JP6955054B2 - Aqueous antibacterial film-forming composition for nipple treatment by spray application - Google Patents

Description

The present invention relates to a sprayable aqueous antibacterial film-forming composition. In particular, the present invention provides compositions and formulations for suppressing mastitis in lactating animals.

The present invention relates to the field of topical antibacterial liquid compositions of the type that can be used to control or destroy pathogenic microorganisms. Antibacterial compositions are used to reduce the risk of infection and can be used to control pathogenic organisms on the surface of the skin, especially to control or prevent mastitis. Prevention of mastitis is a major goal of dairy farming. Contact with pathogenic microorganisms, usually bacteria, but sometimes yeast or fungi, with the bovine or sheep mammary glands can cause mastitis.

Large-scale cow milking is almost completely done in a milking machine. The milking machine mimics the milking of a cow by hand, by pulsing the vacuum, for example, attaching a teat cup connected to a vacuum pump and pulsing the vacuum from the breast and teat area to alternately inject and drain milk. By letting it pull milk from the cow's milk. The tendency is to minimize milking time by using a high vacuum that can cause irritation or damage to the teat and udder.

Following tissue damage caused by a milking machine, exposure of damaged tissue to certain microorganisms can cause an infection known as mastitis. Controlling mastitis is of great economic importance to dairy farmers, as contaminated milk from infected cows cannot be marketed. Infected bovine udders and teats can be treated with antibiotics that block the spread of the pathogen that causes mastitis. However, milk from such cows cannot be sold until the antibiotics are no longer contained in the milk, which is usually about 3-5 days after the last treatment.

To reduce mastitis, commercially available teat-dip solutions have been developed that are usually administered to the teat by dipping or spraying the teat before milking and after removing the milking cup. The teat dipping solution applied after milking can form a concentrated composition, membrane or barrier that remains on the teat until the next milking, usually after 8-12 hours. According to experts, prevention of mastitis by immersion of the teat in an antibacterial (biostatic or fungicide) solution is one of the most effective treatments that dairy farmers can follow.

The essential function of the teat immersion fluid is to prevent mastitis by killing or suppressing infectious microorganisms. The teat dipping solution preferably has a broad spectrum of antibacterial activity (ie, it can kill or inhibit the growth of microorganisms that cause widespread mastitis) and prevent irritation of the skin to which it is applied. Has softening properties.

Many teat dipping solutions or mastitis inhibitors are available to dairy workers and they have varying degrees of effectiveness. These products or agents commonly have an antibacterial agent that is the active ingredient (usually the main active ingredient) of the therapeutic solution. Commercially available teat immersion fluids can be divided into two main categories: non-barrier and barrier immersion fluids. The non-barrier papilla immersion solution is strictly antibacterial and is applied to kill microorganisms already present on the surface of the papillary duct or papilla skin. By design, the microbiological effects are substantially immediate and target infectious organisms that can migrate between animals in the pre-milking, during-milking and post-milking processes. The barrier dip solution may be antibacterial and is applied to form a protective film or coating that prevents microorganisms from coming into contact with the teat.

Papillary immersion liquids are iodophore, PVP-iodo (specific iodophore), hypochlorites, chlorine dioxide, chlorinated isocyanurate (chlorinated-S-triazen-trione), bromine, hydroxyquinone, ammonium chloride, chlorhexidine, Various antibacterial agents are used, including hexachlorophene, diaphene, cetylpyridinium chloride, and quaternary ammonium fungicides. Of the locally applied antibacterial agents (ie, agents applied directly to the skin) investigated to control bovine mammary inflammation, iodophore, quaternary ammonium compounds, and chlorine release agents (particularly hypochlorous acid). Sodium acid acid, and more recently chlorinated isocyanurate, is among dairy farmers, despite the fact that some of the disinfectants that release chlorine (eg, 4% NaOCl aqueous solution) can irritate the nipples of cows. Seems to be the most accepted in.

Rapid killing of bacteria is essential because long-term treatment with teat immersion (eg, 15 minutes or longer, or even 1 minute or longer) is usually not practical in controlling bovine mastitis. Sterilization tests of teat immersion formulations are most beneficial when performed for the purpose of measuring their short-term mortality.

Ref. WO 98/04136 discloses a teat immersion composition for protection from infections comprising membrane building elements and one or more active disinfectants. Membrane-forming agents include polyvinyl alcohol polymers or copolymers as film-forming agents and iodine and ether carboxylic acids in the form of polyvinylpyrrolidone iodine and / or chlorhexidine as active bactericides. This composition is particularly suitable for protecting the teats and udders of cows, ewes and goats after milking, forming a clearly mechanically resistant membrane.

Objectives of the Invention Some of the available teat dipping agents have serious drawbacks. The prior art film-forming papilla dip solution is not suitable for spraying on the skin. In addition, the use of existing film-forming compositions for spray coating results in nozzle failure, which renders the latest compositions for such spray coating useless. Existing spray products with microbiological effects do not create a protective barrier after treatment. We have found that excessive foam formation is a barrier property when using currently available barrier products for spraying when conducting studies to provide antibacterial film-forming compositions for spray application. It was found that the protection of the nipple and ducts was inadequate. The use of antifoaming agents to prevent the formation of foam on the papilla significantly improved the spray properties, but adversely affected the wettability and adhesion to the skin. Due to the increasing herd size and the continuous automation of the milking process, the demand for barrier products for spray application is increasing. Therefore, an object of the present invention is an antibacterial film-forming composition having excellent spraying properties and not causing nozzle breakage, which composition has good wettability and adhesion properties to the skin. Its antiseptic and antibacterial properties are comparable to existing products, i.e. the composition is suitable for use as a sprayable composition to prevent the development of mastitis or reduce the incidence of mastitis. , To provide an antibacterial film-forming composition.

The technical subject of the present invention is in an aqueous base,
(A) Membrane-forming polymer and
(B) Antibacterial agent and
It is solved by a sprayable aqueous antibacterial film-forming composition comprising (c) a hydrophobic modified urethane ethoxylated as a rheology modifier and (d) optionally an antifoaming agent.

In a preferred embodiment, the sprayable aqueous antibacterial film-forming composition according to the invention is contained in an aqueous base.
(A) 0.1 to 10.0% by weight of the film-forming polymer and
(B) 0.1 to 10.0% by weight of antibacterial agent and
(C) 0.001 to 3.0% by weight of hydrophobically modified urethane ethoxylated as a rheology modifier,
(D) optionally contains 0.001 to 3.0% by weight of antifoaming agent.

In a more preferred embodiment, the sprayable aqueous antibacterial film-forming composition according to the invention is contained in an aqueous base.
(A) 1.0 to 5.0% by weight of the film-forming polymer and
(B) 0.5 to 7.0% by weight of antibacterial agent and
(C) 0.01 to 1.0% by weight of hydrophobic modified urethane ethoxylated and
(D) optionally contains 0.005 to 1.0% by weight of antifoaming agent.
More preferably
(A) 2.0 to 4.5% by weight of film-forming polymer and
(B) 0.5 to 5.0% by weight of antibacterial agent and
(C) 0.05 to 0.5% by weight of hydrophobic modified urethane ethoxylated,
(D) optionally comprises 0.02 to 0.2% by weight of antifoaming agent.

In a more preferred embodiment, the sprayable aqueous antibacterial film-forming composition according to the invention is contained in an aqueous base.
(A) 0.1 to 10.0% by weight of polyvinyl alcohol as a film-forming polymer,
(B) 0.1 to 10.0% by weight of antibacterial agent and
(C) Containing 0.001 to 3.0% by weight of hydrophobically modified urethane ethoxylated as a rheology modifier and (d) optionally 0.001 to 3.0% by weight of defoaming agent.
More preferably
(A) 1.0 to 5.0% by weight of polyvinyl alcohol as a film-forming polymer,
(B) 0.5 to 7.0% by weight of antibacterial agent and
Containing (c) 0.01-1.0% by weight of hydrophobic modified urethane ethoxylated and (d) optionally 0.005 to 1.0% by weight of defoaming agent.
Even more preferably
(A) 2.0 to 4.5% by weight of polyvinyl alcohol as a film-forming polymer,
(B) 0.5 to 5.0% by weight of antibacterial agent and
(C) 0.05 to 0.5% by weight of hydrophobic modified urethane ethoxylated,
(D) optionally comprises 0.02 to 0.2% by weight of antifoaming agent.

The sprayable aqueous antibacterial film-forming composition according to the present invention is formulated and suitable for reducing the incidence of both infectious mastitis and environmental mastitis in dairy livestock herds.

We present antibacterial agents, particularly effective mastitis preventive or therapeutic agents, and rheological modifiers in the form of film-forming polymers, preferably polyvinyl alcohol, and hydrophobically modified urethane ethoxylated. Formulations of aqueous compositions containing thickeners and, optionally, antifoaming agents, are sprayable, have membrane-forming properties, antibacterial properties against typical infectious mastitis by pathogens and environmentally friendly animals. We have found that we provide a nipple treatment composition that can exhibit barrier properties that protect against rheological mastitis. This material can be formulated to form a film that can be easily removed prior to milking. The aqueous substances of the present invention can be used to treat dairy livestock herds. After milking, the substance is applied to the skin of the udder and nipple by spray application to form an antibacterial barrier coating to prevent or reduce infectious mastitis. Animals are then freed from the environment in which this substance can protect them from environmental pollution, but are resistant to environmental water such as rain, ponds and mud remaining in the animals during milking. When the animal returns to the milking site, the antibacterial barrier coating can be easily removed in minutes using aqueous washing. Milking can continue without delay, and after milking is complete, the animal can be treated again with an aqueous substance to form a new antibacterial barrier membrane.

In particular, the aqueous antibacterial membrane-forming compositions of the present invention are suitable for spraying onto the skin of the nipple and breast and create a protective barrier after treatment. Moreover, the composition does not cause nozzle breakage, even if it remains in the spray gun and nozzle for extended periods of time.

Surprisingly, when using hydrophobically modified urethane ethoxylated as a rheology modifier, we have good spraying properties, good wetting and adhesion properties to the skin, as well as spray coating. Later, they found that a film-forming composition capable of producing a film having good barrier properties could be provided.

Furthermore, we have surprisingly found that the combination of antifoaming agent and hydrophobic modified urethane ethoxylated as a rheology modifier has better spraying properties, wetting and adhesion properties to the skin. It has been found that a film-forming composition that also produces a film having a good barrier property after spray coating can be provided.

Furthermore, the compositions of the present invention can be sprayed in a temperature range of 0 ° C. to 40 ° C., preferably at least 5 ° C. to 30 ° C.

As mentioned above, in the compositions of the present invention, hydrophobically modified ethoxylated urethane, which is a polymer having polyethylene glycol constituent units and urethane constituent units, is used in which the polymer chains are endcapped with hydrophobic groups.

In a preferred embodiment of the invention, the antibacterial agent is I ₂ , iodophore, in particular polyvinylpyrrolidone iodo (PVP-iodo), straight or branched aliphatic C _{4 to} C ₁₀ carboxylic acids, especially capric acid and capric acid. octanoic acid, nonanoic acid, decanoic acid, lactic acid, salicylic acid, peroxycarboxylic acids, sulfo peroxycarboxylic _acids, C 1 -C ₄ alkanol, isopropyl alcohol, benzyl alcohol, bromo pole (2-bromo-2-nitro-1,3 Propanediol), sodium pyridinathione, chlorohexidine, chlorhexidine diacetate, chlorhexidine digluconate, quaternary ammonium compounds such as alkyldimethylbenzylammonium salts, dialkyldimethylammonium compounds and benzethonium, sulfonic acids, hypohalogenates, Alkali hypohalite, chlorine dioxide precursor, chlorine release agent (especially sodium hypochlorite and more recently chlorinated isocyanurate), hypochlorate, chlorine dioxide, chlorinated isocyanurate (chlorination-S- Triazen-trione), bromine, hydroxyquinone, ammonium chloride, hexachlorophene, diaphen, cetylpyridinium chloride, acid anionic (eg alkylarylsulfonic acid, arylsulfonic acid, alkylsulfonic acid, alkylarylsulfate, arylsulfate) , Alkyl sulphate, Alkyl aryl sulphate), orthophenylphenol, 2,4,4'-trichloro-2 "-hydroxydiphenyl ether, 4-chloro-3,5-dimethylphenol, polyhexa Methylbiguanide (CAS32289-58-0), guanidine salts such as polyhexamethyleneguanidine hydrochloride (CAS57028-96-3), polyhexamethyleneguanidine hydrophosphate (CAS89697-78-9), and poly [2- (2-ethoxy). ) -Eethoxyethyl] -guanidinium chloride (CAS374572-91-5), as well as mixtures thereof, are selected from the group. Typically, the compositions of the present invention comprise two or more antibacterial agents. ..

In a more preferred embodiment of the invention, the antimicrobial agent comprises an iodophore in the form of polyvinylpyrrolidone iodo (PVP-iodine). However, in other preferred embodiments, additional antibacterial agents can be included in addition to polyvinylpyrrolidone iodine.

More preferably, the composition of the present invention further comprises an alkylbenzene sulfonic acid used as an antibacterial agent.

In a more preferred embodiment, the composition of the present invention particularly comprises the following formula RO- (C ₃ H _6- O) _m- (C ₂ H _4- O) _n- CH _2- COOH, in the formula. R is an alkyl group having 4 to 10 carbon atoms, m is an integer from 0 to 8, n is an integer from 0 to 8, and at least one of m or n is not 0. It further comprises a polyoxypropylene alkyl ether carboxylic acid. Preferably, the composition of the present invention has the following formula RO- (C ₂ H _4- O) _n- CH _2- COOH, in which R is an alkyl group having 4 to 10 carbon atoms. n contains a polyoxyethylene alkyl ether carboxylic acid, which is an integer of 2-8.

In a more preferred embodiment of the sprayable aqueous antibacterial film-forming composition, polyvinyl alcohol and / or polysulfonic acid is present, preferably both polyvinyl alcohol and polysulfonic acid are in the composition as a film-forming agent (film-former). Exists in. In a particularly preferred embodiment, polyvinyl alcohol and / or polysulfonic acid and polyvinylpyrrolidone iodine are present, preferably polyvinyl alcohol and polysulfonic acid as a membrane-forming agent and polyvinylpyrrolidone iodine as an antibacterial agent are present in the composition.

In a particularly preferred embodiment of the invention, the sprayable aqueous antibacterial film-forming composition is contained in an aqueous base.
(A) 0.1 to 10.0% by weight of polyvinyl alcohol as a film-forming polymer,
(B) 0.5 to 10.0% by weight of polyvinylpyrrolidone iodine as an antibacterial agent,
(C) The rheology modifier contains 0.001 to 3.0% by weight of a hydrophobic modified urethane ethoxylated and (d) 0.001 to 3.0% by weight of an antifoaming agent.

In another particularly preferred embodiment of the invention, the sprayable aqueous antibacterial film-forming composition is contained in an aqueous base.
(A) 0.1 to 10.0% by weight of polyvinyl alcohol as a film-forming polymer,
(B) 0.5 to 10.0% by weight of polyvinylpyrrolidone iodine as an antibacterial agent,
(C) 0.001 to 3.0% by weight of hydrophobically modified urethane ethoxylated as a rheology modifier,
(D) 0.001 to 3.0% by weight of antifoaming agent and
(E) 0.05 to 5.0% by weight of polysulfonic acid and
f) The following formula RO- (C ₂ H _4- O) _n- CH _2- COOH, in the formula, R is an alkyl group having 4 to 10 carbon atoms, and n is an integer of 2 to 8. With 0.05-5.0 wt% polyoxyethylene alkyl ether carboxylic acid,
g) Optionally, under the condition that (b) is 5.0% by weight or less, 0.01 to 5.0% by weight of alkylbenzene sulfonic acid, chlorhexidine, orthophenylphenol, lactic acid, carboxylic acid, especially decanoic acid and Includes additional antibacterial agents, selected from the group consisting of mixtures thereof.

In yet another preferred embodiment, the defoaming agent is a silicone-based defoaming agent.

In a particularly preferred embodiment of the invention, the sprayable aqueous antibacterial film-forming composition is a Brookfield viscosity measured in cPs at a temperature of 25 ° C. with a Brookfield LV viscometer using spindle # 1 at 60 rpm. It has 1 to 50 cPs, preferably 1 to 20 cPs, more preferably 1 to 5 cPs.

The present invention also provides the use of the compositions of the present invention to suppress mastitis in lactating animals.

Furthermore, the present invention provides a method for controlling mastitis in lactating animals, which comprises spraying and applying the composition of the present invention to a teat.

Simply, a novel sprayable antibacterial film-forming composition is available in an aqueous base,
(A) With a film-forming polymer, preferably polyvinyl alcohol,
(B) Antibacterial agent and
(C) Hydrophobic modified urethane ethoxylated as a rheology modifier and (d) optionally an antifoaming agent, especially the occurrence of both infectious mastitis and environmental mastitis within dairy livestock herds. Formulated and appropriate to reduce the rate.

Aqueous film-forming compositions may include other useful substances in the formulation to improve the properties of the substance or to add new properties required by dairy farmers. This aqueous composition can be used to form a barrier membrane with antibacterial properties on the sensitive skin surface of the papillae of dairy animals. This barrier has a long life, is flexible, provides barrier properties and is antibacterial, but can be quickly removed using an aqueous wash with normal milking operations before milking. can. The material can be applied to dairy animals in a variety of ways and the material can be sprayed, brushed, dubbed or soaked in sensitive areas. The most preferable coating method is spray coating. The material dries quickly to form a barrier layer. The barrier layer is flexible and resistant to cracking. This layer contains antibacterial substances that kill microorganisms on the surface of the skin.
Such antibacterial activity is important, because the milking operation can cause inflammation and infection under certain circumstances in the scraped or affected skin caused by contact with the milking machine during the milking operation. This is because the microorganisms that cause mastitis can often spread.

The terms "teat dip" or "teat dipping" shall be broadly construed according to the terms used in the field of dairy farming. Although the composition is applied topically, it is not only intended for nipple immersion, but can of course be applied by other methods, such as, for example, a particularly preferred spray, and is still a recognized term for nipple immersion or nipple immersion composition. Included in the range of substances or drugs. The composition of the present invention is characterized by being suitable for spray coating.

As used herein, unless otherwise specified, the term "antibacterial" refers to a biological effect that can be, for example, an antibacterial, antifungal, antiviral, bacteriostatic, antiseptic or bactericidal effect. Describe.

As used herein, the term "killing" is meant to include actual killing as well as inhibition or mitigation of microbial growth.

The term "topical" refers to any composition that can be applied to the epidermis or other animal parts to which the composition can be applied.

The term "additive" shall mean any ingredient that is not an antibacterial agent or a pharmaceutical carrier. The pharmaceutical carrier is generally a bulk solvent used to dilute or solubilize the components of the composition, such as water.

All numbers herein are modified by the term "about", whether explicitly stated or not. The term "about" generally refers to a range of numbers that one of ordinary skill in the art would consider to be equivalent (ie, have the same function or result) to the listed values. In many cases, the term "about" can include a number rounded to the closest significant digit.

As used herein and in the appended claims, the singular forms "a", "an" and "the" include a plurality of referents unless their content explicitly dictates. Thus, for example, a reference to a composition containing a "compound" comprises a mixture of two or more compounds. As used herein and in the appended claims, the term "or" is commonly used in that sense, including "and / or", unless its content is expressly otherwise indicated.

Percentage by weight, percent by weight,% by weight,% by weight, etc. are synonyms for the concentration of a substance divided by the weight of the composition and multiplied by 100.

Unless otherwise stated, all weight percent provided herein reflect the effective weight percent of each component. The weight percent of the raw material provided by the manufacturer is easily determined from the information provided using the product data sheet provided by the manufacturer.

The composition is further selected from buffers, emollients, moisturizers, preservatives, surfactants or wetting agents, foaming agents, colorants, opaque agents, skin conditioning agents and any combination thereof. The above additives can be included.

Membrane-forming polymers Barriers and film-forming agents are components of the teat immersion composition that maintain contact with the teat during the milking cycle. Barriers and membrane-forming agents cover the papillary skin and, in some cases, the breast. The barrier agent can form a plug at the end of the open papillary duct. Typical barrier and film-forming agents used in accordance with the present invention include viscous creams or emollients (made with viscosity modifiers), membranes, polymers, latex and the like. In addition to contributing to surface wetting, some nonionic surfactants can help further enhance the barrier properties of the composition. Examples of such surfactants include, but are not limited to, polyoxyethylene-polyoxypropylene glycol (commercially available as Pluronic® F108). Preferred barrier forming agents are, for example, latex, arabinoxylan, glucomannan, guar gum, Johannitree gum, cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, carboxyethyl cellulose, carboxymethyl cellulose, starch, hydroxyethyl starch, Arabia. Rubber, curdran, pullulan, dextran, polysulfonic acid, polyacrylamide, high molecular weight polyacrylate, high molecular weight crosslinked polyacrylate, polyacrylic acid (carbomer), sodium alginate, sodium alginate crosslinked with calcium salt, xanthan gum, poly (vinyl) Alcohol) (PVA), and poly (N-vinylpyrrolidone) (PVP) may be included. A good example of a polysulfonic acid is polyacrylamide methylpropanesulfonic acid, which is commercially available as Rheocare ™ HSP-1180.

In a particularly preferred embodiment of the invention, in the sprayable aqueous antibacterial film-forming composition, polyvinyl alcohol is used as the film-forming polymer and optionally additional agents with film-forming properties are used in the composition. , Preferably polysulfonic acid and / or polyvinylpyrrolidone, which can be used to polymerize iodine and thus can itself be included in the composition as an antibacterial agent, ie polyvinylpyrrolidone iodo.

Polyvinyl alcohol (PVOH) is a polyhydroxydopolymer having a polymethylene skeleton having a pendant hydroxy group, and is a water-soluble synthetic resin. The resin is produced by hydrolysis of polyvinyl acetate. Polyvinyl alcohol is one of the limited numbers in the class of water-soluble polymeric substances. The resin is generally available as a dry solid and is available in granular or powdered form. The grade of polyvinyl alcohol includes a partially hydrolyzed version having a degree of hydrolysis of about 87-about 91% (percentage of acetate groups removed from polyvinyl alcohol leaving free hydroxyl groups). Moderate hydrolysis in polyvinyl alcohol produces polymers with removal of about 91-about 98% acetate groups. A fully hydrolyzed grade of polyvinyl alcohol has about 98 to about 99.5% of acetate groups removed. The polyvinyl alcohol product, called hyperhydrolyzed PVOH, has more than 99.5% of the removed acetate groups.

Polyvinyl alcohol is typically produced with a nominal number average molecular weight of about 4,000 to about 100,000. Generally, the molecular weight of a commercially available polyvinyl alcohol grade is 4% by weight of a% solution measured by centipoise (cP) at 20 ° C. (Hepler falling ball method). Variations in film flexibility, water sensitivity, solvation ease, viscosity, film strength, adhesive strength, and dispersion force can only be altered by adjusting the molecular weight or degree of hydrolysis. Solutions of polyvinyl alcohol and water can be made with large amounts of lower alcohol cosolvents and salt cosol and numerous other small or macromolecular additives or active ingredients. Polyvinyl alcohol is produced by first forming a vinyl acetate-containing copolymer such as polyvinyl acetate or ethylene vinyl acetate copolymer and removing the acetate groups by base hydrolysis. The production of polyvinyl acetate or vinyl acetate-containing copolymers can be carried out using conventional polymerization methods that control the ultimate molecular weight. Catalyst selection, temperature, solvent selection, and chain conversion can be adjusted by those skilled in the art of polymerization to control molecular weight and structural attributes of other polymers. The degree of hydrolysis is controlled by preventing the completion of the alkanol reaction. Polyvinyl alcohol is commercially available from DuPont and others. Preferred polyvinyl alcohols have a degree of hydrolysis of greater than 92.0%, preferably greater than 98.0%, most preferably greater than 98.5%. In the case of the sprayable aqueous film-forming antibacterial composition of the present invention, a fully hydrolyzed polyvinyl alcohol having a degree of hydrolysis of more than 98.5% is particularly preferably used. Most preferred polyvinyl alcohols have a degree of hydrolysis greater than 98.5%.

The compositions according to the invention can form a durable, continuous and uniform barrier membrane based on polyvinyl alcohol when applied to the skin. This composition is particularly useful as a barrier papilla dip used prophylactically against mastitis.

This composition is a persistent protective bactericidal barrier membrane that, for prophylactic treatment of dairy animal teats, exhibits persistence between milkings and is controllably reproducible to produce a continuous and uniform persistent barrier. Can be provided. This therapeutic process involves milking the animal, coating the teat with the composition after milking, drying the composition and forming a layer of persistent barrier membrane on the teat. The composition can be applied topically by painting, foaming, dipping or spraying, especially spraying by spraying. Moreover, the use of the composition is not limited to its use for mastitis, and the composition can be commonly used to treat or prevent infectious skin conditions.

A composition capable of forming a long-lasting, continuous and uniform barrier membrane is from about 0.1% to about 10.0% by weight, preferably about 1.0%, for use as a barrier forming agent. It contains from% to about 5.0% by weight, more preferably from about 2.0% to about 4.5% by weight of polyvinyl alcohol.

Rheology modifiers and tackifiers According to the present invention, in a sprayable antibacterial film-forming composition, hydrophobically modified urethane ethoxylated is included as a rheology modifier and tackifier. The hydrophobically modified urethane ethoxylated is a nonionic associative thickener and is obtained by reacting diisocyanate with a diol and a hydrophobic blocking component. In a polymer molecule, it can be distinguished among the following three moieties: i) hydrophobic end moieties, ii) some hydrophilic moieties, and iii) urethane groups. The polymer is a hydrophobic moiety, preferably a C _{2 to} C ₄₀ hydrocarbon, more preferably a straight or branched C _{2 to} C ₄₀ alkyl group, more preferably a straight or branched C _{8 to} C ₂₄ alkyl group. Then, the end cap is done. Possible preferred hydrophobic moieties are, for example, octyl group, dodecyl group, myristyl group, cetyl group, oleyl group, stearyl group, dodecylphenyl group, octylphenyl group and nonylphenyl group. A decisive factor in the viscosity-increasing effect is that each molecule contains at least two terminal hydrophobic moieties. The hydrophilic moiety used is a polyether or polyester. An example is a polyester of maleic acid and ethylene glycol, a polyether such as polyethylene glycol or a polyethylene glycol derivative. Polyesters are the preferred hydrophilic moiety, as these polymers provide the best chemical resistance during storage of their respective compositions and thus provide the best viscosity stability. The polymer chain is extended by polyisocyanate.

The hydrophobically modified ethoxylated urethane preferably used herein is a polymer having a polyethylene glycol constituent unit and a urethane constituent unit, and the polymer chain is endcapped with a hydrophobic group, preferably the following hydrocarbons. Types: C _{8 to} C ₄₀ linear alkyl, aryl substituted C _{2 to} C ₄₀ alkyl, C _{2 to} C ₄₀ alkyl substituted phenyl, C _{8 to} C ₄₀ branched alkyl, C _{8 to} C ₄₀ carbocyclic alkyl, and Particularly preferred are _{C 8 to} C ₈₀ complex esters selected from the group of straight or branched C _{8 to} C ₂₂ alkyl groups, C _{8 to} C ₂₂ aryl alkyl groups, and C _{8 to} C _{22 alkyl aryl groups.}

Preferred hydrophobic groups are linear or branched alkyl groups having about 8 to about 40 carbon atoms, such as capryl (C ₈ ) group, isooctyl (branched C ₈ ) group, nonyl (C ₉ ). Group, decyl (C ₁₀ ) group, undecyl (C ₁₁ ) group, lauryl (C ₁₂ ) group, tridecyl (C ₁₃ ) group, myristyl (C ₁₄ ) group, pentadecyl (C ₁₅ ) group, cetyl (C ₁₆ ) group , Cetearyl (C _16- C ₁₈ ) group, palmitoyl (C ₁₆ ) group, heptadecyl (C ₁₇ ) group, stearyl (C ₁₈ ) group, isostearyl (branch C ₁₈ ) group, nonadecil (C ₁₉ ) group, arachidyl (C ₂₀ ) group, heneikosyl (C ₂₁ ), behenyl group (C ₂₂ ), lignoceryl (C ₂₄ ) group, ceryl (C _{26 ) group, montanyl (C 28} ) group, melisyl (C ₃₀ ) group, laceryl (C 30) group ₃₂ ) Group, oleyl group, methyl ricinolate, preferably n-octyl group, n-dodecyl group, isotridecyl group, myricityl group, cetyl group, oleyl group, stearyl group, octylphenyl group, nonylphenyl group, dodecylphenyl group. be.

In other embodiments, the hydrophobic group is a linear and branched alkyl group having about 8 to about 40 carbon atoms derived from natural sources, including, but not limited to, hydrogenated peanut oil. Soybean oil and canola oil (all mainly C ₁₈ ), hydrogenated tallow (C _16- C ₁₈ ), etc., and hydrogenated C _10- C ₃₀ terpenol, for example hydrogenated geraniol (branched C ₁₀ ), hydrogenated farnesol (branched C 10). Examples thereof include alkyl groups derived from branch C ₁₅ ), hydrogenated phytol (branch C _{20), and the like.}

_{Other preferred hydrophobic groups are C 2 to} C ₄₀ alkyl substituted phenyl groups, including octylphenyl, nonylphenyl, decylphenyl, dodecylphenyl, hexadecylphenyl, octadecylphenyl, isooctylphenyl, sec-butylphenyl and the like.

More preferred hydrophobic groups are, but are not limited to, animal sources such as cholesterol, lanosterol, 7-dehydrocholesterol, plant sources such as phytosterols, stigmasterols, campesterols, and ergosterols, mycosterols and the like. C8 to C40 carbocyclic alkyl groups containing groups derived from sterols derived from various yeast sources. Other carbocyclic alkyl hydrophobic end groups useful in the present invention are derived from cyclooctyl, cyclododecyl, adamantyl, decahydronaphthyl, and natural carbocyclic materials such as pinene, retinol hydride, camphor, isobornyl alcohols. The groups of, but are not limited to these.

Typical aryl-substituted _C 2 _{-C 40} alkyl group, styryl (e.g., 2-phenylethyl), distyryl (e.g., 2,4-diphenyl-butyl), tristyryl (e.g., 2,4,6-triphenyl-hexyl ), 4-Phenylbutyl, 2-methyl-2-phenylethyl, tristyrylphenoxy and the like.

Non-limiting examples of suitable C _{8 to} C ₈₀ complex esters are hardened castor oil (mainly triglycerides of 12-hydroxystearic acid); 1,2-distearylglycerol, 1,2-dipalmitylglycerol, 1,2-Diacylglycerols such as 1,2-dimyristylglycerol; di-, tri-, or polyesters of sugars such as 3,4,6-tristearylglucose, 2,3-dilaurylfluctus, and sorbitan. Contains esters.

In another preferred embodiment, the hydrophobically modified urethane ethoxylated is a polymer having a polyethylene glycosyl constituent unit and a urethane constituent unit, the polymer chain is endcapped with a hydrophobic group, and the urethane constituent unit is m / p. -Tetramethylene xylylene diisocyanate, trimethylhexamethylene diisocyanate, 4 / 2,4'-diphenylmethane diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate ("HDI"), 1,10-decamethylene diisocyanate , 1,4-Cyclohexylene diisocyanate, 4,4'-methylenebis (isocyanatocyclohexane), 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate), m- and p-phenylene Diisocyanate, 2,6- and 2,4-tolylene diisocyanate (“TDI”), xylene diisocyanate, 4-chloro-1,3-phenylenediocyanate, 4,4′-biphenylenediocyanate, 4,4′-methylene diphenyl isocyanate It is formed by the use of a diisocyanate monomer in a polymerization reaction selected from the group consisting of (MDI), 1,5-naphthylene diisocyanate, 1,5-tetrahydronaphthylene diisocyanate and tetramethylximethylene diisocyanate.

In yet another preferred embodiment, the hydrophobic modified urethane ethoxylated is a polymer having a polyethylene glycol moiety and a urethane moiety, the polymer chain being endcapped at the hydrophobic moiety, and the polyethylene glycol building block used is 1500. It is 10000 daltons, preferably 3000-10000 daltons, more preferably 4500-7500 daltons, and even more preferably 6000-7500 daltons.

Suitable hydrophobic modified urethane ethoxylated (HEUR) are TAFIGEL® PUR (Munzing Chemie GmbH), Rheovis® PU, Rheovis® PE (BASF), Acrysol®, Acusol. It is commercially available under the trade names of (registered trademark) 880 and Acusol (registered trademark) 882 (Rohm & Haas).

Antibacterial agents Antibacterial agents are components of compositions that destroy microorganisms or prevent or inhibit their replication. In one aspect, only one antibacterial agent can be used in the compositions of the present invention. In another preferred embodiment, for example, a combination of antimicrobial agents of different chemical classes or structures may be used to achieve effective sterilization at lower concentrations of conventional antimicrobial agents.

The composition of the present invention contains at least one antibacterial agent. In a preferred embodiment of the invention, the antibacterial agent is in the form of I ₂ , iodophore, in particular polyvinylpyrrolidone iodo (PVP-iodo), straight or branched aliphatic C _{4 to} C ₁₀ carboxylic acids, especially capric acid and capric acid. , octanoic acid, nonanoic acid, decanoic acid; lactic, salicylic, peroxycarboxylic acids, sulfo peroxycarboxylic _acids, C 1 -C ₄ alkanol, isopropyl alcohol, benzyl alcohol, bronopol (2-bromo-2-nitro-1,3 Propanediol), sodium pyridinathione, chlorhexidine, chlorhexidine diacetate, chlorhexidine digluconic acid, quaternary ammonium compounds such as alkyldimethylbenzylammonium salts, dialkyldimethylammonium compounds, benzethonium, sulfonic acid, hypohalous acid, Alkaline hypohalite, chlorine dioxide precursors, chlorine release agents (especially sodium hypochlorite, and more recently chlorinated isocyanurate), hypochlorite, chlorine dioxide, chlorinated isocyanurate (chlorinated-S-triazen-trione) ), Bromine, hydroxyquinone, ammonium chloride, hexachlorophene, diaphen, cetylpyridinium chloride, acid anion system (eg alkylarylsulfonic acid, arylsulfonic acid, alkylsulfonic acid, alkylarylsulfate, arylsulfate, alkylsulfate, alkylarylsulfate) ), Orthophenylphenol, 2,4,4'-trichloro-2 "-hydroxydiphenyl ether, 4-chloro-3,5-dimethylphenol, a phenolic antibacterial agent, polyhexamethylbiguanide (CAS32289-58). -0), guanidine salts such as polyhexamethyleneguanidine hydrochloride (CAS57028-96-3), polyhexamethyleneguanidine hydrophosphate (89697-78-9), and poly [2- (2-ethoxy) -ethoxyethyl]. -Selected from the group consisting of guanidinium chloride (CAS374572-91-5) and mixtures thereof.

In another preferred embodiment, the aqueous antimicrobial film-forming composition according to the invention, as antimicrobial agents, particularly a iodophor in the form of polyvinyl pyrrolidone iodine (PVP-iodine), straight or branched chain aliphatic C ₄ -C _{10-carboxylic} acid, especially capric acid and caprylic acid, octanoic acid, nonanoic acid, decanoic acid; lactic, salicylic, peroxycarboxylic acids, sulfo peroxycarboxylic acids, C ₁ -C ₄ alkanol, isopropyl alcohol, benzyl alcohol, bronopol (2-bromo -2-nitro-1,3-propanediol), sodium pyridinathione, chlorhexidine, chlorhexidine diacetate, chlorhexidine digluconic acid, quaternary ammonium compounds such as alkyldimethylbenzylammonium salts, dialkyldimethylammonium compounds, benzethonium. , Sulfonic acid, hypohalic acid, alkaline hypohalite, chlorine dioxide precursors, chlorine release agents (especially sodium hypochlorite, and more recently chlorinated isocyanurate), hypochlorite, chlorine dioxide, chlorinated isocyanurate (Chlorinated-S-triazen-trione), bromine, hydroxyquinone, ammonium chloride, hexachlorophene, diaphen, cetylpyridinium chloride, acid anion system (eg alkylaryl sulfonic acid, aryl sulfonic acid, alkyl sulfonic acid, alkylaryl sulphate, Arylsulfate, alkylsulfate, alkylarylsulfate), orthophenylphenol, 2,4,4'-trichloro-2 "-hydroxydiphenyl ether, 4-chloro-3,5-dimethylphenol, a phenolic antibacterial agent that can be selected. , Polyhexamethylbiguanide (CAS32289-58-0), guanidine salts such as polyhexamethyleneguanidine hydrochloride (CAS57028-96-3), polyhexamethyleneguanidine hydrophosphate (89697-78-9), and poly [2- Includes (2-ethoxy) -ethoxyethyl] -guanidinium chloride (CAS374572-91-5), and at least one additional antibacterial agent, including one selected from the group consisting of mixtures thereof.

As mentioned above, the preferred antibacterial agent is iodophore, and a particularly preferred iodine compound is provided in the form of polyvinylpyrrolidone iodine (PVP-iodo).

Iodine Compounds The iodine compounds of the present invention are selected to provide some of the antibacterial activity of the compositions of the present invention and provide antibacterial activity to disinfect or sanitize. Iodine compounds suitable for the compositions of the present invention are known, for example, US Pat. Nos. 4,271,149, 5,310,549, 5,368,868 and 5,503,838. The entire disclosure thereof is incorporated herein by reference.

The most preferred antibacterial agents used in the composition are nominally available on average from about 0.05% to 2.0% by weight, more preferably from about 0.1% to 1.0% by weight (titration). Possible) Iodine form with iodine levels. In a preferred embodiment, the iodine compound can be present in the form of iodophore. That is, the iodine compound exists as a complex with one or more suitable surfactants, or other suitable complex compounds such as, for example, polyvinylpyrrolidone (PVP). Typically, iodophore is present in the compositions of the invention and can provide about 500 ppm to 6000 ppm, preferably about 1000 ppm to 3000 ppm of free iodine in the working composition. Iodofores are known and are described, for example, in US Pat. Nos. 5,618,841 and 5,310,549. Suitable surfactants suitable for preparing an iodophore having one or more surfactants are further discussed below.

In one embodiment, the invention comprises a complex of iodine or triiodide with a carrier capable of producing elemental iodine under conditions of use, such as _{iodine (I 2), iodofore, i.e. povidone-iodine, and.} An antibacterial agent selected from the group consisting of these combinations, wherein the antibacterial agent is available in an amount of about 0.05% to 2.0% by weight, preferably 0.1% to 1.0% by weight. Provided is a disinfectant composition comprising an antibacterial agent, which is present in an amount sufficient to provide a high iodine concentration.

The complexed iodine of the present invention is preferably prepared by the use of iodine and a complexing agent selected from the group consisting of ethoxylated surfactants, celluloses, cellulose derivatives and polyvinylpyrrolidone components. Alkenylated (usually ethoxylated) surfactants include alkylphenol ethoxylates, ethoxylated fatty acids, alcohol ethoxylates, alcohol alkoxylates, polysorbates (sorbitol ethoxylated) and ethylene oxide-propylene oxide copolymers (poloxamers). Not limited to. Preferred poloxamer surfactants are described in US Pat. No. 5,368,868, the entire disclosure of which is incorporated herein by reference. These surfactants contain a polyoxypropylene moiety having an average molecular weight of more than 2600, more preferably about 2600-4000. The polyoxyethylene content typically ranges from about 30.0 to 75.0% by weight, more preferably from about 40.0 to 70.0% by weight. Generally, the complexing agent is used at a level of about 0.4 to 10.0% by weight, more preferably about 0.4 to 4.0% by weight.

In a particularly preferred embodiment, the antibacterial agent iodine is provided in the form of a complex with polyvinylpyrrolidone. The polyvinylpyrrolidone component is preferably selected from the group of K-30 to K-90 povidone. The PVP acts primarily as an iodine complexing agent and thus as an antibacterial agent, but may serve as a single film-forming agent or other film-forming agent or film-forming polymer. The level of use is typically about 0.5-5.0% by weight of PVP, more preferably about 1.0-2.5% by weight. When iodine is used as an antibacterial agent, PVP can perform two functions: a film-forming agent and an iodine complex.

Anionic Surfactants The anionic surfactants useful in the present invention have maximum bactericidal activity and / or biostability against organisms that cause mastitis at pH ranges from 2.0 to 5.0. Therefore, these surfactants are generally present in the composition in the range of 0.05% by weight to 5.0% by weight, preferably 0.1% by weight to 2.0% by weight.

Preferred anionic surfactants are linear alkylbenzene sulfonic acid, linear alkylbenzene sulfonate, alkyl α-sulfomethyl ester, α-olefin sulfonate, alcohol ether sulfate, alkyl sulfate, alkyl sulfosuccinate, dialkyl. Sulfosuccinate, and its alkali metals, alkaline earth metals, amines and ammonium salts. Preferred specific examples are linear C _{10 to} C ₁₆ alkylbenzene sulfonic acid, linear C _{10 to} C ₁₆ alkylbenzene sulfonate or its alkali metal, alkaline earth metal, amine and ammonium salt, for example sodium dodecylbenzene sulfonic acid, C. _{14 to} C ₁₆ Sodium α-olefin sulfonate, sodium methyl α-sulfomethyl ester, disodium methyl α-sulfo fatty acid, and the like can be mentioned.

Linear alkylbenzene sulfonic acid salt, or linear alkylbenzene sulfonic acid (hereinafter collectively referred to as "LAS"), is a moderately effective fungicide, especially a weakly acidic medium. However, linear alkylbenzene sulfonic acid is generally more active than Gram-negative bacteria, especially at "skin" pH, i.e., against Gram-positive bacteria such as Staphylococcus aureus above 5.0. The sources of these microorganisms can be water, soil, improperly cleaned tools, fertilizers, infected cattle, human hands and the like. Most Gram-positive bacteria, such as Staphylococcus aureus, occur in mammals (including humans), but many Gram-negative bacteria are present in the feces of animals as well as humans. Linear alkylbenzene sulfonate is a useful type of anionic detergent that appears to provide activity against both Gram-positive (eg, Staphylococcus aureus) and Gram-negative (eg, Pseudomonas aeruginosa) bacteria. be. LAS is not required to provide acceptable biocidal results for the compositions of the invention, but improves the antibacterial effect of the compositions of the invention. The linear alkyl chains of LAS should not be short enough to reduce antibacterial activity, but not long enough to cause incompatibility with water. Therefore, the alkyl chain should preferably have a length of 9-18, preferably 10-16, more preferably 10-13 carbon atoms. In a preferred embodiment, dodecylbenzyl sulfonic acid is used.

In a preferred embodiment of the present invention, the alkylbenzene sulfonic acid is C _9-18 alkylbenzene sulfonic acid, more preferably C _10-16 alkylbenzene sulfonic acid, more preferably C _10-13 alkylbenzene sulfonic acid. More preferably, the alkylbenzene sulfonic acid is a linear alkylbenzene sulfonic acid, more preferably a linear C- _10-13 alkylbenzene sulfonic acid. In certain preferred embodiments, the alkylbenzene sulfonic acid is a linear alkylbenzene sulfonic acid having an average number of carbon atoms in the alkyl group of 10-13. In another particularly preferred embodiment, the alkylbenzene sulfonic acid is a linear alkylbenzene sulfonic acid in which at least 95.0% by weight of the alkylbenzene sulfonic acid has 10 to 13 carbon atoms in the alkyl group. Preferred alkylbenzene sulfonic acids are commercially available as MARLON® AS3 (Sasol Germany GmbH, Marl, Germany). Preferably, the composition of the present invention is 0.05% by weight to 5.0% by weight, more preferably 0.1% by weight to 2.0% by weight, particularly preferably 0, based on the total weight of the composition. .1% by weight to 0.5% by weight alkylbenzene sulfonic acid, preferably C _9-18 alkylbenzene sulfonic acid, more preferably C _10-16 alkylbenzene sulfonic acid, more preferably C _10-13 alkylbenzene sulfonic acid, still more preferably. Linear alkylbenzene sulfonic acid, more preferably linear C _{10 to 13} alkylbenzene sulfonic acid, with an average number of carbon atoms in the alkyl group of 10 to 13, preferably 0.05 to 5.0% by weight, even more preferably. Contains 0.1 to 2.0% by weight, and particularly preferably 0.1% to 0.5% by weight of C _{10 to} C ₁₃ alkylbenzene sulfonic acid.

Percarboxylic Acid The sprayable aqueous antibacterial film-forming composition according to the invention also comprises a peroxy acid, also called a peroxycarboxylic acid, which is present as a chemical equilibrium consisting of a peracid, a corresponding carboxylic acid, hydrogen peroxide and water as an antibacterial agent. Can include.

Generally, when a peroxycarboxylic acid is prepared according to the present invention, a monocarboxylic acid such as acetic acid is combined with an oxidizing agent such as hydrogen peroxide. The result of this combination is a reaction that produces peroxycarboxylic acids such as peroxyacetic acid and water. The reaction follows an equilibrium according to the following equation.
H ₂ O ₂ + RCOOH ======= RCOOOH + H ₂ O
In the formula, K _eq is 2.0.

The importance of equilibrium is due to the simultaneous presence of hydrogen peroxide, carboxylic acid and peroxycarboxylic acid in the same composition. This combination provides enhanced hygiene compared to carboxylic acid alone.

The first component of the equilibrium mixture comprises one or more carboxylic acids. Carboxylic acids serve as precursors of the reaction product, peroxycarboxylic acids, while providing a source of acidity and antibacterial potency. Acidity helps stabilize and otherwise maintain the equilibrium concentration of peroxycarboxylic acid.

Another main component of the antibacterial composition of the present invention is an oxidized carboxylic acid. This oxidized or peroxycarboxylic acid provides enhanced antibacterial efficacy when combined with hydrogen peroxide and monocarboxylic acids in the equilibrium reaction mixture. In general, any number of peroxycarboxylic acids are useful according to the methods of the invention.

Peracids are present in sufficient amounts to exhibit antibacterial activity. Various peroxycarboxylic acids can be used in the compositions of the present invention. According to a preferred embodiment of the invention, suitable peroxycarboxylic acids include the ester peroxycarboxylic acids, alkyl ester peroxycarboxylic acids, and / or combinations of several different peroxycarboxylic acids described herein. Is done.

The aqueous antibacterial composition according to the present invention contains at least one percarboxylic acid. In some embodiments, the composition of the invention comprises at least two or more percarboxylic acids.

In a preferred embodiment of the invention, the composition is
a) Corresponding to the general formula (I) R ^1- O ₂ C- (CH ₂ ) _p- CO ₃ H, in the formula, R ¹ is an alkyl group containing a hydrogen atom or 1 to 4 carbon atoms. p is an integer of 1 to 4, peracid or a salt thereof,
b) Phthalimide percarboxylic acid (II) or a salt thereof, wherein the percarboxylic acid contains 1 to 18 carbon atoms.
c) Formula ^(III) corresponds to ^{R 2} -CO ₃ H, R 2 is 1 to 22 carbon atoms, peracetic preferably an alkyl or alkenyl group containing 1 to 18 carbon atoms, selected from compounds, Contains acid.

In a still more preferred embodiment of the composition,
a) Corresponds to the general formula (I) R _1- O ₂ C- (CH ₂ ) _p- CO ₃ H, in which R ¹ is a hydrogen atom or a methyl group and p is an integer of 1-4. , Peracid or its salt,
b) Phthalimide percarboxylic acid (II) or a salt thereof, wherein the percarboxylic acid contains 1 to 8 carbon atoms.
c) Corresponding to formula (III) R ^2- CO ₃ H, in the formula R ² contains a peracid selected from a compound, which is an alkyl or alkenyl group containing 1-12 carbon atoms. ..

More preferably, the peracids are peracetic acid, perpropionic acid, peroctanoic acid, phthalimide perhexanoic acid, phthalimide peroctanoic acid, persuccinic acid, persuccinic acid monomethyl ester, perglutaric acid, perglutaric acid monomethyl ester, hyper. It is selected from adipic acid, perazipic acid monomethyl ester, persuccinic acid and persuccinic acid monomethyl ester.

In yet another preferred embodiment, the carboxylic acid for use with the compositions of the present invention is to provide a corresponding peroxycarboxylic acids include C ₁ -C ₂₂ carboxylic acids. In one embodiment, any suitable C ₁ -C ₂₂ carboxylic acids can be used in the compositions of the present invention. In some _embodiments, C 1 _{-C 22} carboxylic acid _is a C 2 _{-C 20} carboxylic acid. In some _embodiments, C 1 _{-C 22} carboxylic _{acids, C 1, C 2, C} 3, C 4, C 5, C 6, C 7, C 8, C 9, C 10, C 11, C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , C ₁₈ , C ₁₉ , C ₂₀ , C ₂₁ , or C ₂₂ carboxylic acid. More preferred carboxylic acids for use with the compositions of the invention are C _1- C ₁₈ carboxylic acids, more preferably C _1- C ₁₂ carboxylic acids. In particular, the carboxylic acid for use with the composition of the present invention _{may be C 5 to} C ₁₂ carboxylic acid. In a particularly preferred embodiment, the carboxylic acids for use with the compositions of the invention are C _1- C ₄ carboxylic acids. Examples of suitable carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, and their branched isomers. , Lactic acid, maleic acid, ascorbic acid, citric acid, hydroxyacetic acid, neopentanoic acid, neoheptanic acid. Includes, but is not limited to, neodecanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, and mixtures thereof. A particularly preferred carboxylic acid is acetic acid. The composition can utilize a combination of several different carboxylic acids. In some preferred embodiments, the composition comprises one or more C _{1 to} C ₄ carboxylic acids and one or more C _{5 to} C ₁₂ carboxylic acids. In a further preferred _embodiment, C 1 -C ₄ carboxylic acid is acetic _acid, C 5 _{-C 12} acid is octanoic acid.

Corresponding to the carboxylic acid, the aqueous antibacterial composition of the present invention comprises at least one peroxycarboxylic acid. In a preferred embodiment, peroxycarboxylic acids for use with the compositions of the present invention include C ₁ -C ₂₂ peroxycarboxylic acid. In one embodiment, any suitable C ₁ -C ₂₂ percarboxylic acid can be used in the compositions of the present invention. In some _embodiments, C 1 _{-C 22} percarboxylic acid _is a C 2 _{-C 20} percarboxylic acid. In other _embodiments, C 1 _{-C 22} percarboxylic _{acid, C 1, C 2, C} 3, C 4, C 5, C 6, C 7, C 8, C 9, C 10, C 11, C 12 , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , C ₁₈ , C ₁₉ , C ₂₀ , C ₂₁ and C ₂₂ percarboxylic acids. Further preferred peroxycarboxylic acids for use with the compositions of the present _invention, the C 1 _{-C 18,} more preferably peroxycarboxylic acid _C 1 _{-C 12.} In particular, the peroxycarboxylic acid for use with the composition of the present invention _{may be C 5 to} C ₁₂ peroxycarboxylic acid. In a particularly preferred embodiment, the carboxylic acids for use with the compositions of the present invention are C ₁ -C ₄ peroxycarboxylic acid. Examples of peroxycarboxylic acids useful in the compositions of the present invention include peroxygiic acid, peroxyacetic acid, peroxypropionic acid, peroxybutyric acid, peroxypentanoic acid, peroxyhexanoic acid, peroxyheptanic acid, peroxyoctanoic acid, peroxynonanoic acid, peroxy. Decanoic acid, peroxyundecanoic acid, peroxidedecanoic acid, and their branched isomers peracid, peroxylactic acid, peroxymaleic acid, peroxyascorbic acid, peroxycitrate, peroxyhydroxyacetic acid, peroxyneopentanoic acid, peroxyneoheptan Includes acids, peroxyneodecanic acid, peroxyshuic acid, peroxymalonic acid, peroxysuccinic acid, peroxyglutaric acid, peroxyadipic acid, peroxypimelic acid, peroxysveric acid, peroxysevacinic acid, and mixtures thereof. A particularly preferred peroxycarboxylic acid is peroxyacetic acid. The composition can utilize a combination of several different peroxycarboxylic acids. In some preferred embodiments, the composition comprises one or more C _{1 to} C ₄ peroxycarboxylic acids and one or more C _{5 to} C ₁₂ peroxycarboxylic acids. In a further preferred _embodiment, C 1 -C ₄ peroxycarboxylic acid is peroxyacetic _acid, C 5 _{-C 12} acid is peroxyoctanoic acid.

In a preferred embodiment, the composition comprises peroxyacetic acid. The peroxyacetic acid (or peracetic acid) acid is a peroxycarboxylic acid having the _{formula: CH 3 COOOH.} In general, peroxyacetic acid is a liquid with a higher concentration and a pungent odor and is freely soluble in water, alcohols, ethers, and sulfuric acid. Peroxyacetic acid can be prepared by a number of methods known to those of skill in the art, including preparation from acetaldehyde and oxygen in the presence of cobalt acetate. A solution of peroxycarboxylic acid can be obtained by mixing the corresponding carboxylic acid with hydrogen peroxide. A solution of peroxyacetic acid can be obtained by mixing acetic acid and hydrogen peroxide. A 50% solution of peroxyacetic acid can be obtained by mixing acetic anhydride, hydrogen peroxide and sulfuric acid.

In a preferred embodiment, the composition comprises peroxyoctanoic acid, peroxynonanoic acid, or peroxyheptanic acid. In a more preferred embodiment, the composition comprises peroxyoctanoic acid. Peroxyoctanoic acid (or peroctanoic acid) is, for example, a peroxycarboxylic acid having the formula _{n-peroxyoctanoic acid: CH 3} (CH ₂ ) _{6 COOOH.} Peroxyoctanoic acid can be an acid with a linear alkyl moiety, an acid with a branched alkyl moiety, or a mixture thereof. Peroxyoctanoic acid can be prepared by a number of methods known to those of skill in the art. A solution of peroxyoctanoic acid can be obtained by mixing octanoic acid with hydrogen peroxide and a hydrotrope, solvent or carrier.

Useful peroxycarboxylic acids also include the ester peroxycarboxylic acids described herein and the compositions of the invention comprising ester peroxycarboxylic acids thereof. A peroxy form of a carboxylic acid having two or more carboxylate moieties can have one or more carboxyl moieties that are present as peroxycarboxyl moieties. These peroxycarboxylic acids have been found to provide good antibacterial activity as well as good stability in aqueous mixtures. In a preferred embodiment, the compositions of the invention utilize a combination of several different peroxycarboxylic acids. Examples of suitable alkyl ester carboxylic acids include monomethyloxalic acid, monomethylmalonic acid, monomethylsuccinic acid, monomethylglutaric acid, monomethyladiponic acid, monomethylpimelic acid, monomethylsveric acid and monomethylsevacinic acid; Monoethylmalonic acid, monoethylsuccinic acid, monoethylglutaric acid, monoethyladiponic acid, monoethylpimelic acid, monoethylsveric acid and monoethylsevacinic acid; propyl may be n-propyl or isopropyl, monopropyl Shuic acid, monopropylmalonic acid, monopropylsuccinic acid, monopropylglutaric acid, monopropyladipic acid, monopropylpimelic acid, monopropylsveric acid and monopropylsevacinic acid; butyl is n-butyl, isobutyl or tertiary butyl Included are monobutyloxalic acid, monobutylmalonic acid, monobutylsuccinic acid, monobutylglutaric acid, monobutyladipic acid, monobutylpimelic acid, monobutylsveric acid and monobutylsevacinic acid.

In a more preferred embodiment, the aqueous antibacterial composition comprises 0.01% to 10.0% by weight of peracid. More preferably, the composition contains 0.01-18.0% by weight of hydrogen peroxide. Even more preferably, the composition comprises at least a mixture of hydrogen peroxide, a peracid and the corresponding carboxylic acid. Most preferably, the composition comprises at least hydrogen peroxide, peroxyacetic acid and acetic acid. In a more preferred embodiment, the aqueous antibacterial composition of the present invention comprises 0.01% to 10.0% by weight of peroxyacetic acid. Peracid, also called peroxycarboxylic acid, exists as a chemical equilibrium consisting of peracid, the corresponding carboxylic acid, hydrogen peroxide and water, the amount of which is "0.01% by weight to 10.0% by weight of peracid". Alternatively, "0.01% by weight to 10.0% by weight of peroxyacetic acid" means "0.01% by weight to 10.0% by weight of peracid and the corresponding 0.000% by weight to 20.0% by weight of peroxyacetic acid". It means "carboxylic acid" and "0.01% by weight to 10.0% by weight of peroxyacetic acid and 0.000% by weight to 20.0% by weight of acetic acid", respectively.

As will be appreciated by those skilled in the art, peroxycarboxylic acids are not as stable as carboxylic acids, but their stability generally increases with increasing molecular weight. Pyrolysis of these acids can generally proceed by free radical and non-radical pathways, photolysis or radical induction decomposition, or the action of metal ions or complexes. Percarboxylic acids can be produced from the direct acid-catalyzed equilibrium action of hydrogen hydrogen and carboxylic acids, the automatic oxidation of aldehydes, or the acidifieds, hydrides or carboxylic acid anhydrides and hydrogen or hydrogen peroxide. Can be done.

Production of Peroxycarboxylic Acids Exemplary methods and equipment for producing peroxycarboxylic acids are US Pat. No. 7,547,421 and US Pat. No. 8,017,082 (invention title "Apparatus and Method for Making"). a PeroxycarboxyAcid ”), which is expressly incorporated herein by reference in its entirety. These and other known methods and devices for producing certain peroxycarboxylic acids used in accordance with the present invention are included within the scope of the present invention.

In some embodiments, under ambient conditions, the reaction to produce a peroxycarboxylic acid composition may take a week or more to reach the desired concentration of peroxycarboxylic acid in equilibrium. In other embodiments, the conditions can be modified to reach the maximum amount of peroxycarboxylic acid composition within about 60 minutes or hours. One of ordinary skill in the art will recognize various changes to the conditions of the peroxycarboxylic acid reaction to obtain the desired concentration within a particular time period.

Sulfoperoxycarboxylic Acid The term "sulfoperoxycarboxylic acid" or "sulfonated peroxycarboxylic acid" as used herein refers to the peroxycarboxylic acid form of the sulfonated carboxylic acid. The sulfoperoxycarboxylic acid can be used alone as an antibacterial agent or in combination with other antibacterial agents.

Sulfonated peroxycarboxylic acids, sulfonated peroxycarboxylic acids and / or derivatives thereof that can be used as antibacterial agents according to the present invention are described in International Application WO2009 / 118714 A2 and are fully incorporated by reference.

In a preferred embodiment of the invention, the following formula: R ^3- CH (SO _3- X ⁺ ) R ^4- COOOH, where R ³ is a hydrogen atom or a substituted or unsubstituted alkyl group and R ⁴ is substituted. Alternatively, it is an unsubstituted alkyl group, and X is a sulfoperoxycarboxylic acid, or a salt or ester thereof, which is a hydrogen atom, a cationic group or an ester-forming moiety.

In some embodiments, R ³ is a substituted or unsubstituted _Cm alkyl group, X is a hydrogen atom, a cationic group, or an ester forming moiety, and R ⁴ is a substituted or unsubstituted C _n. It is an alkyl group, m = 1-10, n = 1-10, m + n is less than 18, or is a salt, ester or mixture thereof.

In some embodiments, R ³ is a hydrogen atom. In another embodiment, R ³ is a substituted or unsubstituted alkyl group. In some embodiments, R ³ is a substituted or unsubstituted alkyl group does not contain a cyclic alkyl group. In some embodiments, R ³ is a substituted alkyl group. In some embodiments, R ³ is an unsubstituted C _1- C ₉ alkyl group. In some embodiments, R ³ is an unsubstituted C ₇ or C ₈ alkyl. In other embodiments, R ³ is a substituted C _{8 to} C ₁₀ alkyl group. In some embodiments, R ³ _{is a substituted C 8 to} C ₁₀ alkyl group substituted with at least one or at least two hydroxyl groups. In yet another embodiment, R ³ is a substituted C _1- C ₉ alkyl group. In some embodiments, R ³ is a substituted C _1- C ₉ substituted alkyl group substituted with at least one SO _{3 H group.}

In other embodiments, R ³ is a C _9- C ₁₀ substituted alkyl group. In some embodiments, R ³ _{is a substituted C 9-} C ₁₀ alkyl group in which at least two of the carbons on the carbon backbone form a heterocyclic group. In some embodiments, the heterocyclic group is an epoxide group.

In some embodiments, R ⁴ is a substituted C _1- C ₁₀ alkyl group. In some embodiments, R ⁴ is a substituted C _8- C ₁₀ alkyl. In some embodiments, ^{R 4} is unsubstituted _C 6 -C ₉ alkyl. In other embodiments, R ⁴ _{is a C 8 to} C ₁₀ alkyl group substituted with at least one hydroxyl group. In some embodiments, R ⁴ is C ₁₀ alkyl group substituted with at least two hydroxyl groups. In another embodiment, ^{R 4} is _{C 8} alkyl group substituted with at least one SO ₃ H group. In some embodiments, R ⁴ is a C ₉ groups at least two substituted to form a heterocyclic group of the carbon on the carbon backbone. In some embodiments, the heterocyclic group is an epoxide group.

In some embodiments, R ³ is a C _{8 to} C ₉ substituted or unsubstituted alkyl and R ⁴ is a C _{7 to} C ₈ substituted or unsubstituted alkyl.

In some embodiments, the compounds of the invention are
10-Hydroxy-9-sulfooctadecane peroxo acid,
9,10-Dihydroxy-8-sulfooctadecane peroxo acid,
9-Sulfooctadecane peroxo acid,
11-Sulfondecane peroxo acid,
10,11-disulfoundecane peroxo acid,
8- (3-octyloxylan-2-yl) -8-sulfooctaneberoxo acid,
9,10-Dihydroxy-11-sulfooctadecane peroxo acid,
9- (1-sulfoheptyloxylan-2-yl) -9-nonane peroxo acid,
9-Hydroxy-10-sulfooctadecane peroxo acid,
10-Sulfooctadecane peroxo acid,
9,10-Disulfooctadecane peroxo acid,
10-Sulfone undecane peroxo acid,
9- (3-octyloxylan-2-yl) -9-sulfononane peroxo acid,
10,11-Dihydroxy-9-sulfooctadecane peroxo acid,
It is selected from the group consisting of 8,9-dihydroxy-10-sulfooctadecane peroxo acid.

In some embodiments, the antibacterial agent for the preparation of the peroxycarboxyl fatty acid can be a sulfonated fatty acid. Sulfonized fatty acids suitable for use as antibacterial agents include 11-sulfon undecanoic acid, 10,11-disulfoundecanoic acid, sulfonated oleic acid, sulfonated linoleic acid, sulfonated palmitic acid and sulfonated stearic acid. However, it is not limited to these.

Sulfoperoxy acids can be formed using a variety of reaction mechanisms. For example, in some embodiments, this peracid is formed by the direct acid-catalyzed equilibrium between hydrogen peroxide and the substance.

Polyoxyalkylene Ether Carboxylic Acid / Alkyl Ether Carboxylic Acid A further compound that can be used as a surfactant in the compositions of the present invention is polyoxyalkylene ether carboxylic acid. Therefore, in a preferred embodiment of the composition according to the invention, the polyoxyalkylene ether carboxylic acid is also referred to as an alkyl ether carboxylic acid and particularly includes polyoxypropylene or polyoxyethylene ether carboxylic acid. Polyoxypropylene or polyoxyethylene ether carboxylic acids, especially polyoxyethylene ether carboxylic acids, first propoxylate or ethoxylate the corresponding alkanol with substituent R, respectively, and react the propoxylate and ethoxylate with chloroacetic acid, respectively. Can be prepared by Because the propoxylation / ethoxylation step results in a mixture of propoxylation / ethoxylation products with varying degrees of propoxylation / ethoxylation rather than a pure material with a specified number of propoxy / ethoxylation groups. , Ethercarboxylic acids are generally the corresponding mixture products. In addition, products with propoxy and ethoxy groups can be prepared. An alkyl ether carboxylic acid having an alkyl group R having 4 to 8 carbon atoms is preferably used. The film-forming composition of the present invention preferably contains 0.5 to 2.0% by weight of a polyoxyalkylene ether carboxylic acid. Preferably, a mixture of polyoxyalkylene ether carboxylic acids is included in the compositions of the invention, in particular Caprilueto-9 carboxylic acid (RO- (C ₂ H _4- O) _n- CH _2- COOH, R = in the formula. C ₈ alkyl group, n is about 5, CAS number 53563-70-5) and butet-2 carboxylic acid (RO- (C ₂ H _4- O) _n- CH _2- COOH, R = C ₄ alkyl group , N is about 2, and CAS number 75427-76-8) is commercially available from KAO Chemicals as Akypto® LF6.

In a preferred embodiment, the composition particularly comprises the following formula RO- (C ₃ H _6- O) _m- (C ₂ H _4- O) _n- CH _2- COOH, in which R is An alkyl group having 4 to 10 carbon atoms, m is an integer of 0-8, n is an integer of 0-8, and at least one of m or n is non-zero, polyoxy. Contains propylene alkyl ether carboxylic acid.

A more preferable composition has the following formula RO- (C ₂ H _4- O) _n- CH _2- COOH, in which R is an alkyl group having 4 to 10 carbon atoms. n contains a polyoxyethylene alkyl ether carboxylic acid, which is an integer of 2-8.

Antifoaming Agents In general, antifoaming agents or antifoaming agents that can be used in accordance with the present invention include silica and silicones, fatty acids or esters, alcohols, sulfates or sulfonates, amines or amides, fluorochlorocarbonates. Halogen compounds such as hydrogen, vegetable oils, waxes, mineral oils and their sulfonated or sulfated derivatives, fatty acids and / or their soaps such as alkalis, alkaline earth metal soaps, and phosphates and phosphate esters such as Includes alkyl and alkaline diphosphates, tributyl phosphates, and mixtures thereof.

One of the more effective antifoaming agents includes silicone. Silicones such as dimethyl silicone, glycol polysiloxane, methylphenol polysiloxane, trialkyl or tetraalkylsilane, hydrophobic silica defoaming agents and mixtures thereof can all be used for defoaming applications. Commercially available commercially available defoamers include silicone, silicone and non-silicone type defoamers and silicone esters such as Ardefoma® from Armour Industrial Chemical Company, which is a silicone bound in an organic emulsion. Foam Kill® or Klesseo®, Dow Corning Corporation's Anti-Foam A®, DC-200m, Xiameter® ACP-0544 Anti, available from a Silicone Silicone Company. Contains silicone. These antifoaming agents have a concentration of about 0.001% by weight to about 3.0% by weight, about 0.005% by weight to about 1.0% by weight, and about 0.02% by weight to about 0.2% by weight. Can exist in range.

Other antifoaming agents that can be used in preferred embodiments of the invention include organic amides such as Clarian's Antimussol®, or oils and / or polyalkylenes such as Munzing's Agitan®. Includes base compounds, or branched fatty alcohols such as Isofol® from Sasol.

The compositions of the present invention may further comprise an alcohol alkoxylate-based defoaming or defoaming agent that is stable in an alkaline environment and oxidatively stable.
For this purpose, one of the more effective antifoaming agents has an alcohol chain length of about C _{8 to} C ₁₂ , more specifically C _{9 to} C ₁₁ , and all or part of the alkylene oxide moiety. It is an alcohol alkoxylate having a polypropylene oxide alkoxylate. Commercially available commercially available defoamers of this type include, in particular, Degressal SD20 alkoxylates, such as BASF Degressal.

In addition, so-called cloud spot defoamers (typically nonionic surfactants consisting of ethoxylated / propoxylated alcohols) such as BASF's Purafac® type and Cognis' Dehypon® type are available. It can be used in the invention.

Buffers and pH Adjusters The pH value of the composition can be selectively adjusted by the addition of acidic or basic components. Generally, acidic pH is preferred. Acids suitable for use as a pH regulator include, for example, citric acid, acetic acid, lactic acid, phosphoric acid, phosphorous acid, sulfamic acid, nitrate, nitrite and hydrochloric acid. It will be appreciated by those skilled in the art that organic acids selected as antibacterial organic acids, such as lactic acid, also affect pH and therefore have a regulating effect as discussed in this paragraph. Mineral acids can be used to significantly lower the pH. Raise or make the pH alkaline by adding alkaline agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, monosodium acid diphosphonate, triethanolamine or a combination thereof. be able to. Traditional acid buffers such as citric acid, lactic acid, and phosphoric acid can also be used to maintain the desired pH. The pH value of the composition can be adjusted by the addition of acidic or basic or buffering substances.

The physical properties of pH can be adjusted by the addition of acids or bases and are 2.0-8.0 for use in teat dipping compositions and other compositions intended to come into contact with the skin. Wide range is preferred. In a more preferred sense, this range is 2.0 to 5.5, even more preferably 2.0 to 5.0, and even more preferably 2.5 to 4.5.

Skin Conditioning Agents The teat immersion compositions of the present invention also lubricate, condition, and generally reduce irritation, as well as antibacterial ingredients, mechanical action of milking machines, or frigid temperatures wind. Includes emollients, moisturizers, wetting agents or re-fatting agents to promote healing of the papilla surface resulting from environmental conditions such as chill), dehydration, scratches, wind tans and sunburns. be able to. Any water-miscible, soluble or dispersible skin conditioning agent can be used in the present invention. Compositions such as polyhydric alcohols include glycerin, sorbitol, mannitol, and propylene glycol and homopolymers thereof, polyethylene glycol (PEG) 200-10,000, polyethylene glycol ester, acyllactylate, polyquaternium-7, glycerol cocoate /. Laurate, PEG-7 glycerol cocoate, stearic acid, hydrolyzed silk peptide, silk protein, guarhydroxypropyltrimonium chloride, alkylpolyglucoside / glyceryl laurate, shea butter and coco butter, isopropyl palmitate or isopropyl myristate and similar. Simple monohydryl alcohol fatty acid esters, D-pantenol, glyceride polyol esters; ethoxylated lanolin, vegetable oils, and similar naturally occurring derivatives such as aloe, titanium dioxide, zinc oxide, octylmethoxycinnamate. Sunscreens such as (OMC), 4-methylbenzylidene camphor (4-MBC), oxybenzone and homosalate; anti-itch agents such as aloe vera, caramine, mint, menthol, camphor, antihistamine, corticosteroids, benzokine and paroxamine HCl Examples include agents or paralytic agents. Preferred emollients used in the present invention include glycerin, and propylene glycol and lanolin. Preferably, the freezing point depression component in the carrier medium also acts as a emollient / moisturizer / wetting agent. For example, in some preferred embodiments, propylene glycol and glycerin are present in high concentrations in the composition and act as both a freezing point depressant and a emollient.

Opaque agents and dye compositions can also include dyes, pigments, marking agents, or other such ingredients, as is generally known. The opaque agent or dye is optionally included in the composition of the present invention. For example, the teat color tells the dairy farmer that a particular cow has been treated. It is preferable to use only FD & C certified (food grade) dyes, such as tartrazine E102, to eliminate potential problems of milk contamination. Titanium dioxide (TiO ₂ ) is widely used as an opaque agent and can also be used in combination with various colorants.

The compositions and methods are further described by the following non-limiting examples.

Example 1: Formulations and Methods 1.1 Formulations A series of antibacterial teat immersion formulations were prepared. The amount of each component to be added is described in the examples shown as formulations F1 to F9, A1 to A7 and F10 to F22 in Tables 1-4.

Unless otherwise specified, the amounts of ingredients reported in these tables are based on weight percent of the total composition. The formula is dairy cow teats using a Jetstream Gun (AJS / 2402) with a fixed nozzle tip with an O-ring (AJS2415) from the vacuum-actuated sprayer Ambic® (Ambic Equipment Limited, UK). Sprayed on. After spraying, criteria for film formation quality, spray shadows and wetting on the skin were evaluated. The results are summarized in Tables 1-4.

1.2 Comparative Membrane Evaluation The continuous and uniform membrane quality of the teat immersion was evaluated by the following method. After preparing the composition, it was sprayed on the teat of a dairy cow. The barrier properties of the membrane and the wettability on the skin were evaluated on a scale of 3 and 2, respectively.
The numerical evaluation is as follows:
Membrane formation -1 Insufficient film formation 0 Moderate film formation 1 Good film formation Wetting on the skin -1 Insufficient wetting on the skin 1 Sufficient wetting on the skin

In addition, the spray shadow of the composition was evaluated. The numerical evaluation is as follows:
Spray Shadow-1 Insufficient Spray Shadow 0 Attenuated Conical Spray Shadow 1 Good Conical Spray Shadow

1.3 Viscosity measurement The viscosity of some samples was measured according to the Fordcup measurement method. The principle of this viscosity measurement method is that the viscosity of a sample is measured as the time required for the cup to be emptied by the liquid draining through its bottom orifice. Since viscosity is a flow resistance, highly viscous substances take time to drain through the holes in the cup. The measured times are shown in the table and can be converted to centistokes by multiplying the size of each cup by the discharge time with a given conversion factor. The viscosity of the sample was measured at a temperature of 25 ° C. using a Ford cup 3.

In addition, Brookfield viscosities of some samples were also measured in cPs using a Brookfield LV viscometer at a temperature of 25 ° C. using Spindle # 1 at 60 rpm.

Example 2: Spraying, Wetting and Adhesion Properties of Aqueous Antibacterial Membrane-Forming Nipple Immersion Compositions Various Nipple Immersion Formulations were prepared and tested. First, the composition is described in Document WO 98/04136, which comprises polyvinyl alcohol as a film-forming element, polyvinylpyrrolidone iodine (PVP-iodo) and alkylbenzene sulfonic acid as an active bactericidal substance, and alkyl ether carboxylic acid as a surfactant. It was essentially formulated according to the technical standards used. Formulations on dairy cow teats using Jetstream Gun (AJS / 2402) with a fixed nozzle tip with an O-ring (AJS2415) made by the vacuum operated atomizer Ambic® (Ambic Equipment Limited, UK). After spraying. After spraying, the quality of film formation, spray shadows and wetting on the skin were evaluated. As shown in Table 1, prior art spray shadows, film formation and / or wetting on the skin were not sufficient for the intended use. Therefore, formulations F1 to F9 are reference examples (“reference examples”).

Formulations further containing a rheology modifier and tackifier in the form of xanthan gum (Rhodopol® G, Kelzan® T) and a mineral-based rheology modifier (Optiggel® CK) are tested. bottom. As shown in Table 2, the spray shadows of these formulations were not sufficient. Therefore, formulations A1 to A7 are reference examples (“reference examples”).

Tests on the formulations have shown that excessive foam formation adversely affects barrier properties when using currently available barrier products for spray application. However, the low barrier properties resulted in inadequate protection of the nipple and ducts, and therefore the formulations shown in Tables 1 and 2 were unsuitable for the desired and intended spray application.

Formulations containing hydrophobic modified urethane ethoxylated (HEUR) as rheology modifiers and tackifiers and / or defoamers were then tested. Surprisingly, the use of hydrophobically modified urethane ethoxylated (HEUR) as the rheology modifiers and tackifiers (F10, F11, F12, F14) improved the spray shadows of these formulations, and this HEUR It was found that when the rheology modifier was combined with the antifoaming agent (formulations F13, F15, F16, F18, F19, F20, F21, F22), further improvement was found.

The results summarized in Tables 3 and 4 show that the antibacterial film-forming composition comprising hydrophobic modified urethane ethoxylated (HEUR) as a rheology modifier and tackifier according to the invention is successfully sprayed onto the skin. , Wetting and adhesion properties, and further improved these properties with the addition of antifoaming agents (formulations F13, F15, F16, F18, F19, F20, F21 and F22).

Example 3: Effect of Storage on Spray Nozzles In addition, the formulations of the present invention were tested for their properties in spray guns and spray nozzles over an extended period of time. Therefore, Jetstream Gun (AJS / 2402) with a fixed nozzle tip with an O-ring (AJS2415) made by Ambic® (Ambic Equipment Limited, UK), which is a vacuum actuated sprayer at ambient temperature (20 ° C.). Was stored for 1 week and then the formulations were tested for spray shadow quality. Criteria for film formation quality, spray shadows and wetting on the skin were evaluated. The observed results show that the formulations according to the invention (F10 to F16, F18 to F22) have good membrane construction not only when freshly prepared but also when sprayed after 1 week of storage in Jetstream Gun. It showed properties, good conical spray shadows and good wetness on the skin. Furthermore, when the formulations of the present invention (formulations F13, F19, F22) were used, no nozzle breakage was observed after 1 week of storage in Jetstream Gun.

Example 4: Temperature Effects As an example, formulation F22 was tested for its properties at different temperatures with respect to viscosity and freezing point. The viscosity of the sample was measured according to the Ford cup measurement method using the cup 3. The viscosity of the sample was measured at a temperature in the range of 20 ° C to −8 ° C. The viscosity is reflected by the amount of time required for the cup to be emptied by the liquid drained through the bottom orifice of the cup. The results are shown in Table 5.

Claims (19)

In an aqueous base,
(A) With a film-forming polymer other than hydrophobic modified urethane ethoxylated,
A sprayable aqueous antibacterial film-forming composition comprising (b) an antibacterial agent, further (c) a hydrophobic modified urethane ethoxylated as a rheology modifier, and (d) optionally an antifoaming agent. (A) 0.1 to 10.0% by weight of the film-forming polymer and
(B) 0.1 to 10.0% by weight of antibacterial agent and
(C) 0.001 to 3.0% by weight of hydrophobically modified urethane ethoxylated as a rheology modifier,
(D) The sprayable aqueous antibacterial film-forming composition according to claim 1, optionally with 0.001 to 3.0% by weight of an antifoaming agent. In an aqueous base,
(A) 1.0 to 5.0% by weight of the film-forming polymer and
(B) 0.5 to 7.0% by weight of antibacterial agent and
(C) 0.01 to 1.0% by weight of hydrophobic modified urethane ethoxylated and
(D) The sprayable aqueous antibacterial film-forming composition according to claim 1, optionally comprising 0.005 to 1.0% by weight of an antifoaming agent. In an aqueous base,
(A) 2.0 to 4.5% by weight of the film-forming polymer and
(B) 0.5 to 5.0% by weight of antibacterial agent and
(C) 0.05 to 0.5% by weight of hydrophobic modified urethane ethoxylated,
(D) The sprayable aqueous antibacterial film-forming composition according to claim 1, optionally comprising 0.02 to 0.2% by weight of an antifoaming agent. The sprayable aqueous antibacterial membrane according to any one of claims 1 to 4, which is formulated and suitable for reducing the incidence of both infectious and environmental mastitis within a dairy livestock herd. Formable composition. The hydrophobic modified urethane ethoxylated is a polymer having a polyethylene glycol constituent unit and a urethane constituent unit, and the polymer chain is end-capped with a hydrophobic group, according to any one of claims 1 to 5. A sprayable aqueous antibacterial film-forming composition. The antibacterial agent is I ₂ , iodophore, especially in the form of polyvinylpyrrolidone iodine (PVP-iode), linear or branched aliphatic C _{4 to} C ₁₀ carboxylic acids, especially capric acid and capric acid, octanoic acid, nonanoic acid. , decanoic acid; lactic, salicylic, peroxycarboxylic acids, sulfo peroxycarboxylic _acids, C 1 -C ₄ alkanol, isopropyl alcohol, benzyl alcohol, bronopol (2-bromo-), sodium pyridinium Dinathione, chlorhexidine, chlorhexidine diacetate, chlorhexidine digluconate, quaternary ammonium compounds such as alkyldimethylbenzylammonium salts, dialkyldimethylammonium compounds and benzethonium; sulfonic acid, hypohalic acid, alkaline hypohalite, chlorine dioxide Precursors, chlorine release agents (especially sodium hypochlorite, and more recently chlorinated isocyanurate), hypochlorite, chlorine dioxide, chlorinated isocyanurate (chlorinated-S-triazen-trione), bromine, hydroxy Kinone, ammonium chloride, hexachlorophene, diaphene, cetylpyridinium chloride, acid anion system (eg alkylarylsulfonic acid, arylsulfonic acid, alkylsulfonic acid, alkylarylsulfate, arylsulfate, alkylsulfuric acid, alkylarylsulfate), orthophenyl Polyhexamethylbiguanide (CAS32289-58-0), a phenolic antibacterial agent that can be selected from phenol, 2,4,4'-trichloro-2 "-hydroxydiphenyl ether, 4-chloro-3,5-dimethylphenol, Guanidin salts such as polyhexamethyleneguanidine hydrochloride (CAS57028-96-3), polyhexamethyleneguanidine hydrophosphate (CAS89697-78-9) and poly [2- (2-ethoxy) -ethoxyethyl] -guanidinium chloride. (CAS374572-91-5), and the sprayable aqueous antibacterial film-forming composition according to any one of claims 1 to 6, selected from the group consisting of mixtures thereof. The sprayable aqueous antibacterial film-forming composition according to any one of claims 1 to 7, which comprises an iodine fore in the form of polyvinylpyrrolidone iodine (PVP-iodine) as an antibacterial agent. The sprayable aqueous antibacterial film-forming composition according to any one of claims 1 to 8, further comprising an alkylbenzene sulfonic acid. It has a polyoxypropylene alkyl ether carboxylic acid, particularly the following formula RO- (C ₃ H _6- O) _m- (C ₂ H _4- O) _n- CH _2- COOH, in which R is 4 to 4 to An alkyl group having 10 carbon atoms, m being an integer of 0-8, n being an integer of 0-8, and at least one of m or n is a non-zero polyoxypropylene alkyl ether. The sprayable aqueous antibacterial film-forming composition according to any one of claims 1 to 9, further comprising a carboxylic acid. The following formula RO- (C ₂ H _4- O) has _n- CH _2- COOH, in which R is an alkyl group having 4 to 10 carbon atoms, and n is an integer of 2 to 8. The sprayable aqueous antibacterial film-forming composition according to any one of claims 1 to 9, further comprising a polyoxyethylene alkyl ether carboxylic acid. The sprayable aqueous antibacterial film-forming composition according to any one of claims 1 to 11, wherein polyvinyl alcohol and / or polysulfonic acid is present in the composition. The sprayable aqueous antibacterial film-forming composition according to any one of claims 1 to 11, wherein polyvinyl alcohol and / or polysulfonic acid and polyvinylpyrrolidone iodine are present in the composition. In an aqueous base,
(A) 0.1 to 10.0% by weight of polyvinyl alcohol as the film-forming polymer,
(B) 0.5 to 10.0% by weight of polyvinylpyrrolidone iodine as an antibacterial agent,
(C) 0.001 to 3.0% by weight of hydrophobically modified urethane ethoxylated as a rheology modifier,
(D) The sprayable aqueous antibacterial film-forming composition according to claim 1 or 2 , which comprises 0.001 to 3.0% by weight of an antifoaming agent. In an aqueous base,
(A) 0.1 to 10.0% by weight of polyvinyl alcohol as the film-forming polymer,
(B) 0.5 to 10.0% by weight of polyvinylpyrrolidone iodine as an antibacterial agent,
(C) 0.001 to 3.0% by weight of hydrophobically modified urethane ethoxylated as a rheology modifier,
(D) 0.001 to 3.0% by weight of antifoaming agent and
(E) 0.05 to 5.0% by weight of polysulfonic acid and
(F) It has the following formula RO- (C ₂ H _4- O) n-CH _2- COOH, and in the formula, R is an alkyl group having 4 to 10 carbon atoms, and n is 2 to 2. 0.05-5.0 wt% polyoxyethylene alkyl ether carboxylic acid, which is an integer of 8,
(G) optionally an additional 0.01-5.0% by weight antibacterial agent, preferably under conditions where (b) is 5.0% by weight or less, alkylbenzene sulfonic acid, chlorhexidine, orthophenylphenol. The sprayable aqueous antibacterial film-forming composition according to claim 1 or 2 , comprising an antibacterial agent selected from the group consisting of lactic acid, carboxylic acids, particularly decanoic acids, and mixtures thereof. The sprayable aqueous antibacterial film-forming composition according to any one of claims 1 to 15, wherein the defoaming agent is a silicone-based defoaming agent. 10. One of claims 1-16, wherein the spindle # 1 is used at 60 rpm and has a Brookfield viscosity of 1 to 50 cPs, preferably 1 to 20 cPs, more preferably 1 to 5 cPs at a temperature of 25 ° C. A sprayable aqueous antibacterial film-forming composition. Use of the composition according to any one of claims 1 to 17, for suppressing mastitis in lactating animals. A method for suppressing mastitis in a lactating animal, which comprises spraying the teat with the composition according to any one of claims 1 to 17.