CN108697082A - Surface disinfection agent with remaining biocidal properties - Google Patents

Abstract

The present invention provides the biomembrane sealing agent for giving remaining biocidal properties.Handle surface with biomembrane sealing agent has the ability for quickly killing bacterium and other germs to give film on treated surface at least 24 hours after deposition film.Biocide preparation biomembrane sealing agent includes polymer adhesive, the wherein amplification or polymer-modified of polymer adhesive Wei oxazolines homopolymer or Ji Yu oxazoline homopolymers;And Biocidal compounds.

Description

Surface germicide with residual biocidal properties

Cross reference to related applications

This application claims priority to U.S. patent application Ser. No. 15/162,094, filed on U.S. patent and trademark office 2016, 5/23, 2016, U.S. patent application Ser. No. 15/162,094, a continuation-in-part application claiming priority to U.S. patent application Ser. No. 14/949,046, filed on 11/23, 2015, U.S. provisional patent application Ser. No. 62/084,917, filed on 26, 11, 2014, and U.S. provisional patent application Ser. No. 62/127,075, filed on 3, 2, 2015, and U.S. provisional patent application Ser. No. 62/166,403, filed on 26, 5, 2015. The disclosure of which is incorporated herein by reference in its entirety.

Technical Field

The present invention relates to the field of germicidal formulations, and more particularly to germicidal formulations that impart residual biocidal properties.

Background

Microorganisms are ubiquitous in the modern world. While some are beneficial to humans and the environment, others can have significant negative consequences for contaminated items and humans, animals, and ecological members in contact with them. There are several industries and environments in which these microorganisms are particularly prevalent.

Health care

Hospital-acquired infections (HAIs; or "nosocomial infections") are infections that are promoted to occur in a hospital or healthcare setting. These diseases are typically fungal or bacterial infections and can afflict the patient locally or systemically. Nosocomial infections can cause severe pneumonia and infections of the urinary tract, bloodstream, and other body parts.

Nosocomial infections present a serious medical problem for patients and care providers. In the united states, data indicates that about 1,700,000 cases of hospital-related infection occur annually, with nearly 100,000 deaths resulting. European data and investigations have shown that gram-negative infections alone cause 8,000-10,000 deaths per year.

There are several aggravating factors contributing to high HAI rates. Hospitals, emergency care centers, nursing homes, and similar facilities focus treatment on patients with severe disease and injuries. Thus, these facilities accommodate an abnormally high concentration of patient populations with weakened immune systems.

A group of three pathogens are commonly found in healthcare environments and collectively account for about one-third of nosocomial infections: coagulase-negative staphylococci (15%), candida (11%) and escherichia coli (10%).

Worse yet, present in these environments are more persistent pathogenic pathogens. There are six so-called "ESKAPE pathogens" that are antibiotic resistant and involved in nearly half of all nosocomial infections, and they are enterococcus faecalis ((r))Enterococcus faecium)、Staphylococcus aureus (1)Staphylococcus aureus)、Pneumonia of lungKlebsiella bacterium (Klebsiella pneumoniae)Klebsiella pneumoniae)、Acinetobacter baumannii (A), (B)Acinetobacter baumannii)、Pseudomonas aeruginosa (Pseudomonas aeruginosa) And enterobacteria: (Enterobacterspecies). Resistance to one or more biocides makes these infections particularly dangerous.

In particular, the wide nutritional versatility of pseudomonas allows it to survive in extreme environments, including on surfaces that are not thoroughly cleaned and sterilized. The ubiquitous presence of this pathogen in the hospital setting makes it a cause of gram-negative nosocomial infections. Particularly vulnerable are immunocompromised patients (e.g., those with cystic fibrosis, cancer, or burns).

The most common mode of HAI is by direct or indirect contact infection. Direct contact infection includes contact with a contaminated patient or a patient who is a worker. As care providers move through healthcare facilities, they come into contact with many of their patients. These workers unknowingly move in a manner similar to honey peaks in gardens, and "pollinate" rooms and wards as they attend their accommodators.

Indirect contact infection occurs when a patient contacts a contaminated object or surface. The healthcare environment provides a collection of items that can passively guide pathogens.

Nosocomial infections also present a significant hurdle to the amount, quality, and cost of health care provided by hospitals and other institutions. In addition to the emergence of roughly 100,000 HAI-related deaths annually in the united states, an estimated two million or more patients are forced to suffer the physical and mental distress associated with these serious and avoidable illnesses.

Organizations have responded by institutional policies, placing more stringent cleanliness and sterilization requirements on the staff and patient environment. These procedures typically include frequent hand washing and frequent surface sterilization. Despite the implementation of procedures to control nosocomial infections, infections still occur at unacceptably high rates.

Home care and family

The domestic environment is also faced with microorganisms. A major disadvantage associated with consumer disinfectants and sanitizers is that, while they are effective in initially killing microorganisms, the surfaces are easily and quickly recontaminated by contact, airborne microorganisms, and residual microorganisms that have not been killed prior to treatment. While some biocides continue to give some control if left on a surface simply, this can produce a grease or sticky residue that is susceptible to failure by inadvertent contact with the surface. Thus, there is a need for a home care and household cleaner that rapidly kills microorganisms upon contact and then acts as a residual biocide, but without such undesirable stickiness or blocking effects. These cleaners are useful in general-purpose household cleaning, bathroom cleaning, and spray protection.

The difference between hospital and health care cleansers and household products is the allowable VOC (volatile organic content). The regulation for most non-aerosol consumer fungicides for home use is a 1% VOC maximum.

Diet service

The food service industry is also faced with incidents of pathogen contamination and disease transmission to consumers in workplaces. Even if food manufacturers adopt strong sanitary equipment and comply with strict government health regulations, significant incidents of microorganisms causing serious diseases in consumers are occasionally reported. Residual active biocides should be effective in alleviating this problem.

Biological membrane

Biofilm is generally defined as a layer of microorganisms that secrete a protective coating of biological origin, which adheres to the surface of a structure, which may be organic or inorganic. Biofilms pose a great problem for public health due to increased resistance of biofilm-associated organisms to antimicrobial agents, and the possibility of infection by biofilm-carrying organisms. Thus, a need exists for a biofilm-related sterilization protocol. Current biocides do not have the ability to kill biofilms or biofilms on closed or occluded surfaces to prevent cross-contamination events and to prevent hyperplasia. There are limited solutions to the surface biofilm problem. For example, there is evidence that surface biofilms pose health care environmental problems for the reasons described above. In addition, biofilms are a recognized problem of possible contamination within the food industry. Other industries also face similar problems. Thus, there is a need for a solution that can be used to eradicate biofilm in areas of potential biofilm problem.

In summary, there remains a need for formulations that are capable of imparting residual biocidal activity to treated surfaces. It would be further advantageous if the formulation in combination with a surface biocide could achieve a bactericidal and residual biocidal effect in a single cleaning pass.

It is further advantageous that the residual biocidal properties are permanently associated with the treated surface so that microbial reduction can be provided continuously over a long period of time after application.

It would be further advantageous if the formulations were effective in a wide range of industries and applications.

Summary of The Invention

The present invention relates to germicidal formulations that impart residual biocidal properties. The bactericidal formulation comprises a polymeric binder, wherein the polymeric binder is an oxazoline homopolymer or an amplification or modification polymer based on the oxazoline homopolymer; and a biocidal compound. The germicidal formulation further comprises a carrier.

In one aspect of the invention, the oxazoline homopolymer has the structure:

wherein R is₁Is hydrogen, alkyl, alkenyl, alkoxy, alkylamino, alkynyl, allyl, amino, anilino, aryl, benzyl, carboxyl, carboxyalkyl, carboxyalkenyl, cyano, glycosyl, halo, hydroxyl, oxazolinium methanesulfonate, oxazolinium toluenesulfonate, oxazolinium trifluoromethanesulfonate, silyliumAlkyl oxazolinium, phenol, polyalkoxy, quaternary ammonium, thiol or thioether groups; r₂Is hydrogen, alkyl, alkenyl, alkoxy, alkylamino, alkynyl, allyl, amino, anilino, aryl, benzyl, carboxyl, carboxyalkyl, carboxyalkenyl, cyano, glycosyl, halo, hydroxyl, oxazolinium mesylate, oxazolinium tosylate, oxazolinium triflate, silyloxazolinium, phenol, polyalkoxy, quaternary ammonium, thiol or thioether group, or a macrocyclic structure; r₃Is hydrogen, alkyl, alkenyl, alkoxy, aryl, benzyl, hydroxyalkyl or perfluoroalkyl; and n is in the range of 1 to 1,000,000.

In another aspect of the invention, other features of the germicidal formulation are provided.

In another aspect of the invention, articles of manufacture having the germicidal formulations of the invention are provided, as well as methods of making, using, and applying the germicidal formulations.

Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.

Detailed description of the preferred embodiments

The following detailed description of the embodiments of the invention is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. The present invention has a wide range of potential uses and applications, and is expected to be applicable in a wide range of industries. The following detailed description provided herein is offered by way of example only to enable disclosure of the invention and not to limit the scope or content of the invention.

The term "microorganism" or "microbial" as used herein should be interpreted to refer to microscopic organisms studied by microbiologists or found in the environment of use of the treated article. These organisms include, but are not limited to, bacteria and fungi, and other unicellular organisms such as molds, mildews, and algae. Also included in the term microorganism are viral particles and other infectious agents.

It is also understood that "antimicrobial" includes both microbicidal and microbiostatic properties. That is, the term encompasses killing the microorganisms, resulting in a reduction in the number of microorganisms, and microbial growth retardation effects, wherein the number may remain more or less the same (while allowing for a slight increase/decrease).

For ease of discussion, this description uses the term antimicrobial to refer to broad spectrum activity (e.g., against bacteria and fungi). In referring to efficacy against a particular microorganism or classification level, a more specific term is used (e.g., specifically antifungal means efficacy against fungal growth).

Using the above examples, it will be appreciated that efficacy against fungi does not in any way exclude the possibility that the same antimicrobial composition may show efficacy against other types of microorganisms.

For example, the discussion of strong bacterial efficacy shown by the disclosed embodiments should not be interpreted that the embodiments do not exhibit antifungal activity. The expression such a method should not be construed as limiting the scope of the invention in any way.

Bactericidal preparation

The invention relates to a sterilization preparation. In one aspect of the invention, the antiseptic formulation is in liquid form. The germicidal formulation composition includes a biocidal compound and a polymeric binder. The composition may further comprise a solvent (such as water or a low molecular weight alcohol), a surfactant, a colorant, a fragrance, among others.

The formulated liquid composition has surface bactericidal and residual biocidal properties. The formulation may be applied to the surface by spraying, rolling, atomizing, wiping, or other methods. The formulation acts as a surface biocide killing infectious microorganisms present on the surface.

Once dried, the liquid formulation leaves a residual protective film on the surface. The residual film has biocidal properties that enable it to maintain surface protection against microbial contamination over extended periods of time after application.

In a preferred embodiment, the surface antiseptic formulation confers the ability to rapidly kill bacteria and other germs for at least 24 hours after the film is deposited on the treated surface. In one aspect of the invention, fast kill generally refers to a time of about 30 seconds to about 5 minutes. The film will remain on the surface and resist multiple contacts and surface wear.

In another embodiment of the invention, the germicidal formulation is a liquid composition comprising a polymeric binder, a biocidal compound, a carrier (e.g., a solvent), and other optional components (e.g., a fragrance).

Biofilm sealant

In one embodiment of the invention, the antiseptic formulation is a biofilm sealant. Once applied to a surface, the biofilm sealant forms a polymer film. The polymer film is wet applied and dried as a film layer to lock-up and prevent subsequent biofilm microbial proliferation. The biofilm sealant, while preferably in liquid form, may also take other forms, such as a gel or other forms. Once the biofilm sealant is in place, the microorganisms of the biofilm have restricted access to oxygen and exogenous nutrients. Biofilm sealants have the potential to seal bacteria and prolong the release of antimicrobial agents into the membrane to kill microorganisms in the biofilm.

In one embodiment of the invention, a biofilm sealant comprises a polymeric binder and a biocidal compound. The biocidal compound may include, but is not limited to, any of the biocidal compounds described herein.

In one embodiment of the invention, the biofilm sealant comprises an oxazoline homopolymer as the polymeric binder. The oxazoline homopolymer may have any of the structures described herein.

In one embodiment of the invention, a biofilm sealant comprises a polymeric binder, a biocidal compound, and an enzyme. The enzymes help degrade the biofilm and facilitate biocide antimicrobial penetration, ultimately removing the biofilm. Example enzymes include, but are not limited to, proteases, dnases, rnases, and sugar-specific enzymes that degrade the extracellular matrix associated with biological membranes.

In one embodiment of the invention, the biofilm sealant comprises a polymeric binder and an antibody as a biomaterial for slow release into the membrane. Antibody functionality will bind to biofilm microorganisms to prevent cross-contamination.

In one embodiment of the invention, the biofilm sealant comprises a polymeric binder and a bacteriophage or mixture of bacteriophages as the biomaterial for slow release into the membrane. The phage acts as a targeted antimicrobial to kill biofilm-bound organisms.

In one embodiment of the invention, the biofilm sealant comprises a polymeric binder, and a mixture of bacteriophage, antimicrobial agent, enzyme and antibody as a biomaterial for slow release into the membrane.

Polymer adhesive

In one aspect of the invention, the polymeric binder is an oxazoline homopolymer. As another feature of the present invention, the oxazoline homopolymer has the following structure:

wherein

R₁And R₂End groups determined by the polymerization technique used to synthesize the oxazoline homopolymer. R₁And R₂Independently selected and include, but are not limited to, hydrogen, alkyl, alkenyl, alkoxy, alkylamino, alkynyl, allyl, amino, anilino, aryl, benzyl, carboxyl, carboxyalkyl, carboxyalkenyl, cyano, glycosyl, halo, hydroxyl, oxazolinium mesylate, oxazolinium tosylate, oxazolinium triflate, silyloxazolinium, phenol, polyalkoxy, quaternary ammonium, thiol, or thioether groups. Or,R₂macrocyclic structures formed during synthesis due to intramolecular attack may be included.

For example, R₁Is methyl, R₂Is oxazolinium tosylate if methyl tosylate is used as initiator in the cationically initiated polymerization of oxazolines.

R₃Are end groups determined by the type of oxazoline used in preparing the polymer binder of the present invention. R₃Including but not limited to hydrogen, alkyl, alkenyl, alkoxy, aryl, benzyl, hydroxyalkyl, or perfluoroalkyl. For example, R₃Is ethyl if ethyl oxazoline is the monomer used to prepare the polymer binder of the present invention.

n is the degree of polymerization of the oxazoline in the homopolymer. n is in the range of 1 to 1,000,000. Preferably n is in the range of 500 to 250,000, most preferably n is in the range of 2500 to 100,000.

Similar to oxazoline homopolymers, expanded or modified polymers having some variations based on oxazoline homopolymers are also suitable for use in the present invention. The techniques and options for making chemical or molecular structural changes or modifications to the oxazoline would be familiar to those skilled in the art. The type of amplified or modified polymer based on oxazoline homopolymer can be represented by the following molecular structure:

wherein

R₁And R₃Having the same definition as given above for the oxazoline homopolymer.

B is an additional monomer repeat unit linked to the oxazoline in the copolymer. The arrangement type of the repeating units between B and the oxazoline in the copolymer may include, but is not limited to, block, alternating, periodic, or combinations thereof. There is no limitation on the type of B that can be used to copolymerize or modify the oxazoline of the present invention.

n is the degree of polymerization of the oxazoline repeating unit, n in the copolymer is in the range of 1 to 1,000,000, and at the same time, m is in the range of 0 to 500,000 with respect to the degree of polymerization of the B repeating unit in the copolymer. Preferably n is in the range of 500 to 250,000 and m is in the range of 20 to 10,000; most preferably, n is in the range of 2500 to 100,000 and m is in the range of 50 to 5,000. In addition to attaching B to the ethyl oxazoline by copolymerization, B may also be attached to the oxazoline if B itself is already a quaternary ammonium compound, as an end group in cationic polymerization using B as a cationic initiator.

B, not intended to be fully inclusive, may for example be an ethyleneimine having the following molecular structure:

wherein

R₁And R₂The end groups have the same definition as described for the oxazoline homopolymer.

R₃Including but not limited to hydrogen, alkyl, alkenyl, alkoxy, aryl, benzyl, hydroxyalkyl, or perfluoroalkyl.

R₄Including but not limited to hydrogen, alkyl, alkenyl, alkoxy, aryl, benzyl, hydroxyalkyl, or perfluoroalkyl.

m is in the range of 0 to 500,000, preferably in the range of 20 to 10,000, most preferably in the range of 50 to 5,000.

n is in the range of 1 to 1,000,000, preferably 500 to 250,000, most preferably 2500 to 100,000.

For example, the synthesis of oxazoline and ethyleneimine copolymers can be divided into two steps. In the first step, a polyoxazoline homopolymer may be prepared using cationic ring opening polymerization techniques. In a second step, the polyoxazoline prepared in the first step may be hydrolyzed to convert a portion of the polyoxazoline repeat units to polyethyleneimine. Alternatively, oxazoline-ethyleneimine copolymers can be prepared with the appropriate corresponding monomers, oxazoline and aziridine. The result may be a cationic polymer having the above structure.

The polymerization degree n for the oxazoline repeating units in the copolymer is in the range of 1 to 1,000,000, while the polymerization degree m for the ethyleneimine repeating units in the copolymer is in the range of 0 to 500,000. Preferably n is in the range of 500 to 250,000 and m is in the range of 20 to 10,000; most preferably, n is in the range of 2500 to 100,000 and m is in the range of 50 to 5,000.

Alternatively, the nitrogen in the ethyleneimine repeat units can be further quaternized to produce the following cationic copolymers:

the polymers of this example can be quaternized using any quaternization technique familiar to those skilled in the art. R₁、R₂、R₃And R₄Have the same meaning as shown in the oxazoline-ethyleneimine copolymer above. R₅Including but not limited to hydrogen, methyl, ethyl, propyl, or other types of alkyl groups. Corresponding anions X^-Is halogen, sulfonate, sulfate, phosphonate, phosphate, carbonate/bicarbonate, hydroxide, or carboxylate.

The ranges for n and m are also the same as described for the oxazoline-ethyleneimine copolymer.

Another example of B that can be used in the present invention is polydiallyldimethylammonium chloride. The polyethyloxazoline modified with polydiallyldimethylammonium chloride has the following structure:

wherein

R₁And R₄Have the same meaning as described in the previous examples for quaternized oxazoline-ethyleneimine copolymers.

R₂And R₃Independently include, but are not limited to, lower alkyl groups, e.g. C₁To C₆. Corresponding anions X^-Is halogen, sulfonate, sulfate, phosphonate, phosphate, carbonate/bicarbonate, hydroxide, or carboxylate.

n and m are defined and counted as in the previous example.

B may be other olefins including, but not limited to, diallyldimethylammonium chloride, styrene, methoxystyrene, and methoxyethylene. Ethyl oxazoline may also be copolymerized with heterocyclic monomers such as ethylene oxide, thietane, 1, 3-dioxepane, oxetan-2-one, and tetrahydrofuran to enhance the properties of the polymers of the present invention. The adhesives used in the present invention may also utilize oxazoline side groups on the polymer backbone, such as acrylic or styrene based polymers, or acrylic or styrene containing copolymers.

Examples of commercially available polyethyloxazoline include, but are not limited to, Aquazol 500 available from Polymer Chemistry Innovations, Inc.

The amount of polymeric binder that can be used in the liquid formulation can vary to some extent depending on the desired length of residual activity of the composition and the nature of all other components in the composition. The amount of polymeric binder in the liquid formulation is preferably in the range of 0.1% to 20% based on the weight of the liquid formulation. In liquid formulations for healthcare applications, the amount of polymeric binder in the liquid formulation is more preferably in the range of 0.5% to 10%, most preferably in the range of 0.8% to 5%. In liquid formulations for use in general and bathroom cleaners, the amount of polymeric binder in the liquid formulation is more preferably in the range of 0.1% to 10%, most preferably in the range of 0.1% to 5%.

The polymeric binder is preferably water soluble and can be easily removed from the surface if any build-up is noted. However, its presence in small amounts can provide a durable bond between the biocidal compound and the treated surface to promote residual effectiveness.

Biocidal compounds

The biocidal compound may be a Quaternary Ammonium Compound (QAC) having the following molecular structure:

wherein

R₁、R₂、R₃And R₄Independently selected from and including, but not limited to, alkyl, alkoxy, or aryl, with or without heteroatoms, or saturated or unsaturated. Some or all of the functional groups may be the same.

Corresponding anions X^-Including but not limited to halogen, sulfonate, sulfate, phosphonate, phosphate, carbonate/bicarbonate, hydroxide, or carboxylate.

QACs include, but are not limited to, n-alkyl dimethyl benzyl ammonium chloride, di-n-octyl dimethyl ammonium chloride, dodecyl dimethyl ammonium chloride, saccharin n-alkyl dimethyl benzyl ammonium, and 3- (trimethoxysilyl) propyl dimethyl octadecyl ammonium chloride.

Combinations of monomeric QACs are preferred for use in the present invention. Specific examples of QAC combinations are n-alkyldimethylbenzylammonium chloride (40%), n-octyldecyldimethylammonium chloride (30%), di-n-decyldimethylammonium chloride (15%) and di-n-octyldimethylammonium chloride (15%). Percentages are weight percentages of the QAC alone based on the total weight of the mixed QAC composition.

The polymeric species of QACs having the following structures are also useful in the present invention.

Or

Wherein

R₁、R₂、R₅And R₆Independently include, but are not limited to, hydrogen, methyl, ethyl, propyl, or other longer alkyl groups.

R₃And R₄Independently selected and include, but are not limited to, methylene, ethylene, propylene or other longer alkylene linkers.

n is a degree of polymerization, and n is an integer ranging from 2 to 10,000.

Examples of cationic polymers having the above structure include, but are not limited to, polyamines obtained from dimethylamine and epichlorohydrin, such as Superfloc C-572 available from Kemira Chemicals.

Additional polymeric QACs suitable for use in the present invention are poly (diallyldimethylammonium chloride) or poly (DADMAC).

Another class of QACs suitable for use in the present invention are those compounds having a biguanide moiety in the molecule. Examples of such cationic antimicrobial agents include, but are not limited to, PHMB and chlorhexidine.

Examples of commercially available quaternary ammonium compounds include, but are not limited to, Bardac 205M and 208M from Lonza and BTC885 from Stepan Company.

The biocidal compound may be a weak acid, which has been shown to be particularly effective in bathroom cleaners. Among these types of products, citric acid, sulfamic acid (also known as sulfamic acid), glycolic acid, lactic acid, lauric acid, and capric acid are useful as effective biocides and detergents for soap scum and hard water deposits.

Other compounds which may be used are silane quaternary salts, such as 3- (trihydroxysilyl) propyldimethyloctadecyl ammonium chloride. These may have the additional benefit of reacting with the surface to be treated for enhancing residual properties.

Other biocidal compounds suitable for use in the liquid formulations of the present invention span a wide range of antimicrobials, biocides, disinfectants, and bactericides. Water-soluble or dispersible biocidal compounds are preferred, but alcohol-soluble biocides may alternatively be utilized.

A non-exhaustive list of biocidal compounds suitable for use in the formulations of the present invention include triclosan, zinc pyrithione, metal salts and oxides, phenols, plant matter, halogens, peroxides, heterocyclic biocides, aldehydes, and alcohols.

The concentration of the biocidal compound in the formulation may range from 0.05% to 20% based on the weight of the liquid composition. For liquid formulations for healthcare applications, it is preferably in the range of 0.1% to 20%, more preferably in the range of 0.5% to 3%. For liquid formulations for general purpose and bathroom cleaners, a range of 0.05% to 10% is preferred. For formulations used as protectants, it is preferably in the range of 0.05% to 2%.

Carrier

The carrier or vehicle for the liquid formulations of the present invention may be any solvent that is volatile and readily evaporates at ambient conditions. Examples of liquid carriers include, but are not limited to, water and low molecular weight alcohols, such as C1 to C8 alkanols. Specific examples include, but are not limited to, ethanol, isopropanol, butanol, pentanol, and combinations thereof.

Another class of solvents useful in the present invention includes alkylene glycol ethers. Examples include, but are not limited to, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol n-butyl ether, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, and tripropylene glycol methyl ether.

Another class of solvents suitable for use in the present invention are based on terpenes and derivatives thereof, such as terpene alcohols, terpene esters, terpene ethers or terpene aldehydes. Examples of solvents include, but are not limited to, pine oil, lemon oil, limonene, pinene, cymene, myrcene, fenchone, borneol, nopyl alcohol, cineole, ionone, and the like.

A preferred carrier in liquid formulations for home care cleaning applications is water.

If the method of application of the liquid formulation of the present invention is a pressurized aerosol, a propellant may be required in the composition. A variety of propellants or mixtures may be used in the present invention and should be familiar to those skilled in the art. C1 to C10 hydrocarbons or halogenated hydrocarbons are typical propellants in aerosol compositions known in the industry. Examples of such propellants include, but are not limited to, pentane, butane, propane, and methane. Other types of propellants that may be used in the present invention also include compressed air, nitrogen or carbon dioxide. Alternatively, the product can be aerosolized using the capsule valve assembly without adding the propellant directly to the composition.

A single solvent or a mixture of the above solvents may be used in the present invention. The type of solvent used in the present invention may depend on the intended use of the residual germicidal composition. For example, if the compositions of the present invention are intended for home care use, cleaning contaminated surfaces to remove all types of soils or soils may be of major concern. The liquid carrier or medium which aids and facilitates the removal of soils may be a formulation of the present invention. For example, for better cleaning performance in the home care category of the present formulations, the residual germicidal formulations or compositions of the present invention may need to include alkyl or polyalkyl glycol ethers. On the other hand, if the primary goal of the residual germicidal composition is for a health care facility where the primary problem is hospital acquired infections, then rapid drying of the liquid composition of the present invention may be more desirable than removal of dirt or grime from a surface. It is believed that the low molecular weight alcohol contributes to the rapid drying of the liquid formulation of the present invention after application. The low molecular weight alcohol in the liquid formulation will also enhance the disinfecting activity of the liquid composition.

For the health care use of residual biocides, mixtures of water and low molecular weight alcohols are preferred. The amount of alcohol present in the liquid formulation is preferably at a level at which the liquid formulation is capable of forming an azeotrope between the alcohol and water. The minimum amount of alcohol in the liquid composition, if present, is 10%. For the health care use of residual biocide, the alcohol concentration is 30%, and for the health care use of the composition of the present invention most preferably the alcohol concentration is at least 50% based on the weight of the liquid formulation.

Surface active agent

Surfactants or wetting agents may be utilized. The surfactant aids in spreading and uniformly coating the surface to be treated with the liquid formulation. The surfactant additionally aids in the formation of an azeotrope between the alcohol and water, thus promoting rapid and uniform drying of the liquid formulation once applied to a surface. Surfactants also play an important role in the residual germicidal liquid formulation of the present invention for home care applications if soil cleaning performance is a key feature to design the product.

Surfactants suitable for the liquid formulations of the present invention include, but are not limited to, those surfactants that are nonionic, anionic, or amphoteric in nature. Examples of commercially available humectants include, but are not limited to, Ecosurf SA-4 or Tergitol TMN-3 from Dow Chemical and Q2-5211 from Dow Corning.

Amine oxide surfactants are particularly preferred when the QAC is used as a biocidal compound in a formulation.

In the class of nonionic surfactants, ethoxylated alcohols with varying amounts of ethylene oxide or HLB values may be used. Examples of ethoxylated alcohols include, but are not limited to, Triton X-100(Dow Chemical, Midland MI), the Ecosurf EH series of nonionic surfactants available from Dow Chemical, the Tergitol series of nonionic surfactants available from Dow Chemical, the Surfonic series of surfactants available from Huntsman Corp, the Neodol series of surfactants available from Shell, the Ethox series of surfactants available from Ethox Chemicals, and the Tomadol series of surfactants available from Air Products and Chemicals, Inc.

Another class of nonionic surfactants includes alkyl polyglucosides. Examples include the Glucopon series from BASF and the Ecoteric series from Huntsman.

An alternative class of surfactants that are preferred for liquid formulations are silane-based surfactants. Examples include, but are not limited to, silicone polyether organofunctional or reactive silane wetting agents and fluorochemical wetting agents.

The content of the surfactant in the liquid formulation is in the range of 0% to 10%, preferably in the range of 0.01% to 5%.

Depending on the intended use, the liquid formulation of the present invention for home care use may need to be adapted to the pH conditions. For example, if the liquid product is used in a kitchen area, a high pH product may be required in order to effectively remove the oil stains typically found in this area. Soap scum and hard water deposits can be a major problem if the product is used in bathroom areas. In this case, a low pH product may be more suitable for this use. There is no limitation on the type of pH adjusting agent that may be added to the liquid composition of the present invention. Examples of useful pH adjusters include, but are not limited to, triethanolamine, diethanolamine, monoethanolamine, sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, calcium carbonate, citric acid, acetic acid, hydrochloric acid, sulfamic acid, sulfuric acid, and the like.

Additional functional components other than the above-mentioned components may be included in the liquid composition of the present invention. Additional components include, but are not limited to, chelating agents, compatibilizing agents, coupling agents, corrosion inhibitors, rheology modifiers, fragrances, colorants, preservatives, UV stabilizers, optical brighteners, and active ingredient indicators.

In one embodiment of the invention, the liquid solution comprises a polymeric binder, a quaternary ammonium compound, a silicone-based surfactant, and ethanol. The liquid formulation may be prepared or mixed by any conventional method known to those skilled in the art. There is no preferred method of incorporation for the formulations of the present invention, provided that the formulations are ultimately homogeneous, compatible and stable. For example, if the polymeric binder is a solid, it may be preferred to first dissolve or disperse the polymer in a carrier, such as water or alcohol, to prepare a stock polymeric binder liquid dispersion. Stock polymer binder liquid dispersions can be easily added to the formulations of the present invention during the mixing procedure.

Liquid formulation administration

Liquid formulations can be applied in a variety of ways. If sprayed, the liquid formulation may advantageously be provided in a conventional bottle with a nebulizer. The sprayer may be a trigger sprayer. As an option to trigger the nebulizer, the liquid formulation may also be delivered to the surface with an aerosol. Additional methods of application include, but are not limited to, atomization, rolling, brushing, wiping, and wiping with various applicators. Within the scope of the present invention, wipe products comprising or pre-treated with the germicidal formulations of the present invention may also be manufactured, for example, for sale or use on the spot.

To sterilize the contaminated surface, the liquid formulation is sprayed until the area is completely covered. Subsequently, the wet formulation can be wiped dry with a dry cloth or paper towel.

According to aspects of the invention, the invention also relates to articles treated with the germicidal formulation.

Examples

The following examples illustrate liquid formulations prepared according to aspects of the present invention. The test results for these formulations show the desired residual disinfecting or sterilizing properties when applied to a surface and dried. Those formulations were also tested for cleaning performance, and not only did those formulations provide residual germicidal benefits, but also provided cleaning characteristics.

The formulations were tested for residual efficacy using the EPA 01-1A protocol. Briefly, bacteria were applied to a slide and allowed to dry on the surface. The formulation is then sprayed onto a surface and dried to form a transparent film. Once the film was formed, the slides were exposed to alternating wet and dry cycles using a Gardner abrasion tester, as described in the protocol. Between cycles, the slides were re-inoculated with bacteria. After the appropriate number of abrasions and re-inoculations (48 abrasions and 11 re-inoculations for the healthcare formulation, and 24 abrasions and 5 re-inoculations for the home care formulation), the slides were exposed to bacteria for the indicated time range (i.e., 5 minutes) and subsequently recovered in the appropriate neutralization solution.

In addition to the residual efficacy, the compositions of the present invention were also tested for initial efficacy according to ASTM E1153.

The hard surface cleaning performance of the home care compositions of the present invention was evaluated using modified ASTM D4488. The following composition of soil was used for evaluation.

TABLE 1

Components	Weight percentage of each component (%)
		Pure vegetable oil	75
TM-122 AATCC (American tissue CoC) blanket dirt	25

TM-122 AATCC blanket soil was obtained from Textile Innovators.

During the preparation of the soiled tiles for the cleaning trials, approximately 2 grams of liquid soil was placed on the aluminum foil. The dirt is rolled and spread on the foil with the rollers and the rollers pick up as much dirt as possible. Dirt on the roller is uniformly transferred to the glazed surface of the tile by rolling the dirt roller over the tile surface. The soiled tiles were then baked in an oven set at 180 ℃ for 45 minutes. The baked bricks were conditioned at room temperature for 24 hours before being used in the cleaning test.

A Gardner abrasion tester was used in the cleaning tests. A scrub pad of about 1cm width was attached to the wear boat for wear. About 4 grams of the test formulation was placed in a weigh boat. The attached scrubbing pad is immersed in the weigh boat to pick up the test formulation.

The cleaning process begins immediately after the pad is wetted with the cleaning formulation. 7 cycles of abrasion (back and forth) were used in the test.

Examples of residual biocides for health Care

To provide fast drying properties of liquid formulations, the following formulations in the examples used alcohol as the primary carrier.

TABLE 2

The residual efficacy test was carried out using the procedure of EP01-1A and the results are given in the table below.

TABLE 3

Preparation	EP01-1A (mean log reduction of bacteria))
		HE1	3.53
HE2	5.50
		HE3	4.50

These formulations show excellent residual efficacy results based on the EP01-1A test.

The initial biocidal performance of HE2 was also evaluated according to ASTM E1153 test protocol. The test results are shown in the table below.

TABLE 4

These data clearly show that the sample surfaces treated with the exemplary liquid formulations disclosed herein have significant biocidal activity over the indicated time range.

Residual germicidal detergent examples for home care

These compositions are formulated with water as the carrier. They are intended for home care applications where VOC regulations prohibit the use of most high levels of organic solvents such as alcohols.

TABLE 5

The residual efficacy of these formulations was evaluated using the EP01-1A protocol and the results are set forth in the following table.

TABLE 6

Preparation	EP01-1A (mean log reduction of bacteria))
		H1	3.53
H2	5.50
		H3	5.50
H4	4.90
		H5	3.80

Enterobacter aerogenes was the bacterium used in the H1 test, and Staphylococcus aureus was the bacterium used in the tests of the remaining formulations.

The test results show that all H1 to H5 provide residual effectiveness to the treated surface. Cleaning performance was also evaluated using a modified ASTM D4488 test method.

The test results also clearly show visually that the formulations of the present invention not only provide residual efficacy against bacteria, but also provide excellent cleaning performance on soiled surfaces.

Additional formulations shown in the following table were tested for home care and home cleaning applications. To solubilize the fragrance, a premix is prepared comprising the fragrance, quaternary ammonium compound, surfactant, and glycol ether (if present).

TABLE 7 light duty protectant formulations

B represents the balance of water

TABLE 8 general cleaning formulations

TABLE 9 bathroom cleaning formulations

Aqueous-based formulation concentrates are prepared by removing a portion of the water from the formulation and concentrating the remaining raw materials. The resulting concentrate can then be diluted back to use concentration prior to use. In the cleaning and sanitizing provision industry where consumers are located in the reception area, 5-fold and 10-fold concentrates are typically used. Concentrates are desirable in these industries because of reduced transportation costs and storage space savings. Table 10 illustrates an example concentrate formulation in one embodiment of the invention.

TABLE 10 concentrate formulations

Comparative examples

Various polymeric compounds were tested for their ability to provide sustained bioburden reduction to enterobacter aerogenes using the EPA 01-1A protocol. Before being tested, 50 μ L of each formulation was dried on a glass carrier. Each test was performed in the presence of 5% FBS. As shown in table 11, the polyoxazoline and quaternary ammonium combination provides synergistic residual disinfection benefits.

TABLE 11

Means not tested due to poor organoleptic properties

Thus, one skilled in the art will readily appreciate that the compositions and methods of the present invention are susceptible to a wide range of applications and uses. Many embodiments and adaptations of the embodiments and other variations, modifications, and equivalent arrangements, which have been apparent to or reasonably suggested by those skilled in the art in view of this disclosure and the foregoing description, are possible without departing from the spirit or scope thereof.

Thus, while the present compositions and methods have been described in detail with respect to preferred embodiments, it is to be understood that this disclosure is only illustrative and exemplary and is made merely for purposes of providing a full and enabling disclosure.

The foregoing disclosure is not intended to, or should not be construed to, limit or otherwise exclude any such other embodiments, adaptations, variations, modifications and equivalent arrangements.

Claims (21)

1. A biofilm sealant, comprising:

a polymer binder, wherein the polymer binder is an oxazoline homopolymer or an amplifying or modifying polymer based on an oxazoline homopolymer; and

a component selected from the group consisting of a biocidal compound, an enzyme, an antibody, a phage or mixture of phage, and combinations thereof.

2. The biofilm sealant of claim 1, wherein the oxazoline homopolymer has the structure:

wherein

R₁Is hydrogen, alkyl, alkenyl, alkoxy, alkylamino, alkynyl, allyl, amino, anilino, aryl, benzyl, carboxyl, carboxyalkyl, carboxyalkenyl, cyano, glycosyl, halo, hydroxyl, oxazolinium mesylate, oxazolinium tosylate, oxazolinium triflate, silyloxazolinium, phenol, polyalkoxy, quaternary ammonium, thiol, or thioether group;

R₂is hydrogen, alkyl, alkenyl, alkoxy, alkylamino, alkynyl, allyl, amino, anilino, aryl, benzyl, carboxyl, carboxyalkyl, carboxyalkenyl, cyano, glycosyl, halo, hydroxyl, oxazolinium mesylate, oxazolinium tosylate, oxazolinium triflate, silyloxazolinium, phenol, polyalkoxy, quaternary ammonium, thiol or thioether group, or a macrocyclic structure;

R₃is hydrogen, alkyl, alkenyl, alkoxy, aryl, benzyl, hydroxyalkyl or perfluoroalkyl; and is

n is in the range of 1 to 1,000,000.

3. The biofilm sealant of claim 1, wherein the oxazoline homopolymer based amplification or modification polymer has the structure:

wherein

R₁Is hydrogen, alkyl, alkenyl, alkoxy, alkylamino, alkynyl, allyl, amino, anilino, aryl, benzyl, carboxyl, carboxyalkyl, carboxyalkenyl, cyano, glycosyl, halo, hydroxyl, oxazolinium mesylate, oxazolinium tosylate, oxazolinium triflate, silyloxazolinium, phenol, polyalkoxy, quaternary ammonium, thiol, or thioether group;

R₃is hydrogen, alkyl, alkenyl, alkoxy, aryl, benzyl, hydroxyalkyl or perfluoroalkyl;

n is in the range of 1 to 1,000,000;

b is a monomer repeat unit linked to the oxazoline in the copolymer; and is

m is in the range of 0 to 500,000.

4. The biofilm sealant of claim 3, wherein B is an ethyleneimine having the structure:

wherein

R₁Is hydrogen, alkyl, alkenyl, alkoxy, alkylamino, alkynyl, allyl, amino, anilino, aryl, benzyl, carboxyl, carboxyalkyl, carboxyalkenyl, cyano, glycosyl, halo, hydroxyl, oxazolinium mesylate, oxazolinium tosylate, oxazolinium triflate, silyloxazolinium, phenol, polyalkoxy, quaternary ammonium, thiol, or thioether group;

R₂is hydrogen, alkyl, alkenyl, alkoxy, alkylamino, alkynyl, allyl, amino, anilino, aryl, benzyl, carboxyl, carboxyalkyl, carboxyalkenyl, cyano, glycosyl, halo, hydroxyl, oxazolinium mesylate, oxazolinium tosylate, oxazolinium triflate, silyloxazolinium, phenol, polyalkoxy, quaternary ammonium, thiol or thioether group, or a macrocyclic structure;

R₃is hydrogen, alkyl, alkenyl, alkoxy, aryl, benzyl, hydroxyalkyl or perfluoroalkyl;

R₄is hydrogen, alkyl, alkenyl, alkoxy, aryl, benzyl, hydroxyalkyl or perfluoroalkyl;

m ranges from 0 to 500,000; and is

n is in the range of 1 to 1,000,000.

5. The biofilm sealant of claim 3, wherein B has the structure:

wherein

R₁Is hydrogen, alkyl, alkenyl, alkoxy, alkylamino, alkynyl, allyl, amino, anilino, aryl, benzyl, carboxyl, carboxyalkyl, carboxyalkenyl, cyano, glycosyl, halo, hydroxyl, oxazolinium mesylate, oxazolinium tosylate, oxazolinium triflate, silyloxazolinium, phenol, polyalkoxy, quaternary ammonium, thiol, or thioether group;

R₂is hydrogen, alkyl, alkenyl, alkoxy, alkylamino, alkynyl, allyl, amino, anilino, aryl, benzyl, carboxyl, carboxyalkyl, carboxyalkenyl, cyano, glycosyl, halo, hydroxyl, oxazolinium mesylate, oxazolinium tosylate, oxazolinium triflate, silyloxazolinium, phenol, polyalkoxy, quaternary ammonium, thiol or thioether group, or a macrocyclic structure;

R₃is hydrogen, alkyl, alkenyl, alkoxy, aryl, benzyl, hydroxyalkyl or perfluoroalkyl;

R₄is hydrogen, alkyl, alkenyl, alkoxy, aryl, benzyl, hydroxyalkyl or perfluoroalkyl;

R₅is hydrogen, methyl, ethyl, propyl or another type of alkyl;

m ranges from 0 to 500,000;

n is in the range of 1 to 1,000,000; and is

Anion X^-Is halogen, sulfonate, sulfate, phosphonate, phosphate, carbonate/bicarbonate, hydroxide, or carboxylate.

6. The biofilm sealant of claim 3, wherein B is a polyethyloxazoline modified with polydiallyldimethylammonium chloride having the structure:

wherein

R₁Is hydrogen, alkyl, alkenyl, alkoxy, alkylamino, alkynyl, allyl, amino, anilino, aryl, benzyl, carboxyl, carboxyalkyl, carboxyalkenyl, cyano, glycosyl, halo, hydroxyl, oxazolinium mesylate, oxazolinium tosylate, oxazolinium triflate, silyloxazolinium, phenol, polyalkoxy, quaternary ammonium, thiol, or thioether group;

R₂is a short chain alkyl group;

R₃is a short chain alkyl group;

R₄is hydrogen, alkyl, alkenyl, alkoxy, aryl, benzyl, hydroxyalkyl or perfluoroalkyl;

m ranges from 0 to 500,000;

n is in the range of 1 to 1,000,000; and is

Anion X^-Is halogen, sulfonate, sulfate, phosphonate, phosphate, carbonate, bicarbonate, hydroxide, or carboxylate.

7. The biofilm sealant of claim 3, wherein B is an olefin selected from diallyldimethylammonium chloride, styrene, methoxystyrene, methoxyethylene, or another olefin.

8. The biofilm sealant of claim 1, wherein said polymeric binder is prepared with ethyl oxazoline monomers.

9. The biofilm sealant of claim 8, wherein an ethyl oxazoline is copolymerized with a heterocyclic monomer.

10. The biofilm sealant of claim 1, wherein the polymeric binder utilizes oxazoline pendant groups on the polymer backbone.

11. The biofilm sealant of claim 10, wherein the polymer backbone is an acrylic or styrene-based polymer, or an acrylic or styrene-containing copolymer.

12. The biofilm sealant of claim 1, wherein the germicidal formulation is in a liquid form.

13. The biofilm sealant of claim 1, wherein the biocidal compound is selected from the group consisting of quaternary ammonium compounds, citric acid, sulfamic acid, glycolic acid, lactic acid, lauric and capric acid, quaternary silane salts, triclosan, zinc pyrithione, metal salts, metal oxides, phenols, plant matter, halogens, peroxides, heterocyclic antimicrobials, aldehydes, alcohols, and combinations thereof.

14. The biofilm sealant of claim 13, wherein the quaternary ammonium compound has the structure:

wherein

R₁Is alkyl, alkoxy or aryl, with or without heteroatoms, or saturated or unsaturated;

R₂is alkyl, alkoxy or aryl, with or without heteroatoms, or saturated or unsaturated;

R₃is alkyl, alkoxy or aryl, with or without heteroatoms, or saturated or unsaturated;

R₄is alkyl, alkoxy or aryl, with or without heteroatoms, or saturated or unsaturated;

anion X^-Is halogen, sulfonate, sulfate, phosphonate, phosphate, carbonate, bicarbonate, hydroxide, or carboxylate.

15. The biofilm sealant of claim 13, wherein the quaternary ammonium compound is selected from the group consisting of n-alkyl dimethyl benzyl ammonium chloride, di-n-octyl dimethyl ammonium chloride, dodecyl dimethyl ammonium chloride, saccharin n-alkyl dimethyl benzyl ammonium, 3- (trimethoxysilyl) propyl dimethyl octadecyl ammonium chloride, and combinations thereof.

16. The biofilm sealant of claim 13, wherein said quaternary ammonium compound is present in a composition comprising: n-alkyl dimethyl benzyl ammonium chloride, n-octyl decyl dimethyl ammonium chloride, di-n-decyl dimethyl ammonium chloride and di-n-octyl dimethyl ammonium chloride.

17. The biofilm sealant of claim 13, wherein the quaternary ammonium compound is a polymeric species having the structure:

or

Wherein

R₁Hydrogen, methyl, ethyl, propyl or other carbon alkyl;

R₂hydrogen, methyl, ethyl, propyl or other carbon alkyl;

R₃is methylene, ethylene, propylene or other alkylene linker;

R₄is methylene, ethylene, propylene or other alkylene linker;

R₅hydrogen, methyl, ethyl, propyl or other carbon alkyl;

R₆hydrogen, methyl, ethyl, propyl or other carbon alkyl; and is

n is in the range of 2 to 10,000.

18. The biofilm sealant of claim 17, wherein the polymeric species is a cationic polymer.

19. The biofilm sealant of claim 18, wherein the cationic polymer is a polyamine derived from dimethylamine and epichlorohydrin.

20. The biofilm sealant of claim 13, wherein the quaternary ammonium compound is poly diallyldimethylammonium chloride, poly DADMAC, or a compound comprising a biguanide moiety in a molecule.

21. A method of use, the method comprising:

the biofilm is sealed with a polymer adhesive,

wherein the polymer binder is an oxazoline homopolymer or an amplifying or modifying polymer based on an oxazoline homopolymer.