mixed fungal spore of Asper~illus niger, ATCC 9642, Aspergillus flavus, ATCC 9643, Penicilllum ` funiculosum, ATCC 9644 and Chaetomium globosum, ATCC 6205. The ._ 20 weathered samples were exposed to 100 hours of accelerated weathering in an Atlas 600-XW-W Xenon arc Weather Ometer, programmed (No. 7 cam per ATSM-G-2670) for continuous light with 18 minutes of water spray every 2 hours.
Test specimens were placed on nutrient agar inoculated with the bacterial and fungal test organisms. After incubation (bacteria - 24 hours at 37C, fungi - 14 days at 28C), anti-microbiocidal activity was evaluated by measuring the size of the clear zone of no growth around the sample and rating the degree of growth or stain visually. The results arç shown in Table VII.
10~1799 TABLE VII
Antimicrobiocidal Activity Zone of Inhibition (mm)/Stain or Growth Microbiocide Staph. K. Pink Mixed aureu~ pneumonial Stain Spore Fungitrol-ll Unweathered 2/NGCA0/NGCA 0/NS 3/NG
Weathered-100 hrs. l/NGCA 0/NGCA 0/NS 3/NG
1 0 - - -'~-~-- ' Zinc Omadine Unweathered 7/NGCA2.5/NGCA 5/NS 2/NG
Weathered-100 hrs. 0/GCA 0~GCA 0/HS 0/MG
NGCA = No Growth in Contact Area GCA = Growth in Contact Area NS = No Stain NG = No Growth-HS = Heavy Stain MG = Moderate Growth As shown in Table VII, the PVC film containing the Fungitrol-ll concentrate showed good antigungal activity to mixed fungi before and after weathering~and no evidence of stain. At the concentration used (0.75%), antibacterial activity was shown to Sta ~. aureus, but not to the gram negative K. pneumonial. The PVC film containing Zinc Omadine showed excellent antimicrobial activity before weathering to all of the bacterial and fungal test organisms. Activity was lost after 100 hours of weathering.
EXAMPLE VI
This example illustrates that tributyl tin fluoride can be incorporated into thermoplastic resins in high con-centrations.
~071799 .
1 Each of the formulations set forth in Table VIII
were mixed in a Hobart Blender for 5 minutes at about 72F
(ambient temperature). Each resin was added to the blender in particulate form with 1 weight % Mark 275 (tin stabilizer) and the tributyl tin fluoride. The resultant compositions were extruded on a Rheocard extruder at the temperatures shown in Table VIII to form strands. The extruder was operated at 50 RPM screw speed with a 1/8 inch diameter die. The strands were visually evaluated and then ground to small irregular particles, added to a polyvinyl chloride composition, processed into films and were found to impart microbiocidal activity to the films.
TABLE VIII
', ' .
. _ _ . .. . .
Weight %
Tributyl Tin Extrusion Resin Fluorlde Temperature, C Appearance PVC/PVA 10 120, 135, 140, 150 Homogeneous white Qpaque solid suspens- ~ -ion of tribut~l tin fluoride with resin;
- smooth surface PVC/PVA 20 125, 135, 135, 140 Homogeneous white opaque solid sus-pension of tributyl tin fluoride with resin;smooth surface PVC 10 140, 145, 155, 155 Homogeneous white - opaque solid sus-pension of tributyl tin fluoride with resin; rough surface It was found that tributyl tin fluoride was more easily homogeneously added to PVC/PVA than to PVC to form a homogeneous composition wherein the tributyl tin fluoride is dispersed into the resins. All of the composition formed were -- satisfactory as resin-microbiocidal concentrates.
Claims (42)
1. A solid composition comprising a homogeneous mixture of a solid thermoplastic resin and from 1 to 80 weight percent of a microbiocide at a concentration of at least about 20 times greater than the normal upper usage concentration of the microbiocide and wherein said microbiocide is immobilized in said resin, the concentration of said microbiocide in said mixture being sufficient to render a second thermoplastic composition resistant to microbiological degradation when said mixture is added to said second thermoplastic composition at a sufficiently low concentration to render said mixture and said second thermo-plastic composition compatible.
2. The solid composition of claim 1 in particulate form.
3. The solid composition of claim 1 which contains a plasticizer for said solid thermoplastic resin.
4. The solid composition of claim 2 which contains a plasticizer for said solid thermoplastic resin.
5. The solid composition of claim 1 wherein the microbio-cide is 10,10'-oxybisphenoxarsine.
6. The solid composition of claim 2 wherein the microbio-cide is 10,10'-oxybisphenoxarsine.
7. The solid composition of claim 1 wherein the microbio-cide isN-(trichloromethylthio)-4-cyclohexene-1,2-dicarboxxamide.
8. The solid composition of claim 2 wherein the micro-biocide is N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboxamide.
9. The solid composition of claim 1 wherein the micro-biocide is 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine.
10. The solid composition of claim 2 wherein the micro-biocide is 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine.
11. The solid composition of claim 1 wherein the micro-biocide is N-(trichloromethylthio)phthalimide.
12. The solid composition of claim 2 wherein the micro-biocide is N-(trichloromethylthio)phthalimide.
13. The solid composition of claim 1 wherein the micro-biocide is tributyl tin fluoride.
14. The solid composition of claim 2 wherein the micro-biocide is tributyl tin fluoride.
15. The solid composition of claim 1 wherein the solid thermoplastic resin is polyvinyl chloride.
16. The solid composition of claim 2 wherein the solid thermoplastic resin is polyvinyl chloride.
17. The solid composition of claim 1 wherein the solid thermoplastic resin is a copolymer of vinyl chloride and vinyl acetate.
18. The solid composition of claim 2 wherein the solid thermoplastic resin is a copolymer of vinyl chloride and vinyl acetate.
19. The solid composition of claim 6 wherein the said thermoplastic resin is polyvinyl chloride.
20. The solid composition of claim 8 wherein the solid thermoplastic resin is polyvinyl chloride.
21. The solid composition of claim 10 wherein the solid thermoplastic resin is polyvinyl chloride.
22. The solid composition of claim 6 wherein the solid thermoplastic resin is a copolymer of vinyl chloride and vinyl acetate.
23. The solid composition of claim 8 wherein the solid thermoplastic resin is a copolymer of vinyl chloride and vinyl acetate.
24. The solid composition of claim 10 wherein the solid thermoplastic resin is a copolymer of vinyl chloride and vinyl acetate.
25. The process for forming a solid thermoplastic com-position containing an effective concentration of a microbiocide but at a concentration less than that which presents a toxico-logical hazard which comprises mixing the solid composition, defined by claim 2, with a second thermoplastic composition at a temperature above the softening temperatures of the microbiocidally active composition and the second thermoplastic composition, the concentration of the microbiocidally active composition being sufficiently low to render it compatible with said second thermoplastic resin, and cooling the mixture to form a solid containing the microbiocidally active composition and second thermoplastic resin in homogeneous admixture.
26. The process of claim 25 wherein the resin of the microbiocidally active composition is polyvinyl chloride.
27. The process of claim 25 wherein the resin of the microbiocidally active composition is a copolymer of vinyl chloride and vinyl acetate.
28. The process of claim 25 wherein the microbiocide is 10,10'-oxybisphenoxarsine.
29. The process of claim 26 wherein the microbiocide is 10,10'-oxybisphenoxarsine.
30. The process of claim 25 wherein the microbiocide is N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboxamide.
31. The process of claim 26 wherein the microbiocide is N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboxamide.
32. The process of claim 25 wherein the microbiocide is 2,3,5,6-tetrachloro-4-(methylsulfonyl) pyridine.
33. The process of claim 26 wherein the microbiocide is 2,3,5,6-tetrachloro-4-(methylsulfonyl) pyridine.
34. The process of claim 25 wherein the microbiocide is N-(trichloromethylthio) phthalimide.
35. The process of claim 26 wherein the microbiocide is N-(trichloromethylthio) phthalimide.
36. The process of claim 25 wherein the microbiocide is tributyl tin fluoride.
37. The process of claim 26 wherein the microbiocide is tributyl tin fluoride.
38. A thermoplastic resin composition resistant to micro-biological degradation comprising between about 0.5 and 5.0 weight percent of a composition comprising vinyl chloride-vinyl acetate copolymer and between 1 and 80 weight percent of a microbiocide at a concentration of at least 20 times greater than the normal upper usage concentration of the microbiocide wherein said first composition is homogeneously dispersed in a second thermoplastic resin composition comprising a thermoplastic resin which is not a vinyl chloride-vinyl acetate copolymer.
39. The composition of claim 38 wherein the microbiocide is 10,10'-oxybisphenoxarsine.
40. The composition of claim 38 wherein the thermoplastic resin is a polyurethane.
41. The composition of claim 38 wherein the thermoplastic resin is polyethylene.
42. The composition of claim 38 wherein the thermoplastic resin is polyvinyl chloride.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63575575A | 1975-11-28 | 1975-11-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1071799A true CA1071799A (en) | 1980-02-12 |
Family
ID=24548988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA266,657A Expired CA1071799A (en) | 1975-11-28 | 1976-11-26 | Method of making biocide compositions and compositions therefor |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4086297A (en) |
| JP (1) | JPS5266553A (en) |
| BE (1) | BE848812A (en) |
| CA (1) | CA1071799A (en) |
| DE (1) | DE2654014A1 (en) |
| FR (1) | FR2332765A1 (en) |
| GB (1) | GB1564033A (en) |
| IT (1) | IT1123088B (en) |
| NL (1) | NL183430B (en) |
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| WO2014102228A1 (en) * | 2012-12-28 | 2014-07-03 | Sanitized Ag | Formulation for the antimicrobial treatment of polymer compositions |
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| GB898320A (en) * | 1959-11-24 | 1962-06-06 | Astra Ab | Self-sterilizing packing material and method of producing same |
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| FR1602385A (en) * | 1967-10-24 | 1970-11-16 | ||
| DE1792334A1 (en) * | 1968-08-21 | 1971-11-18 | Hoechst Ag | Skin protection component for anionic surfactants |
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| US3755244A (en) * | 1971-06-02 | 1973-08-28 | Hercules Inc | Polyolefin pigment dispersions |
| US3758482A (en) * | 1971-06-30 | 1973-09-11 | Dow Chemical Co | Halopyridyl thiocyanates |
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| PH11607A (en) * | 1974-02-07 | 1978-04-12 | Dow Chemical Co | A process of incorporating a phosphorothioate into solid thermoplastic polymers |
| DE2519126A1 (en) * | 1974-05-07 | 1975-11-20 | Dick | INSECTICIDAL DEVICE AND METHOD FOR MANUFACTURING IT |
-
1976
- 1976-10-29 US US05/736,968 patent/US4086297A/en not_active Expired - Lifetime
- 1976-11-19 JP JP51138563A patent/JPS5266553A/en active Pending
- 1976-11-24 GB GB48926/76A patent/GB1564033A/en not_active Expired
- 1976-11-25 NL NLAANVRAGE7613182,A patent/NL183430B/en not_active IP Right Cessation
- 1976-11-26 CA CA266,657A patent/CA1071799A/en not_active Expired
- 1976-11-26 IT IT29849/76A patent/IT1123088B/en active
- 1976-11-26 FR FR7635850A patent/FR2332765A1/en active Granted
- 1976-11-26 BE BE172758A patent/BE848812A/en not_active IP Right Cessation
- 1976-11-27 DE DE19762654014 patent/DE2654014A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| NL183430B (en) | 1988-06-01 |
| DE2654014A1 (en) | 1977-06-02 |
| US4086297A (en) | 1978-04-25 |
| JPS5266553A (en) | 1977-06-02 |
| NL7613182A (en) | 1977-06-01 |
| FR2332765B1 (en) | 1980-12-12 |
| US4086297B1 (en) | 1988-06-28 |
| GB1564033A (en) | 1980-04-02 |
| FR2332765A1 (en) | 1977-06-24 |
| BE848812A (en) | 1977-03-16 |
| IT1123088B (en) | 1986-04-30 |
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