Acidic aqueous chlorite teat dip with improved visual indicator stability, extended shelf life, sanitizing capacity and tissue protection

Abstract

The mastitis control teat dip composition having a visible indicator aspect of the invention provides a softening, soothing, smoothing, relaxing property, a rapid initial kill, a useful highly pseudoplastic rheology, a barrier/film-forming capacity, a unique antimicrobial composition that is stable over an extended period of time, and unexpected long term microbial control when compared to the prior art materials disclosed in patents and used in the marketplace. The indicator aspect provides ease of visually detecting the material on the animal skin and can indicate efficacy of the material. The compositions of the invention are made by combining an aqueous liquid composition containing the visual indicator combined with the organic components which can be combined with a simple aqueous solution of a salt of chlorous acid, preferably an alkali metal chlorite. The materials after they are combined and blended into a smooth viscous material containing an emollient package generates active antimicrobial chlorine dioxide and can be immediately contacted with the target animals. The compositions of the invention provide stable visual indication, rapid initial kill, consistent long term kill with chemical and rheological stability.

Description

RELATED APPLICATION

porcein
combined with two or more other conjugated or non-conjugated double bonds. Typical compositions of some of the more important drying oils are shown in the following table.

TABLE 1
Typical Fatty Acid Composition of Drying Oils From Seeds, a%
	Oil	Saturatedb	Oleic	Linoleic	Linolenic
	linseed	10	22	16	52
	perilla	7	14	16	63
	safflower	10	13	77
	soybean	16	24	51	9
	sunflowerc	14	14	72
	sunflowerc	9	72	19
	tungd	6	4
	walnut	8	16	72
	aProportions shown are approximate; actual compositions can vary greatly.
	bPalmitic and stearic acids.
	cExamples of the especially large variations in composition of available sunflower oils.
	dAlso 82% I-eleostearic acid.

Such drying oils can be derived from flax seed in the form of linseed oil, other drying oils can be obtained from soybean that can be modified into a useful drying oil. Further, perilla, safflower, sunflower and walnut oil have limited use as drying oils but can be improved.

Such oils can be converted or modified into a drying oil by heating with catalytic materials that can yield a polyunsaturated material. Such oils are classified as drying oils through their capacity to form a solid film upon oxidative exposure to air. Semi-drying oils come up on exposure to air can form tacky, sticky or semi-solid films. Non-drying oils undergo substantially no change in viscosity upon exposure to oxidating conditions. Reactivity of drying oils typically relate to the number of methylene groups found between the double bonds in the molecule. The reactivity of these materials are well understood and form the basis of the reactivity of alkyd paints.

Still further, a stable detectable indicator of the presence of the antimastitis compositions of the invention can be obtained by incorporating a chemiluminescent materials in the composition. Chemiluminescence is the emission of light from chemical reactions at ordinary temperatures. Chemiluminescent reactions produce a reaction intermediate or a product in an electronically excited state. With radiated decay of the excited state, a quantum or quanta of light is produced resulting in the visible indication of the presence of the chemiluminescence system. When the excited state is a singlet, the radiative process is fluorescent, when the excited state is a triplet, phosphorescent emission is obtained. Electronically excited states can emit UV or infrared radiation as well as visible light, however, the visible chemiluminescence is preferred. Because of the oxidative nature of the chemilumnescent reaction, the peroxide generated chemiluminescence is a preferred mechanism. Chemiluminescence systems are selected such that the energy content of the 167 kJ-ein⁻¹ to 293 kJ-ein⁻¹ and an excited state where a visible light must have that same energy with respect to its ground state. The excitation energy requirement is generally met by the sum of total reaction enthalpy and activation energy. Excitation appears to be general for this reaction but yields of excited products vary substantially with the substituents on the cyclic form. In liquid phase, chemiluminescence, two carbonyl groups are often formed by simultaneous decomposition of an intermediate yielding an excited species, carbon dioxide and other by-products. The excited species is often the source of visible light. In such reactions, substantial heat of formation of the carbonyl groups meets the energy requirement for the excited species. Substances that can provide the reaction including 1,2-dioxetanes, alpha peroxy lactones (1,2-dioxetanes), peroxy oxalate, luminol (phthalhydrazide) and organo metallic compounds.

Preferred chemiluminescence systems including peroxy oxalate systems. In such systems, the excited species is activated through the reaction of hydrogen peroxide, a catalyst and an oxalate species. A proposed mechanism for such reaction is shown as follows: ##STR00001##
This system, peroxalate is converted to a dioxetanedione, a highly unstable intermediate which decomposes into carbon dioxide and an activated fluorescing species (flr*) that releases the visible light. Peroxy oxalate chemiluminescence is a very efficient non-enzymatic chemiluminescence. Quantum efficiencies approach 27% for oxalate esters prepared from 2,4,6-trichlorophenol, 2,4-dinitrophenol, and 3-trifluoromethyl-4-nitrophenol with fluorescers including rubrene or 5,12-bis(phenolethynyl)napthacene.

In the antimastitis compositions of the invention, we believe that the organic chemiluminescent species can be included in the acid part while the peroxide materials can be combined in the chlorite part or vice versa or maintain separately as a third oxidizing part (part 3). In use, part 1 containing the chemiluminescence species can be combined with part 2 containing the peroxide or the activating chlorite part or vice versa or optionally such parts can be combined with a third peroxide containing part. The luminescent species can be included in the acid part or vice versa in an amount of about 0.1 to 10 wt %, preferably, 0.5 to about 5 wt %. The peroxide material is included in a chlorite part or vice versa in an amount such that the final combined antimastitis composition contains from about 1 to about 10 wt % hydrogen peroxide. Hydrogen peroxide solutions that are stabilized and contain from about 5 to about 15 wt % hydrogen peroxide can be used since they tend to be relatively storage stable for a sufficient period of time for use in these compositions.

As discussed above, the present invention may generally comprise in a mastitis control and prevention treatment composition a carrier, an acid part, an acidulant or admixture, an antimicrobial agent or admixture, a rheology modifier or admixture, a film-forming agent or admixture, a buffer system, a hydrotrope or admixture, an emollient or admixture, a surfactant or surfactant admixture, a chromophore or colorant, and optional adjuvants. The preferred compositions of this invention comprise ingredients which are generally regarded as safe, and are not of themselves or in admixture incompatible with milk or milk by-products. Likewise, ingredients may be selected for any given composition which are cooperative in their combined effects whether incorporated for antimicrobial efficacy, physical integrity of the formulation or to facilitate healing and the health of the teat. Generally, the composition comprises a carrier which functions to dilute the active ingredients and facilitates application to the intended surface. The carrier is generally an aqueous medium such as water, or an organic liquid such as an oil, a surfactant, an alcohol, an ester, an ether, or an organic or aqueous mixture of any of these. Water is preferred as a carrier or diluent in compositions of this invention because of its universal availability and unquestionable economic advantages over other liquid diluents.

Acidulants are necessary ingredients within the mastitis control treatments of the invention to maintain the appropriate pH for dissociation of the chlorite/chlorine dioxide release agent and to prevent dissociation of heptanoic, octanoic, nonanoic, decanoic and undecanoic carboxylic acids employed as non-fugitive antimicrobial agents. Carboxylic acids become increasingly biocidal as the pH falls below their pK_a value; consequently, for the carboxylic acids mentioned above, a pH ranging from about 2.5 to 5.5, preferably from about 2.5 to 4.5 and most preferably from about 2.5 to 3.5 is desirable. The acidic component used to prepare the acidic teat dip compositions of the invention will comprise a weak inorganic acid or a weak organic acid which can be dissolved in the aqueous system of the invention to produce an acidic pH. A pH substantially less than about 1 can result in substantial irritation, while a pH greater than about 5 can unacceptably reduce the efficiency of the composition. The term “weak” as used in reference to an acidic component is intended to refer to an acid in which the first dissociation step does not proceed essentially to completion when the acid is dissolved in water at ambient temperatures at a concentration within a range useful to form the present compositions. Such inorganic and organic acids are also referred to as weak electrolytes as the term is used in Textbook of Quantitative Inorganic Analysis, I. M. Kolthoff et al., eds., The Macmillan Co. (3d ed., 1952) at pages 34-37, the disclosure of which is incorporated by reference herein.

Most common commercially-available weak inorganic and organic acids can be used in the invention. Preferred weak inorganic acids include phosphoric acid and sulfamic acid. Useful weak organic acids include acetic acid, hydroxyacetic acid, citric acid, tartaric acid and the like. Acidulants found useful include organic and inorganic acids such as citric acid, lactic acid, acetic acid, glycolic acid, adipic acid, tartaric acid, succinic acid, propionic acid, malic acid, alkane sulfonic acids, cycloalkane sulfonic acids, as well as phosphoric acid and the like or mixtures thereof. Preferred acidulants are those commonly referred to as C_2-6 alpha-hydroxycarboxylic acids, that group of acids which contain a hydroxy function in the alpha position directly adjacent to the carbon atom bearing the carboxyl function, examples of alpha-hydroxymonocarboxylic acids being glycolic, lactic and hydroxybutanoic acid; and, examples of hydroxydicarboxylic acids being malic and tartaric acids. We have found a surprising interaction between the acidulant material and a second antimicrobial acid composition. Preferably, the acidulant material comprises the C_2-6 alpha-hydroxy carboxylic acid in combination with a secondary antimicrobial acid composition. The second antimicrobial acid composition can comprise a C_7-11 carboxylic acid or a hydrocarbon sulfonic acid composition. These materials work together to provide a cooperative antimicrobial action which effects initial kill from chlorine dioxide contributed by the acidulated chlorite and a long lasting kill in the barrier layer from the carboxylic acid/sulfonic acid material. This cooperation of ingredients is an important aspect of the invention.

Used in personal care products, alpha-hydroxycarboxylic acids absorb moisture from the atmosphere and therefore, when applied topically, increase moisture content and plasticity of the stratum corneum. They have had significant impact on skin treatment due to their ability to reduce corneocyte adhesion and accelerate cell proliferation within the basal layers. Though mechanism of action is not yet fully understood, alpha-hydroxycarboxylic also are thought to stimulate synthesis of collagen and mucopolysaccharides in the dermis. At use levels under 10%, skin care benefits are derived through a continued pattern of product usage. Continued use of products with alpha-hydroxycarboxylic acids levels below 10% has been shown to result in gradual reduction of fine lines and an improvement in skin texture through accelerated desquamation. Although conjecture at present, it is believed that some, if not all of these advantages may also be transferred upon the bovine teat skin. By incorporating an alpha-hydroxycarboxylic acid, healing may be accelerated; and, by “smoothing” the dermal surface, cleaning and asepsis may be improved. The most preferred alpha-hydroxycarboxylic acid for compositions of this invention is lactic acid.

Numerous inorganic and organic antimicrobial agents may be utilized in teat dip compositions including (but not limited to) chlorine and bromine release compounds (e.g. alkali and alkaline earth hypochlorites and hypobromites, isocyanurates, chlorinated derivatives of hydantoin, sulfamide, amine, etc.), iodine release complexes of surfactants or polymers such as polyvinylpyrrolidone (termed iodophors), quaternary ammonium compounds, chlorhexidine salts, peroxide and peroxyacid compounds, protonated short chain carboxylic acids, acidified anionic surfactants and chlorine dioxide. Of these typically applied antimicrobial agents which have been investigated for control of bovine mastitis, protonated short chain (C_7-11) carboxylic acids, acidified alkylaryl sulfonates and chlorine dioxide are proven efficacious against mastitis causing microorganisms; and, are preferred in compositions of the present invention. More specifically, dodecylbenzene sulfonic acid, protonated C_7-11 carboxylic acids and chlorin dioxide are especially preferred antimicrobial agents.

The composition of the invention may also contain one or more rheology modifiers, to enhance viscosity, or thicken and cause the aqueous treatment to cling to the surface skin of the teat. Clinging enables the composition to remain in contact with transient and resident pathogenic bacteria for longer periods of time, promoting microbiological efficacy and resisting waste because of excessive dripping. The rheology modifier may be a film former or act cooperatively with a film-forming agent to form a barrier that provides additional protection. Water soluble or water dispersible rheology modifiers that are useful can be classified as inorganic or organic. The organic thickeners can further be divided into natural and synthetic polymers with the latter still further subdivided into synthetic natural-based and synthetic petroleum-based.

Inorganic thickeners are generally compounds such as colloidal magnesium aluminum silicate (VEEGUM®), colloidal clays (Bentonites), or silicas (CAB-O-SILS®) which have been fumed or precipitated to create particles with large surface to size ratios. Natural hydrogel thickeners of use are primarily vegetable derived exudates. For example, tragacanth, karaya, and acacia gums; and extractives such as caragheenan, locust bean gum, guar gum and pectin; or, pure culture fermentation products such as xanthan gum are all potentially useful in the invention. Chemically, all of these materials are salts of complex anionic polysaccharides. Synthetic natural-based thickeners having application are cellulosic derivatives wherein the free hydroxyl groups on the linear anhydro-glucose polymers have been etherified or esterified to give a family of substances which dissolve in water and give viscous solutions. This group of materials includes the alkyl and hydroxyllalkycelluloses, specifically methylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethycellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, hydroxypropylcellulose, and carboxymethylcellulose. Synthetic petroleum-based water soluble polymers are prepared by direct polymerization of suitable monomers of which polyvinylpyrrolidone, polyvinylmethylether, polyacrylic acid and polymethacrylic acid, polyacrylamide, polyethylene oxide, and polyethyleneimine are representative.

All thickeners do not work with equal effectiveness in this invention. Preferred aqueous thickening agents which are more useful in this invention are those which are extremely pseudoplastic (non-Newtonian, rapid relaxation), tend not to develop a rigid three-dimensional structure from interpolymer interactions, have a low or negligible viscoelastic character and possess a high gel strength. Such rheological properties are manifested in a teat dip composition which has a smooth flowing appearance, is easy to pour and apply onto the teat, coats uniformly without forming mucilage streamers as the applicator is withdrawn and remains firmly in place without significant sag. Examples of preferred rheology modifiers are xanthan gum and the hydroxylalkylcelluloses. Generally, the concentration of thickener used in the present invention will be dictated by the final composition any by the method of teat application. Spraying or misting requires a lower composition viscosity for easy and effective application of treatment than dipping. Film-forming barrier dips typically require high apparent viscosity necessary to form thick coatings on teats which insures improved prophylactic effect.

For compositions of this invention designed to provide a barrier for prophylactic protection, additional film-forming agents are included which typically work in conjunction with thickeners. In fact, many of the aforementioned rheology modifiers are themselves film formers of greater or lesser effectiveness; however, a preferred grade of polyvinyl alcohol when used with preferred thickeners such as xanthan gum or hydroxyalkylcelluloses affords particularly useful properties to compositions of this teaching, most notably the development of “balanced” films on treated teats which are sufficiently water-sensitive to be stripped off with conventional udder washing, but capably adherent to the teat skin to withstand premature loss of integrity between milkings and intrinsically resistant to environmental exposure; and, in addition, are of such structure as to successfully occlude antimicrobial agents within the film matrix for continuing biocidal effect against mastitis causing organisms. The success of the barriers thus formed by compositions of this invention are, in part, a consequence of a hydrophobic-hydrophilic balance, caused when non-volatile ingredients, especially fatty acids, surfactants and hydrotropes, become resident throughout the film and whose individual properties become additive with those characteristics of the thickeners and film formers. Such inclusions also plasticize the film and render it pliable.

Polyvinyl alcohol compositions can be used as a film former. Variation of film flexibility, water sensitivity, ease of solvation, viscosity, film strength and adhesion can be varied by adjusting molecular weight and degree of hydrolysis. The preferred polyvinyl alcohol for use in compositions herein has a degree of hydrolysis greater than 92%, preferably greater than 98%, most preferably greater than 98.5%; and, has a molecular weight (Mn) that falls in the range of between about 15,000 and 100,000, but preferably between 40,000 and 70,000 corresponding to a solution viscosity (4% wt aqueous solution measured in centipoise (cP) at 20° C. by Hoeppler falling ball method) of 12-55 cP and 12-25 cP respectively.

The classical definition of a buffered solution is one containing both a weak acid and its conjugate weak base, whose pH changes only slightly on addition of acid or alkali. The weak acid becomes a buffer when alkali is added, and the weak base becomes a buffer when acid is added. Maintenance of the pH of compositions described in the present invention is necessary to minimize undesirable chemical changes which may inhibit the microbiological efficacy of the antimicrobial agent or cause toxic or irritating effect upon the teat. Any compatible organic or inorganic material or mixture of materials which has the desired effect of maintaining the composition pH within prescribed ranges can by utilized as the buffering agent or system in the instant invention. Of primary concern are pH shifts caused by naturally occurring chemicals brought into the composition, after application onto the teat, by skin exudations, milk or environmental soils; and, pH drifting which sometimes accompanies chemical equilibriums established within compositions as ingredients are changed or concentrations varied.

In general, the pH of bovine mastitis control treatments can vary from a low of about pH 2.0 to a maximum of approximately 11.0 depending primarily upon the choice of antimicrobial agent being incorporated in the composition because optimal efficacy normally occurs with a specific, narrow, pH range. Therefore the buffering agent or system is chosen accordingly. The preferred pH range of compositions of this invention is typically from 2.5 to 5.5 most preferably, about 2.5 to 3.5—the lower value being a limit to prevent excessive irritation on the teat surface; and, the upper limit set to enhance chlorine dioxide formation and maintain antimicrobial effect of the protonated carboxylic acid(s) and/or acidified anionic surfactant. A typical and preferred buffer system would be citric acid and its alkali metal salt. However, any acidulant and corresponding conjugate weak base could be used.

Solubilizing agents called hydrotropes or couplers may be generally used in compositions of the present invention to maintain physical single phase integrity and storage stability. To this end, any number of ingredients known to those skilled in formulation art may be employed, such as monofunctional and polyfunctional alcohols. These preferably contain from about 1 to about 6 carbon atoms and from 1 to about 6 hydroxy groups. Examples include ethanol, isopropanol, n-propanol, 1,2-propanediol, 1,2-butanediol, 2-methyl-2,4-pentanediol, mannitol and glucose. Also useful are the higher glycols, polyglycols, polyoxides, glycol ethers and propylene glycol ethers. Additional useful hydrotropes include the free acids and alkali metal salts of sulfonated alkylaryls such as toluene, xylene, cumene and phenol or phenol ether or diphenyl ether sulfonates; alkyl and dialkyl naphthalene sulfonates and alkoxylated derivatives. The most preferred hydrotrope for the most preferred embodiments of this invention is 1-octane sulfonate or mixtures of 1-octane sulfonate and 1,2-octane disulfonate manufactured and held for proprietary use under the name NAS by Ecolab Inc, St. Paul, Minn.

Teat dip compositions of the present invention generally also comprise an emollient and/or humectant to lubricate, condition, soothe, smooth, soften, and generally reduce and promote the healing of irritation on the teat surface. Such irritation may result either from the antimicrobial agent, from the mechanical action of the milking machine or from environmental conditions such as wind chill, dehydration, abrasion and sunburn. Any water soluble or dispersible skin conditioning agent may be used in this present invention. Compositions such as polyhydric alcohols are useful in the invention including glycerin, sorbitol, mannitol, and propylene glycol and its homopolymers; fatty acid esters of simple monohydril alcohols including isopropyl palmitate or isopropyl myristate and similar esters; polyol esters of fatty acids; and, ethoxylated lanolins, vegetable oils, and similar natural sourced derivatives such as aloe. Preferred emollients to be used in the invention include glycerin, sorbitol, and propylene glycol. A preferred emollient system for use in the invention comprises a combination of lanolin and a polyhydroxy emollient composition. The preferred emollient composition comprises lanolin, a lanolin derivative combined with a polyhydroxy compound selected from the group consisting of glycerin, sorbitol, glucitol, propylene glycol and mixtures thereof. Lanolin, a commodity material, also known as wool fat, oespios, agnin, alaporin, is a waxy fatty secretion of sheep. In sheep, sebaceous glands secrete a “fat-like” waxy secretion which is deposited onto the wool fiber. Chemically a wax, the material is a complex mixture of esters and polyesters of 33 high-molecular-weight alcohols and 33 fatty acids. The alcohols are of three types: aliphatic alcohols, steroidal alcohols and triterpenoid alcohols; the acids are of three types: saturated non-hydroxylated acids, unsaturated non-hydroxylated acids and hydroxlyated acids. Liquid lanolin is rich in low molecular weight branched aliphatic acids and alcohols while waxy lanolin is rich in high molecular weight straight chain acids and alcohols. Reviews regarding compositions, derivatives, modifications and uses are found in Barnet, Drug and Cosmet. Ind., Ad, 744 (1957); 83, 292 (1958); Leideritz, Chem. Ikerztg., 83, 707 (1959); F. Fawaz et al., Ann. Pharm. Franc., 33, 217, 226 (1973). Rheological properties of lanolin are discussed in F. Poisieux, Pharm. Acta. Helv., 51, 289 (1976). Please also the monograph: E. V. Truter, Wool Wax, Chemistry and Technology, (Interscience, 1956). The typical lanolin product contains about 20-25 wt % water and is yellowish white in color having a slight odor. The material is, for all practical purposes, insoluble in water but is soluble in chloroform or ether with the inherent separation of water from the wax lipid mass. Anhydrous lanolin is yellowish, tenacious, semisolid fatty appearing material, with a slight odor. Anhydrous lanolin melts at 38-42° C., is insoluble in water, but sparingly soluble in alcohol while freely soluble in benzene, chloroform, ether, carbon disulfide, acetone or petroleum ether. Lanolin is a natural product material produced in the manufacture of wool yarn. A preferred emollient composition contains a lanolin derivative in combination with a polyhydroxy compound. A variety of relatively neutral emollient lanolin species are known including a lanolin glycerol ester or ether, acetylated lanolin alcohol, lanolinamide DEA isopropyl lanolate, oleyl lanolate, hydrogenated lanolin, hydroxylated lanolin, lanolin lanoleate, isobutylated lanolin oil, lanolin ricinoleate, lanolin wax and a polyethylene glycol derivative of lanolin (PEG-lanolin). The PEG-lanolin derivative (CAS number 61790-81-6) can contain from about 5 to about 100 moles of ethylene glycol per mole of the PEG lanolin derivative. Preferred derivatives comprise about 40 to 85 moles of ethylene oxide per mole derivative. These materials are sold under the tradenames LANETO-50; SOLAN-50; ETHOXYLAN-50; SOLULAN-75 from a variety of commercial sources. A preferred humectant for use in these materials comprises combining, in a fully formulated teat dip material, about 0.01 to about 100 parts by weight of the PEG lanolin derivative for each one part by weight of a polyhydroxy compound selected from the group consisting of glycerine, sorbitol, glucitol and mixtures thereof. The preferred teat dip compositions contain about 0.1 to about 15 wt % of the polyhydroxy humectant combination, preferably about 0.2 to 5 wt % and about 0.1 to 10 wt. %, preferably 0.5 to 5 wt. % of the lanolin composition. The combination of the lanolin derivative and the polyhydroxy emollient compound provides surprisingly enhanced soothing protection for animals exposed to repeated milking and harsh conditions.

The surfactant or surfactant admixture of the present invention can be selected from compatible water soluble or water dispersible nonionic, or anionic surface-active agents; or mixtures of each or both types. Nonionic and anionic surfactants offer diverse and comprehensive commercial selection, low price; and, most important, excellent detersive effect—meaning surface wetting. Surface-active or “wetting agents” function to increase the penetrant activity of the invention into the tissue surface at risk from mastitis causing pathogens. Nonionic surfactants useful in the invention are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic, alkyl aromatic or polyoxyalkylene hydrophobic compound with a hydrophilic alkaline oxide moiety which in common practice is ethylene oxide or a polyhydration product thereof, polyethylene glycol. Practically any hydrophobic compound having a hydroxyl, carboxyl, amino, or amido group with a reactive hydrogen atom can be condensed with ethylene oxide, or its polydration adducts, or its mixtures with alkoxylenes such as propylene oxide to form a nonionic surface-active agent. The length of the hydrophilic polyoxyalkylene moiety which is condensed with any particular hydrophobic compound can be readily adjusted to yield a water dispersible or water soluble compound having the desired degree of balance between hydrophilic and hydrophobic properties.

Useful nonionic surfactants in the present invention include: Block polyoxypropylene-polyoxyethylene polymeric compounds based upon propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and ethylenediamine as the initiator reactive hydrogen compound. Examples of polymeric compounds made from a sequential propoxylation and ethoxylation of initiator are commercially available under the trade name PLURONIC® manufactured by BASF Corp. PLURONIC® compounds are difunctional (two reactive hydrogens) compounds formed by condensing ethylene oxide with a hydrophobic base formed by the addition of propylene oxide to two hydroxyl groups of propylene glycol. This hydrophobic portion of the molecule weighs from about 1,000 to about 4,000. Ethylene oxide is then added to sandwich this hydrophobe between hydrophilic groups, controlled by length to constitute from about 10% by weight to about 80% by weight of the final molecule. TETRONIC® compounds are tetra-functional block copolymers derived from the sequential additional of propylene oxide and ethylene oxide to ethylenediamine. The molecular weight of the propylene oxide hydrotype ranges from about 500 to about 7,000; and, the hydrophile, ethylene oxide, is added to constitute from about 10% by weight to about 80% by weight of the molecule.

Also useful nonionic surfactants include the condensation products of one mole of alkyl phenol wherein the alkyl constituent, contains from about 8 to about 18 carbon atoms with from about 3 to about 50 moles of ethylene oxide. The alkyl group can, for example, be represented by diisobutylene, di-amyl, polymerized propylene, isoctyl, nonyl, and di-nonyl. Examples of commercial compounds of this chemistry are available on the market under the trade name IGEPAL® manufactured by Rhone-Poulenc and TRITON® manufactured by Union Carbide.

Likewise useful nonionic surfactants include condensation products of one mole of a saturated or unsaturated, straight or branched chain alcohol having from about 6 to about 24 carbon atoms with from about 3 to about 50 moles of ethylene oxide. The alcohol moiety can consist of mixtures of alcohols in the above delineated carbon range or it can consist of an alcohol having a specific number of carbon atoms within this range. Examples of like commercial surfactant are available under the trade name NEODOL® manufactured by Shell Chemical Co. and ALFONIC® manufactured by Vista Chemical Co.

Condensation products of one mole of saturated or unsaturated, straight or branched chain carboxylic acid having from about 8 to about 18 carbon atoms with from about 6 to about 50 moles of ethylene oxide. The acid moiety can consist of mixtures of acids in the above delineated carbon atoms range or it can consist of an acid having a specific number of carbon atoms within the range. Examples of commercial compounds of this chemistry are available on the market under the trade name NOPALCOL® manufactured by Henkel Corporation and LIPOPEG® manufactured by Lipo Chemicals, Inc. In addition to ethoxylated carboxylic acids, commonly called polyethylene glycol esters, other alkanoic acid esters formed by reaction with glycerides, glycerin, and polyhydric (saccharide or sorbitan/sorbitol) alcohols have application in this invention. All of these ester moieties have one or more reactive hydrogen sites on their molecule which can undergo further acylation or ethylene oxide (alkoxide) addition to control the hydrophilicity of these substances.

Other useful surfactants are nonionics made by adding ethylene oxide to ethylene glycol to provide a hydrophile of designated molecular weight; and, then adding propylene oxide to obtain hydrophobic blocks on the outside (ends) of the molecule. The hydrophobic portion of the molecule weighs from about 1,000 to about 3,100 with the central hydrophile comprising 10% by weight to about 80% by weight of the final molecule. These “reverse” PLURONIC®'s are manufactured by the BASF Corporation under the trade name PLURONIC® surfactants. Likewise, the TETRONIC® surfactants are produced by the BASF Corporation by the sequential addition of ethylene oxide and propylene oxide to ethylenediamine. The hydrophobic portion of the molecule weighs from about 2,100 to about 6,700 with the central hydrophile comprising 10% by weight to 80% by weight of the final molecule.

Tertiary amine oxides corresponding to the general formula: ##STR00002##
can be used wherein the ? bond is a conventional representation of a semi-polar bond; and R¹, R², and R³ may be aliphatic, aromatic, heterocyclic, alicyclic groups or a combination of such groups thereof. Generally, for amine oxides of detergent interest, R¹ is an alkyl radical of from about 8 to about 24 carbon atoms; R² and R³ are selected from the group consisting of alkyl or hydroxyalkyl of 1-3 carbon atoms and mixtures thereof; R⁴ is an alkylene or a hydroxyalkylene group containing 2 to 3 carbon atoms; and n ranges from 0 to about 20. Useful water soluble amine oxide surfactants are selected from the coconut or tallow dimethyl amine oxides.

Also useful in the present invention are surface active substances which are categorized as anionics because the charge on the hydrophobe is negative; or surfactants in which the hydrophobic section of the molecule carries no charge unless the pH is elevated to neutrality or above (e.g. carboxylic acids). Carboxylate, sulfonate, sulfate and phosphate are the polar (hydrophilic) solubilizing groups found in anionic surfactants. Of the cations (counterions) associated with these polar groups, sodium, lithium and potassium impart water solubility and are most preferred in compositions of the present invention. Examples of suitable synthetic, water soluble anionic compounds are the alkali metal (such as sodium, lithium and potassium) salts or the alkyl mononuclear aromatic sulfonates such as the alkyl benzene sulfonates containing from about 5 to about 18 carbon atoms in the alkyl group in a straight or branched chain, e.g., the salts of alkyl benzene sulfonates or of alkyl naphthalene sulfonate, dialkyl naphthalene sulfonate and alkoxylated derivatives. Other anionic detergents are the olefin sulfonates, including long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkenesulfonates and hydroxyalkanae-sulfonates and alkylpoly (ethyleneoxy) ether sulfonates. Also included are the alkyl sulfates, alkyl poly (ethyleneoxy) ether sulfates and aromatic poly (ethyleneoxy) sulfates such as the sulfates or condensation products of ethylene oxide and nonyl phenol (usually having 1 to 6 oxyethylene groups per molecule).

Complexed iodines offer the advantage of being chromophoric, i.e. easily visible when applied onto the teat. Other antimicrobial agents do not have this feature; therefore, compositions of this invention may include a water soluble or dispersible coloring agent (dye or pigment or mixtures) which renders the composition chromophoric, having sharp contrast to teat skin and permitting the dairy herd manager to visually discern that the teats have been treated.

Alternatively, the compositions of the invention may be comprised of any number of optional ingredients, i.e. adjuvants. Depending upon the benefits provided, adjuvants may partially or wholly displace the carrier in the composition. Generally, in accordance with the invention, there may be included within this composition formulary adjuvants which assist in the application of the invention with respect to physical and chemical stability, barrier film formation, teat health maintenance, performance, physical form and manufacturing process anesthetics. Of course, these functions may be accomplished exclusively by composition ingredients already described or admixtures thereof; however, formulary or application or performance situations may occur requiring additional effect which may be accomplished by introducing an additional inorganic or organic agent or agents and mixtures thereof into the composition.

The compositions of the invention may optionally include medicaments, for example sunscreens such as paramino benzoic acid and healing agents such as allantoin or urea to provide curative action and stimulation of formation of new tissue; preservatives such as methyl paraben, propyl paraben, sorbic and benzoic acids or salts thereof to retard bacterial growth and prolong shelf life; antioxidants such as BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), TBHQ (tert-butylhydroquinone), or propyl gallate to retard oxidative or hydrolytic degradation; sequestering agents such as aminopolyacetates, polyphosphonates, aminpolyphosphonates, polycarboxylates, and condensed phosphates; dispersants or suspending agents having polyelectrolytic character such as polyacrylate and similar polycarboxylates of homopolymeric or copolymeric structure; and manufacturing processing agents, for example defoam additives employed to facilitate blending and mixing.

A wide variety of ingredients useful in mastitis control treatment can be included in the compositions hereof. This list is not intended to be exhaustive and other optional ingredients, which may not be listed, but which are well known in the art, may also be utilized in the composition. The examples are not intended to be limited in any way. In certain cases, some of the individual adjuvants may overlap other categories. The adjuvants employed will be selected so as not to interfere with the antimicrobial action of the composition and to avoid physical or chemical instability of the product.

Table “Bovine Mastitis Treatment Admixture Compositions”, below, provides guidelines for consistent concentrations in accordance with this invention.

	USEFUL		MORE
	AMOUNT	PREFERRED	PREFERRED
INGREDIENT	(WT. %)	(WT. %)	(WT. %)
CARRIER	40.0-98.0	50.0-98.0	60.0-98.0
BLEND OF	1.0-12.0	1.0-10.0	1.0-8.0
ACIDULANT/
ANTI-MICROBIAL
RHEOLOGY	0.0-10.0	0.01-7.5	0.1-5.0
MODIFIER
FILM FORMER	0.0-12.0	0.01-8.0	0.1-4.0
BUFFER	0.0-15.0	0.01-10.0	0.1-5.0
HYDROTROPE	0.0-20.0	0.0-15.0	0.1-10.0
EMOLLIENT	0.5-60.0	1.0-40.0	1.5-20.0
SURFACTANT	0.0-60.0	0.01-40.0	0.1-20.0
INDICATOR/	0.0-1.0	0.001-0.8	0.002-0.6
COLORANT
UREA	0.01-10	0.1-5	0.2-4
OPTIONAL	0.0-5.0	0.1-4.0	0.1-30
ADJUVANT

The following examples and data are provided to illustrate preferred embodiments of the invention and contain a best mode.

EXAMPLE I

Example I is a representative embodiment of this invention which illustrates a bovine mastitis treatment having barrier film properties. Antimicrobial effect is provided by generation of chlorine dioxide caused by disproportionation of chlorite ion upon admixture of composition base with activator and by the resident biocidal activity of protonated nonanoic acid.

A 16 liter batch of the following experimental base formula part and 1 kilogram of the ClO₂⁻¹ part was activator were prepared by blending the ingredients as shown.

Base Formula (Part I) (pH=2.8)

	Ingredients	Wt %	Grams
	Glycerin, 96%	5.00	800.05
	Isopropanol, 99%	2.00	320.05
	Nonanoic (Pelargonic) Acid	1.50	240.05
	Lactic Acid, 88%	2.95	472.03
	*Xanthan Gum	0.30	48.02
	(KELTROL ® K5C151)
	Deionized Water	60.76	9721.62
	Potassium Benzoate	0.20	32.01
	KOH, 45%	0.29	45.40
	Octane Sulfonate	17.00	2720.02
	**ELVANOL ® Premix, 10%	10.00	1600.00
	TOTAL	100.00	16000.25
	*KELTROL ® K5C151 is a grade of xanthan gum manufactured by Kelco.
	**ELVANOL ® Premix: 10% aqueous solution of ELVANOL ® 90-50. ELVANOL ® 90-50 is a grade of polyvinyl alcohol manufactured by E. I. duPont.

Activator ClO₂⁻¹ Formula (Part II) (pH=12.3):

	Ingredients	Wt %	Grams
	Deionized Water	50.00	500.00
	Sodium Chlorite, 25%	50.00	500.00
	TOTAL	100.00	1000.00

About 3376 grams of the base formula part were blended with about 92.89 grams of the CLO₂⁻¹ ClO₂⁻¹ part (the ClO₂⁻¹ is 0.32% of the total composition). The viscosity (Brookfield Model DV-II Viscometer, spindle No. 1, 20 rpms at 25° C.) was about 304 cps.

EXAMPLE II

Example II is a further example of this invention which differs from Example I in that the resident biocidal activity is contributed by dodecylbenzene sulfonic acid. The hydrotropic agent, octane sulfonate, is not required in this formula for physical stability.

A seven kilogram batch of the following base formula part and a one kilogram batch of the ClO₂⁻¹ activator part was were prepared.

Base Formula (Part II I) (pH=2.9)

	Ingredients	%	Grams
	Glycerin, 96%	5.00	350.10
	Dodecylbenzene Sulfonic	2.00	140.01
	Acid, 97%
	Xanthan Gum	0.30	21.01
	(KELTROL ® K5C151)
	Deionized Water	78.14	5469.90
	Lactic Acid, 88%	2.95	206.51
	KOH, 45%	1.41	98.73
	Potassium Benzoate	0.20	14.00
	**ELVANOL ® Premix, 10%	10.00	700.06
	TOTAL	100.00	7000.32
	*KELTROL ® K5C151 is a grade of xanthan gum manufactured by Kelco.
	**ELVANOL ®* Premix: 10% aqueous solution of ELVANOL ® 90-50. ELVANOL ® 90-50 is a grade of polyvinyl alcohol manufactured by E. I. duPont.

Activator ClO₂⁻¹ Formula (Part II) (pH=12.3)

	Ingredients	%	Grams
	Deionized Water	50.00	500.00
	Sodium Chlorite, 25%	50.00	500.00
	TOTAL	100.00	1000.00

About 3376 grams of the base formula part were mixed with about 92.98 grams of the ClO₂⁻¹ activator part. The stable rheology and pH of the combined formula is shown as follows:

	Viscosity:	As Mixed	pH
		Brookfield (#1, 20 rpm @ 25° C.)
	Brookfield: initial	290 cps	3.08
	Brookfield: 1 week	296 cps	3.09
	Brookfield: 2 weeks	n/a	n/a
	Brookfield: 3 weeks	291 cps	2.97
	Brookfield: 4 weeks	294 cps	3.10

EXAMPLE III

Example III is a representative composition of the invention illustrating a bovine mastitis treatment without a barrier film property and having no thickening nor film-forming agents. A surfactant, NEODOL® 25-9, is included for teat cleansing and surface wetting.

A two hundred gram batch of the following experimental base formula and a I one kilogram batch of the ClO₂⁻¹ activator part was were made.

Base Formula (Part I) (pH=2.7)

	Ingredients	Wt %	Grams
	Glycerin, 96%	5.00	10.0
	C12-15 alcohol (9 mole)	0.50	1.00
	ethoxylate NEODOL*
	25-9
	Pelargonic Acid	0.50	1.00
	Lactic Acid, 88%	2.95	5.90
	Deionized Water	75.44	150.88
	Octane Sulfonate	7.00	14.00
	KOH, 45%	0.61	1.22
	Dye-F, D & C	4.00	8.00
	Green #3-1.0% aq. active
	*Pigment, 5.0%	4.00	8.00
	TOTAL	100.00	200.00
	*Pigment: PYLAKOR ® Yellow LX-10192 and Permanent Green S-722 (50:50 blend) manufactured by Pylam Products Co. Inc.

Activator ClO₂⁻¹ Formula (Part II) (pH=12.3)

	Ingredients	Wt %	Grams
	Deionized Water	50.00	500.00
	Sodium Chlorite, 25%	50.00	500.00
	TOTAL	100.00	1000.00

About 200 grams of the base formula were mixed with about 5.5 grams of the ClO₂⁻¹ activator part. pH of final mixture is about 2.9.

EXAMPLE IV

Example IV is a further modification of Example III using sorbitol as an emollient in place of glycerin. A two hundred gram batch of the following experimental base formula and a 1 kilogram batch of the ClO₂⁻¹ activator part was made.

Base Formula (Part I) (pH=2.7)

	Ingredients	Wt %	Grams
	Sorbitol, 70%	1.00	2.00
	C12-15 alcohol (9 mole)	0.50	1.00
	ethoxylate NEODOL ®
	25-9
	Pelargonic Acid	0.50	1.00
	Lactic Acid, 88%	2.95	5.90
	Deionized Water	79.49	158.98
	Octane Sulfonate	7.00	14.00
	KOH, 45%	0.56	1.12
	Dye-F, D & C Green #3,	4.00	8.00
	1.0% aqueous active
	*Pigment, 5.0%	4.00	8.00
	TOTAL	100.00	200.00
	*Pigment: PYLAKOR ® Yellow LX-10192 and Permanent Green S-722 (50:50 blend) manufactured by Pylam Products Co. Inc.

Activator ClO₂⁻¹ Formula (Part II) (pH=12.3)

	Ingredients	Wt %	Grams
	Deionized Water	50.00	500.00
	Sodium Chlorite, 25%	50.00	500.00
	TOTAL	100.00	1000.00

About 200 grams of the base formula were mixed with about 5.5 grams of the ClO₂⁻¹ activator part. pH of final mixture is about 2.9.

EXAMPLE V

Example V is a further composition of the invention illustrating a bovine mastitis treatment without a barrier film property, again having no thickening nor film-forming agents and using phosphoric acid as the acidulant. A surfactant, NEODOL® 25-9, is included for teat cleansing and surface wetting. A two hundred gram batch of the following experimental base formula and a 1 kilogram batch of the ClO₂⁻¹ activator part was made.

Base Formula (Part I) (pH=2.7)

	Ingredients	%	Grams
	Sorbitol, 70%	1.00	2.00
	C12-15 alcohol (9 mole)	0.50	1.00
	ethoxylate - NEODOL ®
	25-9
	Pelargonic Acid	0.50	1.00
	Phosphoric Acid, 75%	1.00	2.00
	Deionized Water	81.32	162.64
	Octane Sulfonate	7.00	14.00
	KOH, 45%	0.68	1.36
	Dye-	4.00	8.00
	F, D & C Green #3, 1.0%
	*Pigment 5.0%	4.00	8.00
	TOTAL	100.00	200.00
	*Pigment: PYLAKOR ® Yellow LX-10192 and Permanent Green S-722 (50:50 blend) manufactured by Pylam Products Co. Inc.

Activator ClO₂⁻¹ Formula (Part II) (pH=12.3)

	Ingredients	%	Grams
	Deionized Water	50.00	500.00
	Sodium Chlorite, 25%	50.00	500.00
	TOTAL	100.00	1000.00

About 200 grams of the base formula were mixed with about 5.5 grams of the ClO₂⁻¹ activator part. pH of final mixture is about 2.9.

EXAMPLE VI

Examples VI, VII and VIII are compositional variations of Example I which contain the homologous carboxylic acids octanoic, decanoic and a mixture thereof respectively.

A two hundred gram batch of the following experimental base formula and a 1 kilogram batch of the ClO₂⁻¹ activator part was were prepared.

Base Formula (Part 1) (pH=2.7)

	Ingredients	Wt %	Grams
	Glycerin, 96%	5.00	10.05
	Isopropanol, 99%	2.00	4.01
	Octanoic Acid	1.50	3.02
	Lactic Acid, 88%	2.95	5.90
	Xanthan Gum	0.30	0.61
	KELTROL ® K5C151
	Deionized Water	60.93	121.90
	Potassium Benzoate	0.20	0.40
	KOH, 40%	0.12	0.25
	Octane Sulfonate	17.00	34.02
	*ELVANOL ® Premix, 10%	10.00	20.09
	TOTAL	100.00	200.25
	*ELVANOL ® Premix: See p. 27

Activator ClO₂⁻¹ Formula (Part 2) (pH=12.3)

	Ingredients	Wt %	Grams
	Deionized Water	50.00	500.00
	Sodium Chlorite, 25%	50.00	500.00
	TOTAL	100.00	1000.00

The mixed product made with A mastitis treatment composition according to the invention was prepared by mixing 100 grams of Part 1 Base formula (Part 1) and 2.75 grams of Activator ClO₂⁻¹ formula (Part 2). The is buffered to pH of the composition was buffered to 2.9.

EXAMPLE VII

A 200 gram batch of the following experimental base formula and a 1 kilogram batch of the ClO₂⁻ ClO₂⁻¹ activator part was were prepared.

Base Formula (Part 1) (pH 2.6)

	Ingredients	Wt %	Grams
	Glycerin, 96%	5.00	10.05
	Isopropanol, 99%	2.00	4.00
	Decanoic Acid	1.50	3.03
	Lactic Acid, 88%	2.95	5.90
	Xanthan Gum	0.30	0.61
	KELTROL ® K5C151
	Deionized Water	60.93	121.93
	Potassium Benzoate	0.20	0.40
	KOH, 40%	0.12	0.25
	Octane Sulfonate	17.00	34.10
	*ELVANOL ® Premix, 10%	10.00	20.00
	TOTAL	100.00	200.27
	*ELVANOL ® Premix: See p. 27

Activator ClO₂⁻¹ Formula (Part 2)(pH=12.3)

	Ingredients	Wt %	Grams
	Deionized Water	50.00	500.00
	Sodium Chlorite, 25%	50.00	500.00
	TOTAL	100.00	1000.00

The mixed product made with A mastitis treatment composition according to the invention was prepared by mixing 100 grams of the Base Part 1 Formula combined (Part 1) with 2.75 grams of the activator Part 2 ClO₂⁻¹ formula (Part 2). The material is buffered to pH of the composition was buffered to 2.9.

EXAMPLE VIII

A 200 gram batch of the following experimental base formula and a I one kilogram batch of the ClO₂⁻ ClO₂⁻¹ activator part was were prepared.

Base Formula (Part 1) (pH 2.7)

	Ingredients	Wt %	Grams
	Glycerin, 96%	5.00	10.04
	Isopropanol, 99%	2.00	4.01
	*KORTAC1D ® - C8:C10	1.50	3.3
	(3:1)
	Lactic Acid, 88%	2.95	5.90
	Xanthan Gum	0.30	0.61
	KELTROL ® K5C151
	Deionized Water	60.93	121.90
	Potassium Benzoate	0.20	0.40
	KOH, 40%	0.12	0.24
	Octane Sulfonate	17.00	34.04
	*ELVANOL ® Premix, 10%	10.00	20.01
	TOTAL	100.00	200.18
	*KORTAC1D ®: 3:1 Octanoic/decanoic blend manufactured by Akzo Chemical.
	*ELVANOL ® Premix: See p. 27

Activator ClO₂⁻¹ Formula (Part 2) (pH=12.3)

	Ingredients	Wt %	Grams
	Deionized Water	50.00	500.00
	Sodium Chlorite, 25%	50.00	500.00
	TOTAL	100.00	1000.00

The mixed product made using A mastitis treatment composition according to the invention was prepared by mixing 100 grams of Base Formula (Part 1) and 2.75 grams of Activator ClO₂⁻¹ formula (Part 2) and was is buffered to pH 2.9.

EXAMPLE IX

Example IX is an additional variation of Example I containing heptanoic acid and n-propanol in place of nonanoic and isopropanol respectively.

A 1000 gram batch of this experimental base formula was prepared; (Part 1) and, 1000 grams of the ClO₂⁻ Activator ClO₂⁻¹ formula (part was 2) were prepared by blending the ingredients as shown. Two typical admixtures of parts I and II Parts 1 and 2 were then prepared or illustrated as shown.

Base Formula (Part I) (pH 2.8)

	Ingredients	Wt %	Grams
	Glycerin, 96%	5.00	50.00
	n-Propanol, 99%	1.50	15.03
	Heptanoic Acid	1.00	10.03
	Lactic Acid, 88%	2.95	29.51
	KELTROL ® K5C151	0.30	3.02
	Deionized Water	71.13	711.38
	Potassium Benzoate	0.20	2.03
	KOH, 45%	0.42	4.21
	Octane Sulfonate	7.50	75.00
	ELVANOL ® Premix, 10%	10.00	100.07
	TOTAL	100.00	1000.28

Activator Formula (Part II) (pH 12.0)

	Ingredients	Wt %	Grams
	Deionized Water	75.0	750
	Sodium Chlorite, 25%	25.0	250
	TOTAL	100.00	1000.00

Typical Mix Ratios:

	Base (g)	Activator (g)
	100	2.754	(6.25% active) → 0.16% NaClO2
	3376	93	(6.28% active) → 0.16% NaClO2

EXAMPLE X

A 500 gram batch of the following experimental base formula was prepared for preliminary testing. This example is similar to Example I with n-propanol and half of the NaClO₂ amount.

Base Formula (Part I) (pH=2.8)

	Ingredients	Wt %	Grams
	Glycerin, 96%	5.00	25.00
	n-Propanol, 99%	1.50	7.50
	Pelargonic Acid	1.50	7.50
	Lactic Acid, 88%	2.95	14.75
	*KELTROL ® K5C151	0.30	1.50
	Deionized Water	71.13	266.30
	Potassium Benzoate	0.20	1.00
	KOH, 45%	0.29	1.25
	Octane Sulfonate	17.00	85.00
	*ELVANOL ® Premix,	10.00	50.00
	10%
	**Pigment	8.00	40.00
	TOTAL	100.00	500.00
	*ELVANOL ® Premix: See p. 27
	**Pigment: See p. 29

Activator Formula (Part II) (pH=12.0)

	Ingredients	Wt %	Grams
	Deionized Water	75.0	375.00
	Sodium Chlorite, 25%	25.00	125.00
	TOTAL	100.00	500.00

Typical Mix Ratios:

	Base (g)	Activator (g)
	3376	186 g	(6.25% active) → 0.32% NaClO2
	3376	93	(6.28% active) → 0.16% NaClO2

EXAMPLE XI

A 1000 gram batch of the following experimental base formula was prepared for testing. This composition is similar to Example III with NAS and thickener.

Base Formula (Part I) (pH 2.7)

	Ingredients	Wt %	Grams
	Glycerin, 96%	5.00	50.00
	NEODOL ® 25-9	.50	5.00
	Pelargonic Acid	0.50	5.00
	Lactic Acid, 88%	2.95	29.50
	KELTROL ® K5C151	0.10	1.00
	Deionized Water	79.45	794.50
	Octane Sulfonate	7.00	70.00
	KOH, 45%	0.50	5.00
	*Pigment 5.0%	4.00	40.00
	TOTAL	100.00	1000.00	→
			pH = ˜2.70
	*Pigment: See p. 29

Activator Formula (Part II) (pH=12.3)

	Ingredients	Wt %	Grams
	Deionized Water	50.00	500.00
	Sodium Chlorite, 25%	50.00	500.00
	TOTAL	100.00	1000.00

Typical Mix Ratios:

	Base (g)	Activator (g)
	450	12.39	(12.5% active) → 0.32% NaClO2
	225	225

EXAMPLE XII

A 1000 gram batch of the following experimental base formula was prepared for testing. This composition is similar to Example IV with an octane sulfonate.

Base Formula (Part I) (pH 2.7)

	Ingredients	Wt %	Grams
	Sorbitol, 70% active	1.00	10.00
	NEODOL ® 25-9	0.50	5.00
	Pelargonic Acid	0.50	5.00
	Lactic Acid, 88% active	2.95	29.50
	Deionized Water	83.49	834.90
	Deionized Water	79.45	794.50
	Octane sulfonate	7.00	70.00
	KOH, 45%	0.56	5.60
	*Pigment 5.0%	4.00	40.00
	TOTAL	100.00	1000.00	→
			pH = ˜2.70
	*Pigment: See p. 29

Activator Formula (Part II) (pH 12.3)

	Ingredients	Wt %	Grams
	Deionized Water	50.00	500.00
	Sodium Chlorite,	50.00	500.00
	25% active
	TOTAL	100.00	1000.00

Typical Mix Ratios

	Base (g)	Activator (g)
	450	12.39	(12.5% active) → 0.32% NaClO2
	225	225

EXAMPLE XIII

A 1500 gram batch of the following experimental base formula was prepared for testing. Similar to Example III with NAS, thickener and heptanoic acid.

Base Formula (Part I) (pH=2.7)

	Ingredients	Wt %	Grams
	Glycerin, 96%	5.00	75.00
	NEODOL ® 25-9	0.50	7.50
	Heptanoic Acid	0.50	7.50
	Lactic Acid, 88%	2.95	44.25
	KELTROL ® K5C151	0.10	1.50
	Deionized Water	80.45	1206.75
	NAS-FAL	6.00	90.00
	KOH, 45%	0.50	7.50
	Pigment 5.0%	4.00	60.00
	TOTAL	100.00	1500.00

Activator Formula (Part II) (pH 12.0)

	Ingredients	Wt %	Grams
	Deionized Water	75.00	75.00
	Sodium Chlorite, 25%	25.00	25.00
	TOTAL	100.00	100.00

Typical Mix Ratios

Base (g) Activator (g)


50       1.377 (6.25% active)
100      2.754 (6.25% active)
450      12.39 (6.25% active)

EXAMPLE XIV

A 1500 gram batch of the following experimental base formula was prepared for testing. Similar to Example IV with NAS and heptanoic acid.

Base Formula (Part I) (pH 2.7)

	Ingredients	Wt %	Grams
	Sorbitol, 70%	1.00	15.00
	NEODOL ® 25-9	0.50	7.50
	Heptanoic Acid	0.50	7.50
	Lactic Acid, 88%	2.95	44.50
	Deionized Water	80.45	1206.75
	NAS-FAL	6.00	90.00
	KOH, 45%	0.54	8.10
	**Dye/Pigment 5.0%	4.00	60.00
	TOTAL	100.00	1500.00
	**Pigment: See p. 29

Activator Formula (Part II) (pH=12.0)

	Ingredients	Wt %	Grams
	Deionized Water	75.0	75.0
	Sodium Chlorite, 25%	25.00	25.0
	TOTAL	100.00	100.00

Typical Mix Ratios

Base (g) Activator (g)


50       1.377 (6.25% active)
100      2.754 (6.25% active)
450      12.39 (6.25% active)

Germicidal and Detergent Sanitizing Action of Disinfectants Testing Created from AOAC Method 960.09

A test to determine the efficacy of antimicrobial products used for sanitizing precleaned, nonporous food contact surfaces.

Culture Media

• 1. Nutrient Agar A:
• 2. Nutrient Agar B (French Slants):
  Subculture Media
• 1. Tryptone Glucose Extract Agar (TGE):
• 2. Neutralized Tryptone Glucose Extract Agar:
  The neutralizer used should be appropriate for test substance inactivation.
  Reagents
• 1. Neutralizer Stock:
  • a. A mixture of 49.5 mL Chambers solution and 49.5 mL of 1% aqueous Na₂S₂O₃
• 2. Neutralizer Blanks:
  • a. Aseptically dispense 9 ml of neutralizer into sterile 25×1 50 mm test tubes for use in the test.
• 3. Phosphate Buffer Stock (0.25M)
• 4. Phosphate Buffer Dilution Water
  Apparatus
• 1. Glassware
  • 250 ml Erlenmeyer flasks, 100 ml volumetric flasks, pipettes, glass beads, 20×150 and 25×150 mm test tubes. Sterilize for 20 minutes at 121° C. or in a dry air oven at 180° C. for 180 minutes.
• 2. Petri Dishes
  • Sterile disposable petri dishes, 15×100 mm.
• 3. French Bottles (milk dilution bottles)
  • 175 ml flint glass bottles
• 4. Water Bath
  • Constant temperature water bath that can maintain a test temperature ±2° C. of required test temperature. Monitor temperature throughout the test.
• 5. Transfer Loops
  • Suitable metal or plastic disposal transfer loops
• 6. Sterile Buchner Funnel Containing Whatman No. 2 Filter Paper
  Staphylococcus aureus ATCC 6538
  Escherichia coli ATCC 11229
  Maintain on Nutrient Agar A slants at 4° C. with transfers to new stock slants once per month (reference SOP MS031 for culture maintenance). From the stock culture slant, make >3 and <30 consecutive transfers on nutrient agar slants with incubation a 37° C.±2° C. for 20-24 hours. If only one daily transfer has been missed, no special procedures are required; if 2 or more daily transfers are missed, repeat with 3 daily transfers.
  Inoculate french slants by washing the growth from the Nutrient Agar A slant into 99 ml of phosphate buffer as follows: Use 5 ml of buffer on the slant and rinse this into the balance of the 99 ml of buffer. Mix this suspension well and add 2 ml of suspension to each french slant. Tilt the slant back and forth to cover the surface. Remove the excess suspension Aseptically. Incubate the slants at 37° C.±2° C. for 18-24 hours.
  Remove the culture from the agar surface using 3 ml of phosphate buffer and sterile glass beads rotated back and forth to remove the growth. Filter the suspension through a sterile Buchner funnel containing Whatman No. 2 filter paper that has been prewet with 1 ml of phosphate buffer. Collect the suspension in a sterile test tube.
  Standardize the culture suspension by dilution using sterile phosphate buffered water to yield 10×10⁹ organisms per milliliter. 10×10⁹ organisms/ml corresponds roughly to % transmittance readings of 0.1% to 1.0%T at 580 nm. It is recommended that each individual operator determine what %T readings they need to achieve a 10×10⁹ organisms/ml culture suspension prior to performing this test since validity of the test is based on having the proper inoculum.
  Operating Technique
  Dispense 99 ml of test substance into a sterile 250 ml Erlenmeyer flask. Prepare triplicate flasks for each test substance to be tested. Place flasks containing test substance into a 25° C. temperature water and let rest >20 minutes or until reaches test temperature.
  Operating Technique with Milk Challange
  Dispense 90 ml of test substance and 10 mL of milk challange into a sterile 250 ml Erlenmeyer flask, mix and remove 11.0 mL. Prepare duplicate flasks for each test substance to be tested. Place flasks containing test substance into a 25° C. temperature water and let rest >20 minutes or until reaches test temperature
  Enumerate inoculum numbers in sterile phosphate buffer. Enumeration of inoculum numbers will be performed as follows:

Pre-
pared	1:100		1:100		1:100		1:100
Test		→ 100		→ 10−2		→ 10−4		→ 10−6
Cul-
ture

From the 10⁻⁶ dilution, plate 1 ml (10⁶) and 0.1 ml (10⁻⁷) in quadruplicate. Use pour plate technique with TGE medium. Invert and incubate at 37° C.±2° C. for 48 hours. Whirl the test flasks and add 1 ml of culture to 99 ml of the test substance dilution midway between the side of the flask and the center. Avoid touching the sides of the flask with the pipette. Transfer 1 ml portions to the appropriate neutralizer (based on inactivation of the test substance) after 15 seconds exposure and mix well. Longer exposure times may be used depending on the test substance, previous testing and/or the study.
For regulatory documentation testing, plate 1 ml (10⁻¹) and 0.1 ml (10⁻²) from the neutralizer blank tube in quadruplicate. For non-regulatory testing, serial dilutions may be performed in sterile phosphate buffer to yield dilutions of 10⁻¹, 10⁻³, and 10⁻⁵. These dilutions are usually single platings. Use pour plate technique with neutralized (appropriate for test substance inactivation) TGE medium. Invert and incubate at 37° C.±2° C. for 48 hours.
Controls

• 1. Phenol Resistance Method
  • Determine the resistance of the test system to phenol according to standard procedures. The test system must meet the resistance specified in that SOP.
• 2. Neutralization Method (created from ASTM E 1054-91)
  • Duplicate neutralization method check(s) should be performed on each test system. If more than one use-solution concentration is used, test the most concentrate solution. Testing should be performed as follows:
• Test A=Add 1 ml of test substance use-solution to 9 ml of the neutralizer and mix. Add 0.1 ml of ˜10⁻³ cfu/ml test system suspension, mix.
• Test B=Add 1 ml of test substance diluent to 9 ml of the neutralizer and mix. Add 0.1 ml of ˜10⁻³ cfu/ml test system suspension, mix.
• Test C=Add 0.1 ml of ˜10⁻³ cfu/ml test system suspension to 9 ml of phosphate buffered dilution water and mix.
  Let tests stand for 30 minutes, then enumerate by plating 0.1 and 1 ml using pour plate technique and incubating 48 hours at est system specific temperature.
  The data obtained will show the neutralizer to be effective if a≅c. The neutralizer will be observed not be detrimental to the cells if b≅c.
• 3. Diluent Control
  • Plate 1 ml of diluent used in the test. Incubate at 37° C.±2° C. for 48 hours.

TABLE 1
Zero Time Results
	Test	Organic	Time	Log
	Substance	Challenge	Exposure	Reduction
Escherichia coli ATCC 11229
	Ex II Prepared	No Challenge	15 seconds	5.38
	(Jun. 19, 1997)
	Ex II Prepared	10% Milk	15 seconds	5.38
	(Jun. 19, 1997)
	UDDER GOLD	No Challenge	15 seconds	5.38
	PLUS Prepared
	(Jun. 19, 1997)
	UDDER GOLD	10% Milk	15 seconds	5.38
	PLUS Prepared
	(Jun. 19, 1997)
Staphylococcus aureus ATCC 6538
	Ex II Prepared	No Challenge	15 seconds	5.87
	(Jun. 19, 1997)
	Ex II Prepared	10% Milk	15 seconds	5.87
	(Jun. 19, 1997)
	UDDER GOLD	No Challenge	15 seconds	5.87
	PLUS Prepared
	(Jun. 19, 1997)
	UDDER GOLD	10% Milk	15 seconds	5.87
	PLUS Prepared
	(Jun. 19, 1997)

Conclusions:

When freshly prepared both the composition of Example II and UDDER GOLD PLUS achieved a greater than 5 log reduction after 15 seconds with and without a 10% milk challenge against both Staphylococcus aureus ATCC 6538 and Escherichia coli ATCC 11229.

One Week Results
	Test	Organic	Time	Log
	Substance	Challenge	Exposure	Reduction
Escherichia coli ATCC 11229
	Ex II Prepared	No Challenge	15 seconds	5.93
	(Jun. 19, 1997)
	Ex II Prepared	10% Milk	15 seconds	5.93
	(Jun. 19, 1997)
	UDDER GOLD	No Challenge	15 seconds	1.42
	PLUS Prepared
	(Jun. 19, 1997)
	UDDER GOLD	10% Milk	15 seconds	0.61
	PLUS Prepared
	(Jun. 19, 1997)
Staphylococcus aureus ATCC 6538
	Ex II Prepared	No Challenge	15 seconds	5.82
	(Jun. 19, 1997)
	Ex II Prepared	10% Milk	15 seconds	5.82
	(Jun. 19, 1997)
	UDDER GOLD	No Challenge	15 seconds	1.40
	PLUS Prepared
	(Jun. 19, 1997)
	UDDER GOLD	10% Milk	15 seconds	0.59
	PLUS Prepared
	(Jun. 19, 1997)

After one week, Example II achieved a >5 log reduction after 15 seconds with and without a 10% milk challenge against both Staphylococcus aureus ATCC 6538 and Escherichia coli ATCC 11229. UDDER GOLD PLUS achieved a 1.42 log reduction against Escherichia coli ATCC 11229 in 15 seconds without milk, while achieving a 0.61 log reduction with the 10% milk challenge. Against Staphylococcus aureus ATCC 6538 UDDER GOLD PLUS achieved a log reduction of 1.42 without milk, and 0.59 with a 10% milk challenge.

Two Weeks Results
	Test	Organic	Time	Log
	Substance	Challenge	Exposure	Reduction
Escherichia coli ATCC 11229
	Ex II Prepared	No Challenge	15 seconds	5.74
	(Jun. 19, 1997)
	Ex II Prepared	10% Milk	15 seconds	4.00
	(Jun. 19, 1997)
	UDDER GOLD	No Challenge	15 seconds	2.06
	PLUS Prepared
	(Jun. 19, 1997)
	UDDER GOLD	10% Milk	15 seconds	0.26
	PLUS Prepared
	(Jun. 19, 1997)
Staphylococcus aureus ATCC 6538
	Ex II Prepared	No Challenge	15 seconds	5.75
	(Jun. 19, 1997)
	Ex II Prepared	10% Milk	15 seconds	5.75
	(Jun. 19, 1997)
	UDDER GOLD	No Challenge	15 seconds	2.09
	PLUS Prepared
	(Jun. 19, 1997)
	UDDER GOLD	10% Milk	15 seconds	0.32
	PLUS Prepared
	(Jun. 19, 1997)

After two weeks, Example II achieved a >5 log reduction after 15 seconds with and without a 10% milk challenge against Staphylococcus aureus ATCC 6538. Against Escherichia coli ATCC 11229 a reduction of 4.00 was seen with the 10% milk challenge while a 5.74 log reduction was seen without the challenge. UDDER GOLD PLUS achieved a 2.06 log reduction against Escherichia coli ATCC 11229 in 15 seconds without milk, while achieving a 0.26 log reduction with the 10% milk challenge. Against Staphylococcus aureus ATCC 6538 UDDER GOLD PLUS achieved a log reduction of 2.09 without milk, and 0.32 with a 10% milk challenge.

Three Weeks Results
	Test	Organic	Time	Log
	Substance	Challenge	Exposure	Reduction
Escherichia coli ATCC 11229
	Ex II Prepared	No Challenge	15 seconds	5.67
	(Jun. 19, 1997)
	Ex II Prepared	10% Milk	15 seconds	3.91
	(Jun. 19, 1997)
	UDDER GOLD	No Challenge	15 seconds	1.86
	PLUS Prepared
	(Jun. 19, 1997)
	UDDER GOLD	10% Milk	15 seconds	0.26
	PLUS Prepared
	(Jun. 19, 1997)
Staphylococcus aureus ATCC 6538
	Ex II Prepared	No Challenge	15 seconds	5.76
	(Jun. 19, 1997)
	Ex II Prepared	10% Milk	15 seconds	5.76
	(Jun. 19, 1997)
	UDDER GOLD	No Challenge	15 seconds	1.78
	PLUS Prepared
	(Jun. 19, 1997)
	UDDER GOLD	10% Milk	15 seconds	0.36
	PLUS Prepared
	(Jun. 19, 1997)

After three weeks, Example II achieved a >5 log reduction after 15 seconds with and without a 10% milk challenge against Staphylococcus aureus ATCC 6538. Against Escherichia coli ATCC 11229 a reduction of 3.91 was seen with the 10% milk challenge while a 5.67 log reduction was seen without the challenge. UDDER GOLD PLUS achieved a 1.86 log reduction against Escherichia coli ATCC 11229 in 15 seconds without milk, while achieving a 0.26 log reduction with the 10% milk challenge. Against Staphylococcus aureus ATCC 6538 UDDER GOLD PLUS achieved a log reduction of 1.78 without milk, and 0.36 with a 10% milk challenge.

Four Weeks Results
	Test	Organic	Time	Log
	Substance	Challenge	Exposure	Reduction
Escherichia coli ATCC 11229
	Ex II Prepared	No Challenge	15 seconds	>5.5
	(Jun. 19, 1997)
	Ex II Prepared	10% Milk	15 seconds	>5.5
	(Jun. 19, 1997)
	UDDER GOLD	No Challenge	15 seconds	1.2
	PLUS Prepared
	(Jun. 19, 1997)
	UDDER GOLD	10% Milk	15 seconds	0.1
	PLUS Prepared
	(Jun. 19, 1997)
Staphylococcus aureus ATCC 6538
	Ex II Prepared	No Challenge	15 seconds	>6.0
	(Jun. 19, 1997)
	Ex II Prepared	10% Milk	15 seconds	5.3
	(Jun. 19, 1997)
	UDDER GOLD	No Challenge	15 seconds	1.3
	PLUS Prepared
	(Jun. 19, 1997)
	UDDER GOLD	10% Milk	15 seconds	0.6
	PLUS Prepared
	(Jun. 19, 1997)

After four weeks, Example II achieved a >5 log reduction after 15 seconds with and without a 10% milk challenge against both Staphylococcus aureus ATCC 6538 and Escherichia coli ATCC 11229. UDDER GOLD PLUS achieved a 1.2 log reduction against Escherichia coli ATCC 11229 in 15 seconds without milk, while achieving a 0.6 log reduction with the 10% milk challenge. Against Staphylococcus aureus ATCC 6538 UDDER GOLD PLUS achieved a log reduction of 1.3 without milk, and 0.6 with a 10% milk challenge.

Porcine Skin Test

An analysis was made to determine the antimicrobial activity of teat dips applied to porcine skin inoculated with Staphylococcus aureus ATCC 6538 and Escherichia coli ATCC 11229. Using the following Test Method:

• 1. One inch squares of sterile lyophilized porcine skin (Corethium™2, Johnson & Johnson UK) were rehydrated in sterile distilled water for 1 hour.
• 2. Hydrated skin squares were dipped into each teat dip formulation for 10 seconds and hung in a vertical position to allow excess to drain off.
• 3. The squares were then place din a sterile petri dish and inoculated with 10 microliters of a 24 hour broth culture for the organism to be tested. After inoculation, samples were allowed a contact time of 5 minutes.
• 4. Skin squares were then put in a tube containing 20 mL of the appropriate neutralizer.
• 5. Samples were then vortexed and dilutions of 10⁻¹, 10⁻³, and 10⁻⁵ were plated in order to enumerate the survivors.
• 6. Plates were incubated at 37° C. for 48 hours.
• 7. A neutralization test was also performed.
  Method Parameters:

                Active
Test Substance  Ingredients

ClO2 Example II 2.00% LAS
Formulation     ClO2
Prepared Jun. 19, 1997)
UDDER GOLD      ClO2
PLUS
(Prepared Jun. 19, 1997)
Water Control   None

Test Systems:

• • Staphylococcus aureus ATCC 6538
  • Escherichia coli ATCC 11229
    Test Temperature: Room Temperature
    Exposure Time: 5 minutes
    Subculture Medium: Tryptone Glucose Extract Agar
    Incubation: 37° C. for 48 hours
    Results:

TABLE 2
Zero Time
		Exposure Time to
	Test Substance	Teat Dip (min)	Log Reduction
Staphylococcus aureus ATCC 6538
	ClO2 Example II Formula	5	2.73
	(Prepared Jun. 19, 1997)
	UDDER GOLD PLUS	5	No Reduction
	(Prepared Jun. 19, 1997)
	Water Control	5	N/A
Escherichia coli ATCC 11229
	ClO2 Example II Formula	5	1.78
	(Prepared Jun. 19, 1997)
	UDDER GOLD PLUS	5	1.32
	(Prepared Jun. 19, 1997)
	Water Control	5	N/A

Results:

One Week
		Exposure Time to
	Test Substance	Teat Dip (min)	Log Reduction
Staphylococcus aureus ATCC 6538
	UDDER GOLD PLUS	5	No Reduction
	(Prepared Jun. 19, 1997)
	ClO2 Example II Formula	5	3.48
	(Prepared Jun. 19, 1997)
	Water Control	5	N/A
Escherichia coli ATCC 11229
	UDDER GOLD PLUS	5	0.20
	(Prepared Jun. 19, 1997)
	ClO2 Example II Formula	5	1.83
	(Prepared Jun. 19, 1997)
	Water Control	5	N/A

Results:

Two Weeks
		Exposure Time to
	Test Substance	Teat Dip (min)	Log Reduction
Staphylococcus aureus ATCC 6538
	UDDER GOLD PLUS	5	No Reduction
	(Prepared Jun. 19, 1997)
	ClO2 Example II Formula	5	3.52
	(Prepared Jun. 19, 1997)
	Water Control	5	N/A
Escherichia coli ATCC 11229
	UDDER GOLD PLUS	5	0.08
	(Prepared Jun. 19, 1997)
	ClO2 Example II Formula	5	0.60
	(Prepared Jun. 19, 1997)
	Water Control	5	N/A

Results:

Three Weeks
		Exposure Time to
	Test Substance	Teat Dip (min)	Log Reduction
Staphylococcus aureus ATCC 6538
	UDDER GOLD PLUS	5	No Reduction
	(Prepared Jun. 19, 1997)
	ClO2 Example II Formula	5	2.26
	(Prepared Jun. 19, 1997)
	Water Control	5	N/A
Escherichia coli ATCC 11229
	UDDER GOLD PLUS	5	0.77
	(Prepared Jun. 19, 1997)
	ClO2 Example II Formula	5	1.73
	(Prepared Jun. 19, 1997)
	Water Control	5	N/A

Results:

Four Weeks
		Exposure Time to
	Test Substance	Teat Dip (min)	Log Reduction
Staphylococcus aureus ATCC 6538
	UDDER GOLD PLUS	5	0.19
	(Prepared Jun. 19, 1997)
	ClO2 Example II Formula	5	2.78
	(Prepared Jun. 19, 1997)
	Water Control	5	N/A
Escherichia coli ATCC 11229
	UDDER GOLD PLUS	5	0.07
	(Prepared Jun. 19, 1997)
	ClO2 Example II Formula	5	1.72
	(Prepared Jun. 19, 1997)
	Water Control	5	N/A

These test results show the compositions of the invention are superior in these anti-microbial tests to a quality commercial teat dip. These data are representative in anti-microbial properties of the exemplary formulations of the invention.

The teat dip compositions of the invention using nonanoic acid and a sulfonate material in a formulation with 1-propanol, were tested for their properties in coating and forming a useful antimicrobial layer that maintains a sufficient quantity of material on the animal. A simulated test was conducted involving a test tube. In the method a Kimax® brand glass test tube (20 mm×150 mm) is weighted, and dipped approximately 2 inches into the teat dip being tested. The test tube is then removed from the dip and placed on hanging rack for 10 minutes above a beaker that was previously weighted. At the end of 10 minutes the beaker and the test tube are each weighed again and the data is entered into the table. The dry weight is obtained by allowing the resulting teat dip film to dry for 24 hrs.

Simulated Teat Dipping Test
UDDER GOLD PLUS
	Wet Wt.	Wet Wt.	Dry Wt.	Dry Wt.
	UDDER	UDDER	UDDER	UDDER
	GOLD	GOLD	GOLD	GOLD
Sample Name	PLUS 1	PLUS 2	PLUS 1	PLUS 2
Beaker Tare	110.3762	106.9215	110.3762	106.9215
Test Tube	24.5295	18.9019	24.5295	18.9019
Tare
Beaker	111.7136	108.1773	110.5015	107.0377
@ 10 min.
Test Tube	26.6747	19.0028	24.5459	18.9151
@ 10 min.
Product on	0.1452	0.1009	0.0164	0.0132
Test Tube
Product in	1.3374	1.2558	0.1253	0.1162
Beaker
% Product	9.79%	7.44%	11.57%	10.20%
Retained
% Product	90.21%	92.56%	88.43%	89.80%
Lost
Simulated Teat Dipping Test
Composition of Example I
	Wet Wt.	Wet Wt.	Dry Wt.	Dry Wt.
	Example	Example	Example	Example
Sample Name	I	I	I	I
Beaker Tare	108.0534	107.0201	108.0534	107.0201
Test Tube	25.0294	24.9161	25.0294	24.9161
Tare
Beaker	108.3413	107.3925	108.1192	107.1081
@ 10 min.
Test Tube	25.1733	25.0665	25.0596	24.9432
@ 10 min.
Product on	0.1439	0.1504	0.0302	0.0271
Test Tube
Product in	0.2879	0.3724	0.0658	0.0880
Beaker
% Product	33.33%	28.77%	31.46%	23.54%
Retained
% Product	66.67%	71.23%	68.54%	76.46%
Lost
Comments:	Wet Wt. =	Formula Example I = 2.5%	1-Propanol
	10 minutes
	Dry Wt. =	1.5	C9
	24 hours	17.0%	NAS

A brief examination of the tabulated data show that the rheology of the material of Example I maintains a larger quantity of material on the simulated animal when compared to the rheology of the commercial teat dip formulation. These data suggest that the composition of Example I would be somewhat more effective in mastitis treatment because the formulations of the invention would maintain a larger quantity of treating composition in a longer lasting film than the commercial materials. In other testing we have found that the identity of the antibacterial material, carboxylic acid, fatty acid, phosphoric acid or sulfonic acid, does not significantly change the rheology of the material and a fully formulated material having rapid initial kill and long term kill can be formulated in a long lasting film-forming composition.

The following Examples show a preferred emolient/humectant formulation technology.

EXAMPLE XV

Chlorine Dioxide Teat Dip
Acidulant
Item	Ingredients	Wt %
1	Deionized Water	71.92
2	KOH, 45%	1.10
3	Benzoic Acid	0.20
4	Kelzan T	0.301
5	Laneto 50	1.00
6	Sorbitol, 70% (Glucitol)	6.43
7	LAS, 97%	2.002
8	Lactic Acid, 88%	2.95
9	Elvanol Premix, 10%	10.00
10	Pylaklor Yellow	4.00
	LLX1-10192, 5.0%
11	Sunsperse Blue GS	0.103
TOTAL		100.00
1stir at least 1 hr./check clarity
2stir 10 minutes
3pH = → should be ˜2.70

Mixing Instructions:

• 1. Add item 1 to mix tank. Turn on agitator. Slowly add item 2.
• 2. Add item 3 and mix until dissolved.
• 3. Charge item 4 with water through an eductor funnel, Hercules mixing tee or manually continue agitation at a slow addition rate. Lumping may result if added too quickly. Mix for 1 hour or until item 4 is completely solubilized.
  Have QC check for clarity
  Note: Complete solubilization is crucial before additional items are added.
• 4. Add items 5 and 6. Mixing well between each addition.
• 5. Slowly add item 7 to avoid high concentrations of localized acidity. Mix—10 minutes.
• 6. Slowly add item 8 and mix well. Add item 9 and mix well.
• 7. Add items 10 and 11. Final mix is 30 mintues.
• 8. Transfer and filter batch with 80 ( 3/16 inch) mesh strainer. Sample for QC.

Activator
Sodium Chlorite Solution - 6.25% Aqueous
Item	Ingredients	Wt %
1	Deionized Water	75.00
2	Sodium Chlorite, 25%	25.00
TOTAL		100.00

Mixing Instructions:

• 1. Add item 1 to the mix tank.
• 2. Slowly add item 2 (mix ratio 3376 gs. Acidualnt with 93 gs. Of the Activator) and mix well.

EXAMPLE XVI

Chlorine Dioxide Teat Dip; Pre DipFormula

Purpose: Prepare a 1000 g batch of the following experimental predip formula for physical stability testing.

Predip Formula
Item	Ingredients	Wt %
1	Deionized Water	91.580
2	KOH, 45%	1.230
3	Benzoic Acid	0.200
4	Kelzan T	0.1001
5	Neodol 25-9	0.500
6	Sorbitol, 70% (Glucitol)	1.430
7	LAS, 97%	2.0002
8	Lactic Acid, 88%	2.950
9	Sunsperse Blue GS	0.0103
TOTAL		100.00
1stir at least 1 hr./check clarity
2stir 10 minutes
3pH = ˜2.70

Mixing Instructions:

• 1. Add item to mix tank. Turn on agitator. Add item 2 and mix until dissolved.
• 2. Slowly add item 3.
• 3. Charge item 4 with water through an eductor funnel, Hercules mixing tee or manually continue agitation at a slow addition rate. Lumping may result if added too quickly. Mix for 1 hour or until item 4 is completely solubilized. Have QC check for clarity
• 4. Add items 5 and 6. Mixing well between each addition.
• 5. Slowly add item 7 to avoid high concentrations of localized acidity. Mix 10 minutes.
• 6. Slowly add item 8 and mix well.
• 7. Add item 9. Final mix is 30 minutes.
• 8. Transfer and filter batch with 80 ( 3/16 inch) mesh strainer. Sample for QC.

Activator-Sodium Chlorite Solution - 6.25%
Item	Ingredients	Wt %
1	Deionized Water	75.00
2	Sodium Chlorite, 25%	25.00
TOTAL		100.00

Mixing Instructions:

• 1. Add item 1 to the mix tank.
• 2. Slowly add item 2 (mix ratio 3376 gs. Predip Formula with 93 gs. Of the Activator) and mix well.

EXAMPLE XVII

Chlorine Dioxide Teat Dip; Pre/Post Dip Formula

Purpose: Prepare a 5 gallon batch of the following experimental pre/post dip

Pre/Post Formula
Item	Ingredients	Wt %
1	Deionized Water	83.46
2	KOH, 45%	1.25
3	Benzoic Acid	0.20
4	Kelzan T	0.101
5	Neodol 25-9	0.50
6	Laneto 50	1.00
7	Sorbitol, 70% (Glucitol)	6.43
8	LAS, 97%	2.062
9	Lactic Acid, 88%	2.95
10	Pylaklor Yellow LX-10192,	2.00
	5.0%
11	Sunsperse Blue GS	0.053
TOTAL		100.00
1stir at least 1 hr./check clarity
2stir 10 minutes
3pH = ˜2.70

Mixing Instructions:

• 1. Add item 1 to mix tank. Turn on agitator. Slowly add item 2.
• 2. Add item 3 and mix until dissolved.
• 3. Charge item 4 with water through an eductor funnel, Hercules mixing tee or manually continue agitation at a slow addition rate. Lumping may result if added too quickly. Mix for 1 hour or until item 4 is completely solubilized. Have QC check for clarity
• 4. Add items 5, 6 and 7. Mixing well between each addition.
• 5. Slowly add item 8 to avoid high concentrations of localized acidity. Mix until dispersed—approximately 10 minutes.
• 6. Slowly add item 9 and mix well.
• 7. Add items 10 and 11. Final mix is 30 minutes.
• 8. Transfer and filter batch with 80 ( 3/16 inch) mesh strainer. Sample for QC.

Activator Formula-Sodium Chlorite Solution - 6.25%
Item	Ingredients	Wt %
1	Deionized Water	75.00
2	Sodium Chlorite, 25%	25.00
TOTAL		100.00

Mixing Instructions:

• 1. Add item 1 to the mix tank.
• 2. Slowly add item 2 and mix well.

EXAMPLE XVIII

Conc. Chlorine Dioxide Teat Dip; Udder Wash & Teat Dip Formula

Purpose: Prepare a 100 g batch of the following experimental udder wash & teat dip formula for stability testing at 122° F. temperature condition.

CONC Formula
Item	Ingredients	Wt %
1	Deionized Water	27.60
2	KOH, 45%	0.05
3	Benzole Acid	0.20
4	Sunsperse Blue GS	1.10
5	Propylene Glycol	11.90
6	Neodol 25-9	2.15
7	LAS, 97%	2.15
8	Laneto 50	5.50
9	Sortitol, 70%	30.35
10	Lactic Acid, 88%	19.00
TOTAL		100.001
Activator Formula: 3.125% Sodium Chlorite
Item	Ingredients	Wt %
1	Deionized Water	87.50
2	Sodium Chlorite, 25% aqueous	12.50
TOTAL		100.00
Mix Ratios:
Acidulant
Base (g)	Activator	Water
1	1 part	20 parts
Physical Stability:
	122° F.	After 24 hrs. at 122° F., the above product IS stable.
		After 4 days at 122° F., the above product IS stable.
		After 1 week at 122° F., the above product IS stable.
Comments:
	Control	Continue (1 + 1 + 20) Ph = 2.41
	Control	Continue Activator Conc pH = 1.6
	Formula K	use-dil (1 + 1 + 20) pH = 2.62
	CLO2	885 ppm
	1product looked good - no particulates

EXAMPLE XIX

Conc. Chlorine Dioxide Teat Dip Acid Formula
Item	Ingredients	Wt %
1	Deionized Water	27.60
2	KOH, 45%	0.05
3	Benzoic Acid	0.20
4	Sunsperse Blue GS Dye	1.10
5	Propylene Glycol	11.90
6	Neodol 25-9 nonionic	2.15
7	LAS, 97% anionic sulf.	2.15
8	Laneto 50 (EO)75 - lanolin	5.50
9	Sortitol, 70%	30.35
10	Lactic Acid, 88%	19.00
TOTAL		100.00
Activator Formula: 3.125% Sodium Chlorite
Item	Ingredients	Wt %
1	Deionized Water	87.50
2	Sodium Chlorite, 25%	12.50
TOTAL		100.00

Mix Ratios:
1 part Acid Formula: 1 part Activator Formula
Comments:
CLO₂ titr. RTU=885 ppm

The following Examples and data demonstrate that the dyed system can be made resistant, due to the addition of urea, to dye bleaching from the chlorine dioxide generated in the final dip. The product shown is the acid part or base dip. To this acid part is added a sodium chlorite part. The acid adjusts pH and reacts with sodium chlorite (NaClO₂) to form chlorine dioxide.

EXAMPLE XX

Barrier Test Dip Base Part (Part 1)
RAW MATERIAL           WT-%

DI water               70.46
Polyvinyl alcohol      1.00
DI water               10.00
KOH (45% aqueous)      0.40
Sodium benzoate        0.18
Xanthan gum            0.30
Lactic acid            2.95
Urea, prilled          1.50
Lanolin ethoxylate     1.00
Propylene glycol       10.00
Linear Dodecyl benzene 2.06
sulfonic acid
FD&C Blue Dye #1       0.05
FD&C Yellow Dye #5     0.10
TOTAL                  100.00

Activator Part (ClO2−1 Formula; pH = 12.3) (Part 2)
	Ingredients	Wt %	Grams
	Deionized Water	85.00	850.00
	Sodium Chlorite, 25%	15.00	150.00
	TOTAL	100.00	1000.00

The following test examples were prepared similarly to Example XX to test the capacity of the systems of the invention to stabilize the color of FD&C yellow dye #5 and FD&C blue dye #1 in the oxidative enviroment of the formulated materials with a range of chlorite, colorant and urea concentrations.

These data are displayed in FIG. 4.

TEST EXAMPLE XXI-A-B-C, EXAMPLE XXII-A-B-C and EXAMPLE XXIII-A-B-C

						Base	Make
		FDC	FDC		Urea	Dip	up	Total
	ClO2−1	Y #5	B #1	Urea	g of	Conc	Water	Vol.
Sample	(ppm)	(%)	(%)	(%)	100%	(mL)	(%)	(mL)
XXIA	479	0.10	0.05	0.50	0.50	90.00	6.58	93.42
XXIB	479	0.10	0.05	1.00	1.00	90.00	5.58	94.42
XXIC	479	0.10	0.05	1.50	1.50	90.00	4.58	95.42
XXIIA	638	0.10	0.05	0.50	0.50	90.00	6.33	93.67
XXIIB	638	0.10	0.05	1.00	1.00	90.00	5.33	94.67
XXIIC	638	0.10	0.05	1.50	1.50	90.00	4.33	95.67
XXIIIA	825	0.10	0.05	0.50	0.50	90.00	6.03	93.97
XXIIIB	825	0.10	0.05	1.00	1.00	90.00	5.03	94.97
XXIIIC	825	0.10	0.05	1.50	1.50	90.00	4.03	95.97

Increasing concentrations of urea clearly stabilized the color in the formulations.

EXAMPLE XXIII

	CONTROL
	RAW MATERIAL	1	3
	DI water	32.6	35.6
	Benzoic acid	0.2	0.2
	KOH 45%	0.4	0.4
	Propylene glycol	42	38
	Neodol 25-9	2.15	1.15
	Lactic acid 88%	12.5	12.5
	Lanolin	5.5	5.5
	Urea	0	1
	Pluronic F 68	0	1
	LAS acid	2.15	2.15
	FD&C Yellow 5	2.5	2.5
	CAS # 12225-21-7
	100% pH	1.76	1.85

This example shows a formulation made with and without urea stabilizing the organic dye. These materials were equally effective sanitizer materials against a microbial challenge.

The following Examples were made to show that the urea color stability system also lengthens the useful lifetime of the blended materials. The urea slows chlorine dioxide release is delayed resulting in the generation of chlorine dioxide at a somewhat lower but effective concentration for a greater amount of effective life.

EXAMPLE XXIV

	RAW MATERIAL	A (%)	B (%)	C (%)
	DI water	45.600	45.800	44.038
	KOH 45%	0.400	0.400	0.385
	Benzoic acid	0.200	0.200	0.192
	Propylene glycol	30.000	30.000	28.846
	Neodol 25-9	2.150	2.150	2.067
	Lanolin	5.500	5.500	5.288
	Lactic acid	10.500	11.000	14.423
	LAS acid	2.150	2.200	2.115
	Urea	2.000	1.250	1.202
	FD&C Blue 1	1.500	1.500	1.4442
	TOTAL	100.000	100.000	100.000

Chlorine Dioxide Profile of Examples XXIV A-C

		XXIV A	XXIV B	XXIV C
	Hours	ppm ClO2	ppm ClO2	ppm ClO2
	0.50	6.4	8.90	12.0
	0.30	—	11.6	14.4
	0.50	9.4	13.0	16.6
	1.00	16.3	16.9	21.8
	1.50	17.0	16.0	20.0
	3.00	19.6	24.9	32.9
	4.00	24.9	34.0	38.7
	6.00	30.1	44.5	56.7
	24.00	67.0	93.0	121.0

These data show an important aspect of the invention. The use of urea in a chlorine dioxide generating system appears to slow the release of chlorine dioxide after the acidulant part is combined with the chlorite part. The data in the table shows that the increasing concentration of the urea reduces the concentration of available chlorine dioxide and as a result delays the generation of chlorine dioxide, extending the effective lifetime of the treatment material. This demonstrates that the urea component asked to both stabilize color and to extend the effective lifetime (chlorite concentration) of the treatment material.

EXAMPLE XXV

Materials prepared for long term stability testing
RAW MATERIAL	A	B	C	D
DI water	41.800	39.250	36.600	33.850
KOH 45%	0.400	0.400	0.400	0.400
Benzoic acid	0.200	0.200	0.200	0.200
Propylene glycol	30.000	30.000	30.000	30.000
Neodol 25-9	2.150	2.150	2.150	2.150
Lanolin	5.500	5.500	5.500	5.500
Lactic acid	15.000	15.000	15.000	15.000
LAS acid	2.200	4.000	6.000	8.000
KOH 45%	0.000	0.750	1.400	2.150
Urea	1.250	1.250	1.250	1.250
FD&C Blue 1	1.500	1.500	1.500	1.500
TOTAL	100.000	100.000	100.000	100.000
100% pH	1.79	1.70	1.69	1.70
Appearance of Products	Initially	Initially	Initially	Clear
w/o Dye	Hazy	Hazy	Hazy

These materials were storage stable at common storage temperatures and provided were effective sanitizer materials over an extended period. Initial haze cleared after less than one week. The materials were freeze-proof.

EXAMPLE XVI

Chemiluminescent Teat Dips

In the invention, the chemiluminescence process involves three components, an oxidizer (usually hydrogen peroxide or an indirect source of hydrogen peroxide), oxalate ester or amide (examples are Figures (I) and (II)). These esters or amides can be water insoluble and utilize oil-in-water emulsions or they can be water soluble. Likewise, oil soluble fluorescers and/or water soluble fluorescers may be used. The oil phase of the emulsified version may prove useful for solubilizing the fluorescer as well as the oxalate ester or amide.

Additionally, the chemiluminescent system may use Luminol type chemistry, and these may include an oxidizer (again, usually hydrogen peroxide or an indirect source of hydrogen peroxide), Luminol, a metal ion, (i.e., Cu (II) added as Cu(SO₄)₂) and a carbonate buffer system at pH 8-10 is typical.

Suitable oxalate esters include: 4,4′-{oxalyl bis (3-nitrobenzene sulfonic acid)} and oxalyl bis (N-oxysuccinimide) and others.

Composition of Two Part System

EXAMPLE (I)

	INGREDIENT	%	Wt (grams)
Activator Formula (Part I)
	4,4′-(oxalyl bis (3-nitrobenzene	50.0	0.5
	sulfonic acid))
	Rhodamine B (C.I. 45170)	50.0	0.5
Base Formula (Part II)
	Water	88.0	880.0
	Hydrogen peroxide (35% w/v)	3.0	30.0
	Lactic acid	2.8	28.0
	Glycerin	6.0	60.0
	Xanthan gum	0.2	2.0

EXAMPLE (II)

	INGREDIENT	%	Wt (grams)
Activator Formula (Part I)
	Oxalyl bis (N-oxysuccinimide)	50.0	0.5
	Rhodamine B (C.I. 45170)	50.0	0.5
Base Formula (Part II)
	Water	88.0	880.0
	Hydrogen peroxide (35% w/v)	3.0	30.0
	Lactic acid	2.8	28.0
	Glycerin	6.0	60.0
	Xanthan gum	0.2	2.0

Suitable oxalate amides include:

EXAMPLE (III)

	INGREDIENT	%	Wt (grams)
Activator Formula (Part I)
	Bis[2,6-dichloro-4-[(2-	50.0	0.5
	dimethylaminoethyl)
	methylsulfamoyl]phenyl}oxalate
	dihydrochloride
	Rhodamine B (C.I. 45170)	50.0	0.5
Base Formula (Part II)
	Water	88.0	880.0
	Hydrogen peroxide (35% w/v)	3.0	30.0
	Lactic acid	2.8	28.0
	Glycerin	6.0	60.0
	Xanthan gum	0.2	2.0

EXAMPLE (IV)

	INGREDIENT	%	Wt (grams)
Activator Formula (Part I)
	CCPO (bis2,4,5-	50.0	0.5
	trichlorophenyl-6-
	carbopentoxyphenyl)oxalate
	1-Chloro-9,10-	50.0	0.5
	bis(phenynyl)anthracene
Base Formula (Part II)
	Water	87.05	870.5
	Hydrogen peroxide (35% w/v)	3.0	30.0
	Lactic acid	2.8	28.0
	Glycerin	6.0	60.0
	Xanthan gum	0.4	4.0
	Glyceryl laurate (Monolaurin)	0.5	5.0
	Nonylphenol ethoxylate (9.5	0.25	2.5
	EO)

An example of an indirect source of hydrogen peroxide is sodium perborate. The following is an example of a teat dip formula which substitutes sodium perborate for hydrogen peroxide.

EXAMPLE (V)

INGREDIENT	%	Wt (grams)
Activator Formula (Part I)
Bis[2,6-dichloro-4-[(2-	50.0	0.5
dimethylaminoethyl) methylsulfamoyl]phenyl}
oxalate dihydrochloride
Rhodamine B (C.I. 45170)	50.0	0.5
Base Formula (Part II)
Water	88.0	880.0
Sodium perborate	3.0	30.0
Lactic acid	2.8	28.0
Glycerin	6.0	60.0
Xanthan gum	0.2	2.0

EXAMPLE (VI)

	INGREDIENT	%	Wt (grams)
Activator Formula (Part I)
	Sodium chlorite	9.09	1.0
	Sodium perborate	90.91	10.0
Base Formula (Part II)
	Water	90.95	909.5
	Lactic acid	2.75	27.5
	Glycerin	6.0	60.0
	Xanthan gum	0.20	2.0
	Rhodamine B (C.I. 45170)	0.05	0.5
	Bis{2,6-dichloro-4-[(2-	0.05	0.5
	dimethylaminoethyl)
	methylsulfamoyl]phenyl}oxalate
	dihydrochloride

To initiate the chemiluminiscence phenomena, the entire contents of the activator (Part I) is mixed thoroughly, with the entire contents of the respective base (Part II) at ambient temperatures.

DETAILED DISCUSSION OF THE DRAWINGS

FIG. 1A and FIG. 1B are a graphical representations of the data shown in the tables from page 46 to 50 showing the results of a four week biocidal efficacy analysis of Example II using the food contact sanitizing protocol shown at pages 41 to 45 preceding the data in the specification. Clearly, from zero time through four weeks the composition of Example II had a kill substantially greater than a 5 log reduction in microbial populations of both model microorganisms. This data was taken without a milk challenge. However, FIG. 1B shows, within experimental error, similar properties using the same food contact sanitizing protocol with a 10% milk soil challenge. The week 2 and week 3 kill of E. coli is not easily explained in view of the 5.5 log reduction obtained in week 4 for that model microorganism. However, overall the results are strikingly successful in reducing microorganism populations on food contact surfaces.

FIG. 1C and FIG. 1D are graphical representations of data showing the results of the four week biocidal efficacy analysis of a commercial teat dip composition sold under the tradename UDDER GOLD PLUS.

The superiority in performance of the composition of Example II when compared to the UDDER GOLD PLUS compositions is marked particularly in weeks 1 through 4.

FIG. 2A, a graphical representation of the data shown in the tables from page 52 to 56 is a four week efficacy analysis of the UDDER GOLD PLUS chlorine dioxide teat dip formulation measured using the procein skin protocol at pages 51 to 52 in the specification. In all test periods the material failed to achieve greater than a 2 log reduction.

FIG. 2B, prepared from the corresponding data given in the forementioned tables, shows a four week efficacy analysis of Example II using the porcein skin protocol. Clearly, under these more difficult conditions using the porcein skin substrate as a test vehicle, the log reductions in kill are not as great as those for food contact surfaces, however, the biocidal efficacy of Example II exceeded that of the well regarded UDDER GOLD PLUS chlorine dioxide formulations.

FIG. 3, shows a graph of the change in viscosity measured in centipoise plotted against shera rpm for UDDER GOLD PLUS and Example II and Example IX of the invention. The examples of the invention should show classic non-neutonian or nonlinear viscosity with respect to shear. At low shear, i.e., low rpm, the viscosity is high. As shear increases, viscosity drops. In sharp contrast, viscosity of the UDDER GOLD PLUS formulation shows much less pseudoplastic behavior. The viscosity is substantially constant as shear or rpm increases. This viscosity information is consistent with the data of the previous table and demonstrates that the viscoelastic behavior of the compositions of the invention are likely to coat and adhere to teat tissue more efficiently than UDDER GOLD PLUS. Since the materials are sheared somewhat upon application, the materials will flow on to the teat surface. However, when shear is removed, the teat dips obtain high viscosity and tend to adhere more tenaciously than a composition such as UDDER GOLD PLUS having linear viscosity. The substantial difference in viscosity at low shear (low rpm) demonstrates that the materials should coat the teat with substantially more material and after drying have a more effective environmental barrier.

The procedure is as follows. Place ˜500 mls of the experimental teat dip in 600 ml beaker. Record viscosity measurements at various rpms. Apparatus: Brookfield RVT Viscometer, spindle #1 and 2, various rpm (see chart below). Start Temperature: 73.6° F.-Stop Temperature: 73.8° F.

RPM	Example II	Example IX	U Gold Plus	Spindle #
5	940	802	244	1
10	595	501	240	1
20	374	315	234	1
50	247	210	230	2
100	156	141	224	2

FIG. 4 shows the stability is color obtained using a combination of urea and an oxidizable organic dye, not a pigment, in the oxidative systems of the invention (see Examples XXIIA, XXIIIA AND XXIIIC).

The above specification, example and data provide a clear basis for understanding the operation of the compositions and methods of the invention. While the invention can be embodied in a variety of specific examples and processes, the invention resides in the claims hereinafter appended. In the claims, the proportions are expressed in parts by weight per each one hundred parts of the claimed antimastitis composition as a whole.

Claims

1. A physically and chemically stable, visibly indicated, mastitis treatment composition that can effectively reduce microbial populations on contact with an animal skin for an extended period, said composition comprising a blended combination comprising:

(a) an aqueous acidulant part comprising an activator acid, a rheology modifier or a pseudoplastic thickener, a chlorine dioxide stable visual indicator system selected from the group consisting of:

(i) about 0.05-30 wt % of urea and about 0.001-10 wt % of a colorant, based on the weight of the blended composition; and

(ii) comprising about 0.001-50 wt %, based on the weight of the blended composition combination, of a dispersed oil phase, wherein said oil phase contains about 0.001-50 wt % of an oil-soluble dye, based on the weight of said oil phase, and said oil phase is uniformly dispersed in a fine particle size in the blended composition combination and a major proportion of water; and

(b) a chlorite part substantially free of organic component, consisting essentially of comprising an alkali metal chlorite salt;

2. The composition of claim 1 wherein the visual indicator system contains, in the blended composition, about 0.1 to 5.0 wt % of urea and about 0.005 to 2.0 wt % of a blue dye.

3. The composition of claim 2 wherein the blue dye comprises FD&C Blue No.1.

4. The composition of claim 1 wherein the blended composition combination further comprises a first indicator dye having color instability in the presence of chlorite or chlorine dioxide such that the dye substantially loses color within about an hour of blending and a second dye that maintains an effective color for at least 24 hours after blending.

5. The composition of claim 1 4 wherein the indicator stability comprises about one week.

6. The composition of claim 1 4 wherein the indicator stability comprises about two weeks.

7. The composition of claim 1 wherein the oil phase contains a drying oil.

8. A physically and chemically stable visibly indicated mastitis treatment composition that can effectively reduce microbial populations on contact with an animal surface for an extended period of time comprising a combined aqueous acidulant part and a chlorite part, the mastitis treatment composition can effectively reduce microbial populations on contact with an animal surface for an extended period of time,

(a) said aqueous acidulant part comprising an activator acid comprising a phosphoric acid, lactic acid, glycolic acid or mixtures thereof, and a chlorine dioxide stable visual indicator system selected from the group consisting of:

(i) about 0.05-30 wt % of urea and about 0.001-10 wt % of a colorant, based on the weight of the composition; and

(ii) comprising about 0.001-50 wt %, based on the weight of the composition, of a dispersed oil phase, wherein said oil phase contains about 0.001-50 wt % of an oil-soluble dye, based on the weight of said oil phase, and said oil phase is uniformly dispersed in a fine particle size in the composition; , and stable in the combined mastitis treatment composition; and

(b) said chlorite part substantially free of organic component, consisting essentially of comprising an alkali metal chlorite salt;

9. The composition of claim 8 wherein the visual indicator system contains, in the composition, about 0.1 to 5.0 wt % of urea and about 0.005 to 2.0 wt % of a blue dye.

10. The composition of claim 9 wherein the blue dye comprises FD&C Blue No. 1.

11. The composition of claim 8 wherein the composition further comprises a first indicator dye having color instability in the presence of chlorite or chlorine dioxide such that the dye substantially loses color within about an hour of blending and a second dye that maintains an effective color for at least 24 hours after blending.

12. The composition of claim 8 11 wherein the indicator stability comprises about one week.

13. The composition of claim 8 11 wherein the indicator stability comprises about two weeks.

14. The composition of claim 8 wherein the oil phase contains a drying oil.

15. A physically and chemically stable visually indicated mastitis treating composition in an acidulant part and a chlorite part, that can effectively reduce microbial populations, on contact with a teat surface and for an extended period, said composition comprising:

(a) (A) an aqueous acidulant part comprising:

(i) about 0.1 to 15 parts by weight of an organic or inorganic acid, or salts thereof, or mixtures thereof, the acid selected from the group consisting of a phosphoric acid, lactic acid, glycolic acid, a C_7-11 carboxylic acid, a C_6-12 alkyl benzene sulfonic acid, and mixtures thereof;

(ii) a rheology modifier comprising about 0.01 to 10 parts by weight of a pseudoplastic thickener;

(iii) a visual indicator system selected from the group consisting of:

(a) about 0.05-30 wt % of urea and about 0.001-10 wt % of a colorant, based on the weight of the composition; and

(b) comprising about 0.001-50 wt %, based on the weight of the composition, of a dispersed oil phase, wherein said oil phase contains about 0.001-50 wt % of an oil-soluble dye, based on the weight of said oil phase, and said oil phase is uniformly dispersed in a fine particle size in the composition that can retain color stability for at least 24 hours in the presence of chlorite or chlorine dioxide;

(iv) about 0.1 to 15 parts of an emollient;

(v) a major proportion of water; and

(b) (B) a chlorite part consisting essentially of comprising an alkali metal chlorite salt;

16. The composition of claim 15 wherein the alkali metal chlorite salt is sodium chlorite and the organic acid is lactic acid.

17. The composition of claim 15 additionally comprising about 0.01 to 8 parts of a polymeric film-forming agent.

18. The composition of claim 15 wherein the visual indicator contains about 0.01 to 2 wt % urea.

19. The composition of claim 15 wherein the visual indicator system comprises, in the composition, about 0.05 to 0.001 wt % of urea and about 0.001 to 10 wt % of a blue dye.

20. The composition of claim 19 wherein the visual indicator system contains FD&C Blue No. 1.

21. The composition of claim 15 wherein the composition further comprises a first indicator dye having color instability in the presence of chlorite or chlorine dioxide such that the dye substantially loses color within about an hour of blending and a second dye that maintains an effective color for at least 24 hours after blending.

22. The composition of claim 15 21 wherein the indicator stability comprises about one week.

23. The composition of claim 15 21 wherein the indicator stability comprises about two weeks.

24. The composition of claim 21 wherein the oil phase contains a drying oil.

25. The composition of claim 15 wherein the organic acid is a C_7-11 carboxylic acid, a C_6-12 alkyl benzene sulfonic acid or mixtures thereof.

26. The composition of claim 15 wherein the composition further comprises a mixture of about 0.05 to 2 parts by eight weight of a xanthan thickener and about 0.1 to 5 parts by weight of a film-forming agent selected from the group consisting of a polyvinyl alcohol, a polyvinyl acetate and mixtures thereof.

27. The composition of claim 15 wherein the pH of the composition comprising the acidulant part and the chlorine part, is about 2.5 to 4.5.

28. The composition of claim 15 wherein the pH of the composition comprising the acidulant part and the chlorite part is about 2.5 to 3.5.