EP4697962A1

EP4697962A1 - Compositions containing synergistic combination of quaternary ammonium compounds and select polymers

Info

Publication number: EP4697962A1
Application number: EP24721588.2A
Authority: EP
Inventors: Marcella BONESSO; Andre Chieffi; Giulia COLLEDAN; Joseph Frederick CONVERY II; Anna DEL MONACO; Santigie MANSARAY; Remigio Musci; Federico PACINI; Benjamin Aaron PEARL; Antonio Vincenzo PETROZZINO; Tracy Ann Ryan; Anna Kepa SIGMUND; Alberto Simionato; Alessandra TRAVANUT; Elisa VANZETTO; Stephanie Kaitlyn YIU
Original assignee: Reckitt Benckiser LLC
Current assignee: Reckitt Benckiser LLC
Priority date: 2023-04-21
Filing date: 2024-04-22
Publication date: 2026-02-25
Also published as: WO2024218378A1

Abstract

Disinfecting compositions are disclosed comprising a synergistic combination of a benzyl-substituted quaternary ammonium compound and specified polymers. The specified polymers increase the disinfection activity of the benzyl-substituted quaternary ammonium compound in the disinfecting composition. The disclosed disinfecting compositions are substantially free of any other known germ kill actives and do not include any additional quaternary ammonium compound, peroxide, guanide, hypochlorite, isocyanurate, or perborate.

Description

COMPOSITIONS CONTAINING SYNERGISTIC COMBINATION OF QUATERNARY AMMONIUM COMPOUNDS AND SELECT POLYMERS

Cross Reference to Related Applications

This application claims priority to US provisional patent application number 63/497,483, filed 21 April 2023, and GB patent application number 2306664.0, filed 5 May 2023, the contents of each being incorporated herein by reference in its entirety.

Technical Field

Background

Industry leaders have predominantly utilized quaternary ammonium compounds (quats) in order to provide consumers with a germ kill benefit. Quats are typically cheap, readily available, and offer a satisfactory level of disinfection to the consumer. Despite these benefits, quats are known to be toxic to aquatic environments with potential long- lasting effects. Even though quats are expected to biodegrade, regulatory bodies (e.g., the US Environmental Protection Agency) may prohibit individuals from making biodegradability claims if these compounds are present in any amount.

GB2613865 to Gama Healthcare Ltd discloses compositions comprising at least one quaternary ammonium compound which comprises at least one polyquaternium compound, and at least one alcohol ethoxylate.

W02023/036940 to Rhodia Operations discloses an antimicrobial composition comprising a first antimicrobial agent selected from the group consisting of benzalkonium salts, trilocarban, diclosan, triclosan, or combinations thereof, and a second antimicrobial agent which is a cationic polymer (known as polyquaternium 2) having a weight average molecular weight of 1 ,000 to 50,000 represented by the general formula (I):

US2022/233411 to Godrej Consumer Products Ltd discloses a reconstitutable sanitizer formulation which is non-alcoholic in nature and achieves up to 99.9% reduction in microbial load and provides long-lasting protection against microbes for 2-6 hours.

W02020/168046 to Rhodia Operations discloses microbial compositions that include an antimicrobial component having at least one quaternary ammonium compound; a synthetic polymer, such as PQ5, PQ7, PQ11 , or PQ28; an organic acid; a surfactant selected from cationic surfactants, amphoteric surfactants, and combinations thereof; and at least one non-ionic surfactant.

WO201 3/124784 to BASF (China) Company Limited discloses compositions comprising a) an antimicrobial agent selected from the group consisting of biocides containing halogen atoms and/or containing phenolic moieties, formic acid, chlorine dioxide, chlorine dioxide generating compounds, dialdehydes, components containing an antimicrobial metal, such as antimicrobial metal, and b) a polymine, especially polyethyleneimine.

WO201 2/090100 to Kimberly-Clark Worldwide, Inc. discloses durable antimicrobial compositions comprising a carbonate/bicarbonate salt of a quaternary ammonium cation, an organic acid, hydrogen peroxide and a cationic polymer, namely (3-acrylamidopropyl)trimethylammonium chloride monomer combined with another monomer).

RU2235761 to the Gvozdarevas discloses sanitary and hygiene products comprising 1.5-10.5%wt polyhexamethyleneguanidine hydrochloride, 0.5-20.3% wt alkyldimethylbenzyl ammonium chloride, additive, phenoxyethanol and/or phenylethyl alcohol, and/or benzyl alcohol, and/or 1 ,2 propylene glycol, and/or poly-(diallyldimethyl ammonium chloride), and/or cetyl pyridinium chloride, and/or dimethylsulfoxie, and/or amine oxide, and/or carbamide, and/or monoethanolamine, and more.

RU2208048 to Gvozdarev discloses agents comprising polyhexamethylene guanidine, alkyldimethylbenzyl ammonium chloride, phenoxyethanol and/or phenylethyl alcohol and/or benzyl alcohol and/or 1 ,2-propylene glycol and/or poly-(diallyldimethyl- ammonium chlorie), and more.

W02001/030951 to Reckitt & Colman France discloses laundry compositions comprising one or more quaternary ammonium polymers, effective as a textile conditioner on a range of textile materials.

A need remains for disinfecting compositions with low levels of quats.

Summary of Invention

Disclosed are disinfecting composition comprising at least approximately 0.00001 % wt of a benzyl-substituted quaternary ammonium compound, and a polymer selected from the group consisting of poly(diallyldimethylammonium chloride) (PQ6) having a molecular weight <100kDa (PQ6 <100kDa); PQ6 having a molecular weight ranging from 200kDa to 300 kDa (PQ6 200-300kDa); PQ6 having a molecular weight ranging from 400 kDa to 500 kDa (PQ6400-500 kDa); copolymers of vinylpyrrolidone (VP) and quaternized vinylimidazole (QVI)(PQ16) having 5%wt VP and 95% wt QVI (PQ16 5VP-95QVI); PQ16 having 50%wt VP and 95% wt QVI (PQ16 50VP-50QVI); Poly(2-dimethylamino)ethyl methacrylate) methyl chloride quaternary salt (PQ37); 1-propanaminium, N,N,N- trimethyl-3-[(1-oxo-2-propenyl)amino] chloride, homopolymer (A1000); 1- dodecanaminium, N,N-dimethyl-N-[3-[(2-methyl-1-oxo-2-propen-1 -yl)amino]propyl]-, chloride (1 :1), polymer with sodium 2-methyl-2-[(1-oxo-2-propen-1-yl)amino]-1- propanesulfonate (1 :1) and N,N,N-trimethyl-3-[(1 -oxo-2-propen-1-yl)amino]-L propanaminium chloride (1 :1) (C113); and combinations thereof. The disclosed disinfecting compositions may include one or more of the following aspects:

• the disinfecting composition comprising approximately 0.05% wt to approximately 0.2% wt of the benzyl-substituted quaternary ammonium compound and approximately 0.01 % wt to approximately 0.1 % wt of the polymer and the disinfecting composition is an all-purpose cleaner; • the disinfecting composition comprising approximately 0.3% wt to approximately 1.5% wt of the benzyl-substituted quaternary ammonium compound and approximately 0.06% wt to approximately 0.5% wt of the polymer and the disinfecting composition is a dilutable all-purpose cleaner;

• the disinfecting composition comprising approximately 2% wt to approximately 4% wt of the benzyl-substituted quaternary ammonium compound and approximately 0.08% wt to approximately 0.5% wt of the polymer and the disinfecting composition is a laundry sanitizer;

• the disinfecting composition comprising approximately 1 % wt to approximately 2% wt dialkyl dimethyl ammonium chloride, approximately 0.4% wt to approximately 0.75% wt benzyl-substituted quaternary ammonium compound, and approximately 0.08% to approximately 0.15% the polymer and the disinfecting composition is a laundry sanitizer;

• the disinfecting composition comprising approximately 1.25% wt to approximately 3.3% wt of the benzyl-substituted quaternary ammonium compound, approximately 0.25% wt to approximately 4% wt of the polymer, and approximately 4%wt to approximately 6% wt citric acid, and the disinfecting composition is a laundry sanitizer;

• the disinfecting composition comprising approximately 2% wt to approximately 6% wt of the benzyl-substituted quaternary ammonium compound and approximately 0.25% wt to approximately 4% wt of the polymer and the disinfecting composition is a laundry sanitizer;

• the disinfecting composition comprising a reduced concentration of the benzyl- substituted quaternary ammonium compound as compared to a concentration of the benzyl-substituted quaternary ammonium compound in a first comparative disinfecting composition comprising the benzyl-substituted quaternary ammonium compound alone;

• the concentration of the benzyl-substituted quaternary ammonium compound being reduced by fifty percent or more as compared to a concentration of the benzyl- substituted quaternary ammonium compound in a first comparative disinfecting composition comprising the benzyl-substituted quaternary ammonium compound alone; • the disinfecting composition comprising a reduced concentration of the polymer as compared to a concentration of the polymer in a second comparative disinfecting composition comprising the polymer alone;

• the polymer being PQ6 <100kDa, PQ6 200-300 kDa, PQ6 400-500 kDa, PQ16 5VP- 95QVI, A1000, C113, or combinations thereof;

• the polymer being PQ6 <100kDa, PQ6 200-300 kDa, or combinations thereof;

• the polymer being PQ6 <100kDa;

• the polymer being PQ6 200-300 kDa;

• the polymer being PQ6 400-500 kDa;

• the polymer being PQ16 5VP-95QVI;

• the polymer being PQ16 50VP-50QVI;

• the polymer being PQ37;

• the polymer being A1000;

• the polymer being C113;

• the composition being substantially free of a polymer selected from the group consisting of poly(acrylamide-co-diallyldimethylammonium chloride (PQ7), copolymers of vinylpyrrolidone and quaternized vinylimidazole having more vinylpyrrolidone units than quaternized vinylimidazole units (PQ16 70VP-30QVI), 2- pyrrolidinone, 1-ethenyl-polymer with N,N,N-trimethyl-3-[(2-methyl-1-oxo-2- propenyl)amino]-1-propanium chloride (PQ28), and combinations thereof;

• the composition being a laundry composition;

• the laundry composition being a biocide;

• the laundry composition being a sanitizer;

• the laundry composition being a softener;

• the laundry composition being a conditioner;

• the laundry composition being a fabric protector;

• the laundry composition being a fabric protector and biocide;

• the laundry composition being a fabric protector and sanitizer;

• the laundry composition being a conditioner and biocide;

• the laundry composition being a conditioner and sanitizer; • the laundry composition being a softener and biocide;

• the laundry composition being a softener and sanitizer;

• the composition being an all-purpose cleaner;

• the composition being a hard surface disinfectant;

• the composition being a soft surface disinfectant;

• the laundry composition comprising only one benzyl-substituted quaternary ammonium compound;

• the benzyl-substituted quaternary ammonium compound being C12-18 alkyl dimethyl benzyl ammonium chloride;

• the benzyl-substituted quaternary ammonium compound being C12-16 alkyl dimethyl benzyl ammonium chloride;

• the concentration of the benzyl-substituted quaternary ammonium compound being approximately 5% wt to approximately 50% wt less than the concentration of the benzyl-substituted quaternary ammonium compound in the first comparative disinfecting composition;

• the concentration of the benzyl-substituted quaternary ammonium compound being approximately 6% wt to approximately 40% wt less than the concentration of the benzyl-substituted quaternary ammonium compound in the first comparative disinfecting composition;

• the concentration of the benzyl-substituted quaternary ammonium compound being approximately 7% wt to approximately 30% wt less than the concentration of the benzyl-substituted quaternary ammonium compound in the first comparative disinfecting composition;

• the concentration of the benzyl-substituted quaternary ammonium compound being approximately 8% wt to approximately 20% wt less than the concentration of the benzyl-substituted quaternary ammonium compound in the first comparative disinfecting composition;

• the concentration of the benzyl-substituted quaternary ammonium compound being approximately 9% wt to approximately 15% wt less than the concentration of the benzyl-substituted quaternary ammonium compound in the first comparative disinfecting composition; • further comprising water;

• the water comprising less than 17 ppm of calcium and magnesium;

• further comprising approximately 80%wt to approximately 97.5% wt water;

• further comprising approximately 85%wt to approximately 95% wt water;

• the composition being a liquid;

• the composition being a single-phase liquid;

• the composition being substantially free of betaine surfactants

• the composition being substantially free of enzymes;

• the composition being substantially free of an added electrolyte, such as sodium chloride;

• the composition being substantially free of chelant;

• the composition being substantially free of chelant, other than citric acid;

• the composition being substantially free of anionic surfactant;

• the composition being substantially free of alkanolamine, such as monoethanolamine, diethanolamine, triethanolamine, or combinations thereof;

• the composition being substantially free of glycol ether;

• the composition being substantially free of a peroxide;

• the composition being substantially free of hydrogen peroxide;

• the composition being substantially free of bisguanide;

• the composition being substantially free of added alcohol;

• the composition being substantially free of added ethanol;

• the composition being substantially free of an unsaturated fatty alcohol.

Also disclosed are methods of increasing disinfection activity of a benzylsubstituted quaternary ammonium compound in a disinfecting composition by adding a polyquaternium polymer to the disinfecting composition, the polymer being selected from the group consisting of PQ6 <100kDa, PQ6 200-300kDa, PQ6 400-500 kDa, PQ16 5VP- 95QVI, PQ16 50VP-50QVI, PQ37, A1000, C113, and combinations thereof. The disclosed methods may include one or more of the following: the disclosed methods provide reduction of a concentration of the benzylsubstituted quaternary ammonium compound while maintaining the germ kill efficacy of the disinfecting composition; the concentration of the benzyl-substituted quaternary ammonium compound being reduced by 50 % wt or greater.

Terms and Definitions

As used herein: the symbol and terms “approximately” and “about” mean plus or minus 10% of the value stated; the term “a” or “an” means one or more; any and all ranges are inclusive of their endpoints, e.g. a ranging from 1wt% to 10wt% wt includes 1wt% and 10wt% and any concentration between 1wt% and 10wt%; all amounts given in % are % by weight (wt%) unless otherwise stated. When an ingredient does not contain close or equal to 100% active material, two percentages may be provided: one for the weight of the raw material and one for the weight of the active. For example, 7.28 % wt of benzalkonium chloride contains approximately 80% benzalkonium chloride in water, alcohol and/or polypropylene glycol, which equates to approximately 5.82% wt of benzalkonium chloride in the formulation. This would be represented as 7.28 % wt (5.82 % wt) of benzalkonium chloride; the term “benzyl group” is C6H5CH2-; the term “comprising” is inclusive or open-ended and does not exclude any additional elements; the term “consisting of” excludes any additional elements; and the term “consisting essentially of” is in-between, only permitting additional elements that do not materially affect characteristics of the product or process; the phrase “substantially free” means a concentration of less than 0.3 g/L, preferably less than 0.2 g/L, more preferably less than 0.1 g/L, and most preferably less than 0.05 g/L; the abbreviation “q.s.” is short for the Latin term quantum satis which means the amount of which is enough and, as used herein, means the amount of water needed to bring the formulation to 100%wt.; the terms “germ” and “microbe” or “microbial” means microorganisms which causes disease or undesirable effects, such as malodour, and encompasses both bacteria and viruses; the terms “disinfect” or “disinfection” mean no growth observed during the micro testing; the terms “sanitize” or “sanitizer” mean to reduce the level of bacteria (note, not viruses) on a surface to a level that is considered "safe" but not total kill; the terms “biocide” or “biocidal” mean any product that can kill germs, including bacteria and viruses; biocides are substances approved to kill microorganisms and typically registered with a governing body (i.e. , the US Environmental Protection Agency or the European Chemicals Agency (ECHA)); the term “liquid” means a state of matter that conforms to the shape of the container in which it is held at room temperature (18-23°C) and which acquires a defined surface in the presence of gravity; the term “liquid” is readily distinguishable from the terms “solid” and “gas.” Liquids are not pastes, which behaves as a solid until a sufficiently large load or stress is applied, even though a paste is also known as a Bingham plastic fluid; the term “alone” means that no other ingredients are present, in other words, the stated ingredient is the only ingredient; the term “ambient temperature” means room temperature, which may vary depending on the season from approximately 18°C to approximately 28°C, but preferably from approximately 20°C to approximately 25°C.

Detailed Description

Disinfecting compositions are disclosed comprise a synergistic combination of a benzyl-substituted quaternary ammonium compound and a specified polymer. The disclosed compositions comprise a low concentration of quat, but are still able to obtain germ kill.

The disclosed compositions comprise a benzyl-substituted quaternary ammonium compound. Benzyl-substituted quaternary ammonium compounds have the formula: C6H₅CH₂NR3⁺X-, wherein each R is independently a C1 -C18 hydrocarbon group and X is an alkali metal, saccharinate group, or carbonate group. R is not an ether or alkoxy group. A C1-3 alkyl group may also be linked to the benzyl ring (e.g., ethylbenzyl C12-18 dimethyl benzyl ammonium chloride). Preferably the benzyl-substituted quaternary ammonium compound has the formula C6H5CH2N(CH3)2R⁺X wherein R is a C12-C18 or C12-C16 alkyl group and X is Cl.

The polymer is selected from the group consisting of poly(diallyldimethylammonium chloride) (PQ6) having a molecular weight <100kDa (PQ6 <100kDa); PQ6 having a molecular weight ranging from 200kDa to 300 kDa (PQ6 200- 300kDa); PQ6 having a molecular weight ranging from 400 kDa to 500 kDa (PQ6 400- 500 kDa); copolymers of vinylpyrrolidone (VP) and quaternized vinylimidazole (QVI)(PQ16) having 5%wt VP and 95% wt QVI (PQ16 5VP-95QVI); PQ16 having 50%wt VP and 95% wt QVI (PQ16 50VP-50QVI); Poly(2-dimethylamino)ethyl methacrylate) methyl chloride quaternary salt (PQ37); 1-propanaminium, N,N,N-trimethyl-3-[(1-oxo-2- propenyl)amino] chloride, homopolymer (A1000); 1-dodecanaminium, N,N-dimethyl-N- [3-[(2-methyl-1-oxo-2-propen-1-yl)amino]propyl]-, chloride (1 :1), polymer with sodium 2- methyl-2-[(1-oxo-2-propen-1-yl)amino]-1 -propanesulfonate (1 :1) and N,N,N-trimethyl-3- [(1 -oxo-2 -propen-1-yl)amino]-L propanaminium chloride (1 :1) (C113); and combinations thereof.

The concentration of the benzyl-substituted quaternary ammonium compound is approximately 5% wt to approximately 50% wt less than the concentration of the benzyl- substituted quaternary ammonium compound in a comparative disinfecting composition comprising the benzyl-substituted quaternary ammonium compound alone, preferably approximately 6% wt to approximately 40% wt less, more preferably approximately 7% wt to approximately 30% wt less, even more preferably approximately 8% wt to approximately 20% wt less, and more preferably approximately 9% wt to approximately 15% wt less. In other words and as shown in the examples that follow, the same level of germ kill may be obtained by two compositions, the first composition comprising the benzyl-substituted quaternary ammonium compound without the disclosed synergist polymres and a second which contains the disclosed polymers and approximately 5% wt to approximately 50% wt less of the benzyl-substituted quaternary compound than in the first composition. To achieve germ kill with the low level of quat, the disclosed composition comprise a polymer, as defined above.

The combination of benzyl-substituted quaternary ammonium compound and specified polymer may comprise all the ingredients necessary for germ kill. As a result, the disclosed compositions may be substantially free of any other known germ kill actives. The benzyl-substituted quaternary ammonium compound is the only quat used in the disclosed compositions. In other words, the disclosed compositions do not include any additional quaternary ammonium compounds, such as dialkyl dimethyl ammonium chloride. Multiple quaternary ammonium species may help achieve sanitization and/or provide better breadth of germ kill. As a result, most commercial sanitizers include a blend of two or more quaternary ammonium compounds. As shown in the examples that follow, Applicant has surprisingly discovered that a composition comprising only the benzyl-substituted quaternary ammonium compound may achieve better than or equivalent germ kill to a composition comprising a multi-quat system. Dialkyl dimethyl ammonium chlorides are currently more expensive than benzyl-substituted quaternary ammonium compounds. As a result, the disclosed compositions provide equivalent or better germ kill in a more cost effective manner.

Applicant also believes that using the benzyl-substituted quaternary ammonium compound as the only quat in acidic formulations provides an improved safety profile as compared to products containing two or more quaternary ammonium compounds in solutions. In vitro assays in accordance with OECD 437 were performed on multiple different compositions with various levels of quaternary ammonium compounds. Applicant was surprised to find that no eye corrosivity was observed during this testing. Based on these results, packaging for the disclosed compositions will not require a child resistant closure. Currently, US in-market sanitizers require child resistant closures due to eye and/or skin corrosivity.

The disclosed compositions do not include any additional known germ kill actives in order to achieve germ kill. As a result, the disclosed compositions are also substantially free of peroxides, such as hydrogen peroxide or peracids. The disclosed compositions are also substantially free of guanides, such as bisguanide. The disclosed compositions are substantially free of alkali metal hypochlorites. While hypochlorites deliver germ kill, they are also known to damage many types of coloured fabrics. The disclosed compositions are substantially free of isocyanurates. The disclosed compositions are also substantially free of borates, such as boric acid or perborates.

The disclosed compositions may further comprise water, preferably soft water. Soft water comprises less than 17 ppm of calcium and magnesium. The disclosed compositions may comprise approximately 80%wt to approximately 97.5% wt water. As a result the disclosed compositions may be a liquid, preferably a single phase liquid.

The disclosed compositions may further comprise customary ingredients typically included in disinfecting compositions, such as anionic surfactants, non-ionic surfactants, organic acids and their salts, chelants, thickeners, pH adjusters, opacifiers, non-aqueous solvents, fragrances, dyes, and the like.

Alternatively, the disclosed compositions may be substantially free of non-ionic surfactants. Specially, the disclosed compositions may be substantially free of betaine surfactants. The disclosed compositions may also be substantially free of unsaturated fatty alcohols.

The disclosed compositions may be substantially free of anionic surfactants, such as alkyl sulfates and alkyl ether sulfates.

The disclosed compositions may further comprise enzymes for additional benefits. Cellulase keeps clothes looking new longer. Phosphodiesterase helps remove body stains from clothes. Amylase and protease help remove generic stains from clothes, including enzymatic stains left behind by detergents.

Alternatively, the disclosed compositions may be substantially free of enzymes, particularly when other benefits are not needed.

The disclosed compositions may be substantially free of alkanolamine, such as monoethanolamine, diethanolamine, triethanolamine, or combinations thereof.

The disclosed compositions may be substantially free of non-aqueous solvents, such as glycol ethers. The disclosed compositions may also be substantially free of added alcohols, such as ethanol. One of ordinary skill in the art will recognize that the benzyl-substituted quaternary ammonium compounds are frequently supplied in an alcohol or glycol solvent. However, more of these solvents are not deliberately added to the disclosed compositions. The disclosed compositions may be substantially free of an added electrolyte, such as sodium chloride.

The disinfecting composition may be used to disinfect hard or soft surfaces. For example, the disinfecting may be used in all-purpose cleaners or hard surface disinfectants, such as triggers, dilutables, or wipes. Alternatively, the disinfecting composition may be used in laundry products, such as laundry biocides, laundry sanitizers, laundry softeners, laundry conditioners, laundry fabric protectors, or any combination thereof. Preferably, the disclosed laundry compositions may serve two or more functions. For example, the disclosed laundry composition may be a fabric protector and biocide, or a fabric protector and sanitizer, or a softener and biocide, or a softener and sanitizer, or a conditioner and biocide, or a conditioner and sanitizer. Alternatively, the disclosed laundry composition may be a fabric protector and softener and conditioner. Alternatively, the disclosed composition may be a biocide and sanitizer.

Contrary the disclosures in the prior art and as shown in the examples that follow, not all polyquaternium polymers behave in the same manner. Indeed, a large quantity of some polyquaternium polymers would be needed to increase the efficacy of BKC. And BKC is inexpensive. As a result, these polyquaternium polymers may be undesirable to use to increase the germ kill of benzyl-substituted quaternary ammonium compounds, especially if they are toxic to aquatic environment. As a result, the disclosed compositions may be substantially free of a polyquaternium polymer selected from the group consisting of poly(acrylamide-co-diallyldimethylammonium chloride (PQ7), copolymers of vinylpyrrolidone and quaternized vinylimidazole having more vinylpyrrolidone units than quaternized vinylimidazole units (PQ16 70VP-30QVI), 2- pyrrolidinone, 1-ethenyl-polymer with N,N,N-trimethyl-3-[(2-methyl-1-oxo-2- propenyl)amino]-1-propanium chloride (PQ28), and combinations thereof. Based on the chemical structure and to be confirmed by testing, Applicant believes that PQ33 would perform worse antimicrobially than PQ37 and would also be undesirable for use in the teachings herein.

Methods are disclosed for reducing a concentration of a benzyl-substituted quaternary ammonium compound in a disinfecting composition while maintaining the germ kill efficacy of the disinfecting composition by adding a polymer to the disinfecting composition. In other words, the concentration of a benzyl-substituted quaternary ammonium compound in a disinfecting composition may be reduced as compared to the same comparative disinfecting composition comprising the benzyl-substituted quaternary ammonium compound alone by adding a first polyquaternium polymer to the disinfecting composition.

As shown in the example that follows, the concentration of benzyl-substituted quaternary ammonium compounds may be reduced when specific polymers are added to the formulation and still provide equivalent germ kill to compositions of the benzyl- substituted quaternary ammonium compounds without the polymers. Benzyl-substituted quaternary ammonium compounds are known to be toxic to aquatic environments. The ability to reduce the concentration of the benzyl-substituted quaternary ammonium compound is therefore beneficial. Additionally, the formulation does not require a large percentage of these polymers, which helps contain formulations costs. The polymer is selected from the group consisting of poly(diallyldimethylammonium chloride) (PQ6) having a molecular weight <100kDa (PQ6 <100kDa); PQ6 having a molecular weight ranging from 200kDa to 300 kDa (PQ6 200-300kDa); PQ6 having a molecular weight ranging from 400 kDa to 500 kDa (PQ6 400-500 kDa); copolymers of vinylpyrrolidone (VP) and quaternized vinylimidazole (QVI)(PQ16) having 5%wt VP and 95% wt QVI (PQ16 5VP-95QVI); PQ16 having 50%wt VP and 95% wt QVI (PQ16 50VP-50QVI); Poly(2-dimethylamino)ethyl methacrylate) methyl chloride quaternary salt (PQ37); 1- propanaminium, N,N,N-trimethyl-3-[(1-oxo-2-propenyl)amino] chloride, homopolymer (A1000); 1 -dodecanaminium, N, N-dimethyl-N-[3-[(2-methyl-1 -oxo-2-propen-1 - yl)amino]propyl]-, chloride (1 :1), polymer with sodium 2-methyl-2-[(1-oxo-2-propen-1- yl)amino]-1 -propanesulfonate (1 :1) and N,N,N-trimethyl-3-[(1-oxo-2-propen-1-yl)amino]- L propanaminium chloride (1 :1) (C113); and combinations thereof.

Exemplary dilutable all purpose cleansers comprise approximately 0.3% wt to approximately 1.5% wt a benzyl-substituted quaternary ammonium compound and approximately 0.06% to approximately 0.16% a first polyquaternium polymer.

Exemplary dilutable all purpose cleaners comprise:

Exemplary all purpose cleansers cleaners comprise approximately 0.05% wt to approximately 0.5% wt a benzyl-substituted quaternary ammonium compound and approximately 0.01 % to approximately 0.1 % a first polyquaternium polymer.

Exemplary all purpose cleaners comprise: Exemplary laundry compositions comprise approximately 2% wt to approximately

4% wt benzyl-substituted quaternary ammonium compound and approximately 0.08% to approximately 0.5% a first polyquaternium polymer,

Exemplary laundry compositions comprise:

Exemplary laundry compositions comprise approximately 1 % wt to approximately 2% wt dialkyl dimethyl ammonium chloride, approximately 0.4% wt to approximately 0.75% wt benzyl-substituted quaternary ammonium compound, and approximately 0.08% to approximately 0.5% a first polyquaternium polymer, Exemplary laundry compositions comprise:

Exemplary laundry compositions comprise approximately 1.25% wt to approximately 3.3% wt of a benzyl-substituted quaternary ammonium compound, approximately 0.25% wt to approximately 4% of a first polyquaternium compound, and three or more pH adjusters, the pH adjusters being selected from the group consisting of citric acid, sodium citrate, an alkali hydroxide, and combinations thereof.

For example, the exemplary laundry compositions comprise:

When used during the last rinse cycle of a laundry washing process, Applicant believes that these laundry compositions will obtain a 5 logic reduction in Staphylococcus aureus, Enterococcus hirae, Escherichia coli, and Pseudomonas aeruginosa a 4 logic reduction in Candida albicans. This means the above composition will qualify as a laundry disinfectant composition under European regulations.

The laundry compositions may further comprise a softener, which provides softness effect to the fabric, for example to cotton fibers. The exemplary laundry compositions may comprise, consist essentially of, or consist of:

Alternatively, the exemplary laundry compositions comprise, consist essentially of, or consist of: additional benefits to clothes treated with the disclosed compositions. For example, these exemplary laundry compositions comprise, consist essentially of, or consist of: help keep clothes treated with the disclosed compositions looking new for longer. For example, these exemplary laundry compositions comprise, consist essentially of, or consist of: The laundry compositions may further comprise a phosphodiesterase enzyme, which help remove body stains from clothes treated with the disclosed compositions. For example, these exemplary laundry compositions comprise, consist essentially of, or consist of: enzyme, which may help remove generic stains from clothes treated with the disclosed compositions, including enzymatic stains left behind by detergents. For example, these exemplary laundry compositions comprise, consist essentially of, or consist of: For aesthetic reasons, the laundry compositions may further comprise thickeners, fragrances, and/or dyes. For example, these exemplary laundry compositions comprise, consist essentially of, or consist of:

Compositions that meet germ kill, softness, and other aesthetic parameters may comprise, consist essentially of, or consist of:

In another example, the exemplary laundry compositions comprise, consist essentially of, or consist of:

Compositions that meet germ kill and other aesthetic parameters may comprise, consist essentially of, or consist of: may comprise, consist essentially of, or consist of: Compositions that meet germ kill and help remove body stains from clothes treated with the disclosed compositions may comprise, consist essentially of, or consist of:

Compositions that meet germ kill and help remove generic stains from clothes treated with the disclosed compositions, including enzymatic stains left behind by detergents, may comprise, consist essentially of, or consist of:

Inclusion of encapsulated fragrances in the laundry compositions helps fabrics remain fresh long after washing. For example, these exemplary laundry compositions comprise, consist essentially of, or consist of:

Alternatively, exemplary laundry compositions comprise approximately 2% wt to approximately 6% wt of a benzyl-substituted quaternary ammonium compound, approximately 0.25% wt to approximately 4% wt of the polymer, approximately 0.3% wt to approximately 1 .5% wt of an alkylamine oxide, and approximately 0.4% wt to approximately 1 % wt of phenoxyethanol.

Exemplary laundry compositions comprise:

When used during the last rinse cycle of a laundry washing process, Applicants believe these laundry compositions obtain a 5 log reduction as tested according to EN1276 and EN1650 in Staphylococcus aureus, Enterococcus hirae, Escherichia coli, and Pseudomonas aeruginosa and a 4 log reduction in Candida albicans. This means the above formulation qualifies as a laundry disinfectant composition under European regulations.

The laundry compositions may further comprise a fabric conditioner, which provides a softness effect to the fabric, for example to cotton fibers. The exemplary laundry compositions may comprise, consist essentially of, or consist of: For aesthetic reasons, the laundry compositions may further comprise thickeners. The thickeners produce a composition having a viscosity ranging from 100 cPs to 500 cPs as measured using a Brookfield viscometer with LV62 spindle at 50 RPM at ambient temperature. For example, these exemplary laundry compositions comprise, consist essentially of, or consist of:

Formulations that provide germ kill, viscosity, and softness may comprise, consist essentially of, or consist of: These formulations remain clear, single phase solutions, particularly when the cellulose based thickener is 2-hydroxyethyl ether cellulose and the esterquat is a liquid N,N’- di(alkylcarboxyethyl)-N-hydroxyethyl-N-methylammonium methyl sulfate.

For aesthetic reasons, the laundry compositions may further comprise a suspending agent and an opacifier or encapsulated fragrance. Encapsulated fragrances in the laundry formulations helps fabrics remain fresh long after washing. For example, these exemplary laundry compositions comprise, consist essentially of, or consist of:

In this embodiment, polyquaternium 37 may act as both a germ kill booster and suspending agent for the opacifier and/or encapsulated fragrance.

Dye and additional fragrance may be added to improve the aesthetic appeal of the resulting formulation. For example, these exemplary laundry compositions comprise, consist essentially of, or consist of:

Liquid products are also disclosed. The liquid products comprise a container comprising any of the liquid compositions disclosed above. Any container suitable for holding liquids may be used. The disclosed liquid compositions may not trigger the requirement for child-resistant packaging under 40 C.F.R. § 157, subpart B. As a result, the container may not require a child-resistant cap. Child-resistant packaging is required if the formulation: has an acute oral lethal dose of 1 .5 g/kg or less; has an acute dermal lethal dose of 2,000 mg/kg or less; has acute inhalation of lethal concentration of 2 mg/L or less; is corrosive to the eye (causing irreversible destruction of ocular tissue) or causes corneal involvement or irritation persisting for 21 days or more; is corrosive to the skin (causing tissue destruction into the dermis and/or scarring) or causes severe skin irritation (severe erythema or edema) at 72 hours; has such characteristics that, based upon human toxicological data, use history, accident data, or such other evidence as available, the EPA determines there is serious hazard of accidental injury or illness which child-resistant packaging could reduce.

Methods of sanitizing a surface using any of the disclosed compositions are also disclosed. The disclosed methods comprise contacting the surface with the disclosed compositions. Examples

The following examples illustrate exemplary formulations as well as preferred embodiments of the invention. It is to be understood that these examples are provided by way of illustration only and that further useful formulations falling within the scope of the present invention and the claims may be readily produced by one skilled in the art without deviating from the scope and spirit of the invention.

The compositions in the following examples were prepared using the ingredients identified in Table A:

Table A:

Inoculum preparation:

Take well-defined and typical colonies of Staphylococcus epidermidis from a recent plate of tryptic soy agar (TSA), dissolve and vortex them in a tube containing 30mL of tryptic soy broth (TSB) and incubate for 17+/-1 h at 37°C+/-1 °C. Quantify by plate count in TSA (incubated for 48h+/-1 h at 37°C+/-1 °C). Use the broth culture suspension within seven (7) days after the incubation period. Vortex and take 0.2mL from the broth culture and dilute in appropriate volume of 0.85% NaCI to normalize the strain at 3-5x10^A5 CFU/mL

Test sample gradient creation:

Using a micropipette, add 100pL of TSB in a 96-well microtiter plate format.

Dispense 100pL of the test sample (polymer) in column 1 (from row A to row H depending on the number of test samples) and 100pL of the same test sample (polymer) in column 2 in their respective rows within 30 minutes of preparing the solution if it has been previously diluted, (both samples are the same)

Using a micropipette take 100pL of the sample from column 2 and dilute it in column 3 performing a 1 : 1 dilution with the diluent already present in the wells, proceeding with a serial dilution up to column 9. Discard the remaining 100 pL.

Inoculum:

Within 30 minutes of preparing the gradient and inoculum bacterial suspension, dispense 20 pL of a solution of BKC in the wells from columns 2 to 9. Dispense 100 pL of inoculum using a micropipette into each well in columns 2 to 10. Columns 1 and 11 are the sample sterility test and negative test control columns, respectively. No growth should be observed in these columns. Column 10 is the positive test control and growth should be observed.

To test the polymers antimicrobial activity alone (without BKC) repeat the steps above, without the addition of the 20 pL solution of BKC.

The inoculum must be between 2.5 - 4.5 x 10^A5 CFU/mL in each well. Incubate the microwell plate for 24h+/-1 h at 37°C+/-1 °C.

The minimum inhibitory concentration (MIC) is determined by visually checking the wells for growth. The MIC is defined as the minimal concentration of polymer in the corresponding well without visible growth after 24 hours of incubation. The tests were performed two times for most of the listed polyquaternium polymers. The MIC of BKC alone ranged from 5-8 ppm or 0.3-0.8 ppm in R&D test conditions. One of ordinary skill in the art will recognize that micro testing is not an exact science and results may vary significantly, especially in R&D test conditions. However, these results demonstrate the consistent synergy or lack of synergy between BKC and the polymers. The results are provided in Table 1 :

Table 1:

** N/A = not analyzed

As shown in Table 1 above, all 3 kDa of PQ6, PQ16 5VP-95QVI, A1000, and C113 exhibit excellent synergy with BKC, especially PQ6 <100kDa and PQ6 200-300 kDa. The combinations permit the disclosed disinfecting concentrations to significantly reduce the quantity of BKC without adding a large quantity of the polymer to the disinfecting compositions.

PQ16 50VP-50QVI and PQ37 also demonstrate synergy, but require a larger quantity of polymer to do so.

PQ7, PQ16 70VP-30VPI and PQ28 require a large quantity of polymer to increase the efficacy of BKC. And BKC is inexpensive. As a result, these polyquaternium polymers may be undesirable to use to increase the germ kill of benzyl-substituted quaternary ammonium compounds, especially if they are toxic to aquatic environment.

Example 2 - Antimicrobial Activity

The antimicrobial efficacy of the formulations in Table 2 was determined using ASTM E2274-16 entitled the Standard Test Method for Evaluation of Laundry Sanitizers and Disinfectants (version 15 April 2016). A greater than 3-log reduction of all organisms (Klebsiella pneumoniae, Staphylococcus aureus) on both the test fabric swatch & simulated wash water for a contact time of 1 to 60 minutes (determined by product specification) at a testing temperature ranging from 4°C to 60°C+1.0°C (determined by product specification) is required to pass the ASTM E2274-16 for a sanitization product. For a disinfecting product, total kill must be achieved. Additional and optional contact times, temperatures, and test organisms may be used.

Microorganisms were subcultured on Nutrient Agar A (through at least one daily transfer), incubating at 35 ± 2°C. On the day prior to testing, the slant was washed and cells transferred into French square bottles containing 20 mL of solidified Nutrient Agar B. The cells were then incubated between 18 to 24 hours at 35 ± 2°C, agar side down. Growth was then removed using 3-mL dilution fluid and 5 sterile glass beads to suspend the growth. Cultures were then standardized to yield approximately 10⁸ CFUs per mL of S. aureus and 10⁹ CFUs of K. pneumoniae.

The tests were performed using “clean” experimental conditions, which means no organic soil load was included for this test method. For laundry sanitizers/softeners, the desired experimental conditions are “clean conditions” because the laundry sanitizer/softener is used after a laundry detergent in a laundry washing process, i.e. on clean laundry.

As the test is designed to simulate killing bacteria on fabric, the test fabric also needs to be prepared. 300g of test fabric was boiled for 1 hour in 3L of deionized water containing 1.5g NaCOs and 1.5g nonionic wetting agent. The fabric was then rinsed in boiling water, then in cold water, until there was no longer the appearance of foam. The fabric was then air dried for 24 hours at room temperature. Once dry, the fabric was cut into 2 inch strips, weighing 15 ± 0.1 grams each. The fabric was then secured onto a stainless steel spindle & wrapped precisely 12 times & then secured (as to represent laundry ballast). Furthermore, 1 by 1 .5 inch fabric swatches were cut from the remaining fabric & used as carriers for microorganisms. At least 3 carriers were prepared for each organism tested. On the day of testing, these carriers were inoculated with 0.030 mL of prepared inoculum, taking care to distribute evenly across the 1 by 1.5 inch swatches. Swatches were dried in a 35 ± 2°C incubator for no longer than 30 minutes, and were used within 1 hour of drying. When ready, they were to be placed between the 6^th and 7^th folds of the simulated ballast, without any overlap of the swatches.

Experimentally, a 1 :315 dilution of test substance was prepared in hard water (400 ppm CaCOs) within 3 hours of testing. Approximately 150 mL of this test substance (simulated rinse water) was used to submerge the fabric carrier & ballast in a sterile exposure chamber that is agitated for the desired contact time. The test was allowed to proceed for 25 minutes and then the simulated rinse water and fabric carriers were separately neutralized. The carriers were then plated, and both plates/tubes are incubated for 48±2 hours at 35±2°C. The results were evaluated for sanitization (in terms of log reduction) or for disinfection (positive or negative result for growth). The results are provided in Table 2:

Table 2:

These resu ts demonstrate that BKC is more efficacious than Dialkyl Dimethy

Ammonium Chlorides (DDAC or 2080 and 1010) alone (at an equivalent level). The results also suggest that BKC alone is performing better (or at least the same as) a blend of BKC and DDAC. Finally, these results demonstrate that the concentration of BKC can be lowered by addition of PQ37 (E2 and E4) and still obtain germ kill equivalent to that obtained from a higher concentration of BKC (E1).

For context, it is typically observed in the ASTM 2274 method that meeting success criteria on the swatch is more challenging than in the wash water, which may explain the discrepancy between E5 and E6. This is likely due to mobility of the active agents and their ability to penetrate deep into the simulated ballast to reach the inoculated fabric carriers. Inversely, the simulated rinse water is similar to a solution, where there is little interference between the active substance and any particles suspended therein.

Example 3 - Micro Efficacy Synergies - PQ6

The antimicrobial efficacy of the formulations in Table 3 was determined using ASTM E2274-16 entitled the Standard Test Method for Evaluation of Laundry Sanitizers and

Disinfectants (version 15 April 2016), as described in Example 2.

Table 3:

Table 3 demonstrates that adding PQ6 boosts the micro efficacy of the formula. By adding 0.4% active amount of PQ6 to Formula E7, we were able to reduce the quat by 0.7% and to achieve a similar micro result. Formula E8 also shows a significant improvement in micro efficacy as we reduced the quat by 0.25% and added 0.4% PQ6 compared to Formula E6. Because many quats used for germ kill can add corrosivity or environmental hazards to a product, finding synergies such as PQ6 can lead to better optimized formulations.

The foregoing description of various aspects of the invention has been presented for purposes of illustration and description. Embodiments and/or features therein may be freely combined with one another. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and obviously, many modifications and variations are possible. Such modifications and variations that may be apparent to a person skilled in the art are intended to be included within the scope of the invention as defined by the accompanying claims.

Claims

We claim:

1. A disinfecting composition comprising:

- at least approximately 0.00001 % wt of a benzyl-substituted quaternary ammonium compound, and

- a polymer selected from the group consisting of poly(diallyldimethylammonium chloride) (PQ6) having a molecular weight <100kDa (PQ6 <100kDa); PQ6 having a molecular weight ranging from 200kDa to 300 kDa (PQ6 200-300kDa); PQ6 having a molecular weight ranging from 400 kDa to 500 kDa (PQ6 400-500 kDa); copolymers of vinylpyrrolidone (VP) and quaternized vinylimidazole (QVI)(PQ16) having 5%wt VP and 95% wt QVI (PQ16 5VP-95QVI); PQ16 having 50%wt VP and 95% wt QVI (PQ16 50VP-50QVI); Poly(2-dimethylamino)ethyl methacrylate) methyl chloride quaternary salt (PQ37); 1-propanaminium, N,N,N-trimethyl-3-[(1- oxo-2-propenyl)amino] chloride, homopolymer (A1000); 1-dodecanaminium, N,N- dimethyl-N-[3-[(2-methyl-1 -oxo-2-propen-1 -yl)amino]propyl]-, chloride (1 :1), polymer with sodium 2-methyl-2-[(1 -oxo-2-propen-1 -yl)amino]-1 -propanesulfonate (1 :1 ) and N,N,N-trimethyl-3-[(1-oxo-2-propen-1-yl)amino]-L propanaminium chloride (1 :1) (C113); and combinations thereof, wherein the disinfecting composition is substantially free of any other known germ kill active and does not include any additional quaternary ammonium compound, peroxide, guanide, hypochlorite, isocyanurate, or perborate.

2. The disinfecting composition of claim 1 , wherein the disinfecting composition comprises approximately 0.05% wt to approximately 0.2% wt of the benzyl-substituted quaternary ammonium compound and approximately 0.01 % wt to approximately 0.1 % wt of the polymer and the disinfecting composition is an all-purpose cleaner.

3. The disinfecting composition of claim 1 , wherein the disinfecting composition comprises approximately 0.3% wt to approximately 1.5% wt of the benzyl-substituted quaternary ammonium compound and approximately 0.06% wt to approximately 0.5% wt of the polymer and the disinfecting composition is a dilutable all-purpose cleaner.

4. The disinfecting composition of claim 1 , wherein the disinfecting composition comprises approximately 2% wt to approximately 4% wt of the benzyl-substituted quaternary ammonium compound and approximately 0.08% wt to approximately 0.5% wt of the polymer and the disinfecting composition is a laundry sanitizer.

5. The disinfecting composition of claim 1 , wherein the disinfecting composition comprises approximately 1 % wt to approximately 2% wt of a dialkyl dimethyl ammonium chloride, approximately 0.4% wt to approximately 0.75% wt of the benzyl-substituted quaternary ammonium compound, and approximately 0.08% to approximately 0.15% of the polymer and the disinfecting composition is a laundry sanitizer.

6. The disinfecting composition of claim 1 , wherein the disinfecting composition comprises approximately 1.25% wt to approximately 3.3% wt of the benzyl-substituted quaternary ammonium compound, approximately 0.25% wt to approximately 4% wt of the polymer, and approximately 4%wt to approximately 6% wt of citric acid, and the disinfecting composition is a laundry sanitizer.

7. The disinfecting composition of claim 1 , wherein the disinfecting composition comprises approximately 2% wt to approximately 6% wt of the benzyl-substituted quaternary ammonium compound and approximately 0.25% wt to approximately 4% wt of the polymer and the disinfecting composition is a laundry sanitizer.

8. The disinfecting composition according to any one of claims 1 to 7, wherein the polymer is PQ6 <100kDa, PQ6 200-300 kDa, PQ6400-500 kDa, PQ16 5VP-95QVI, A1000, C113, or combinations thereof.

9. The disinfecting composition according to any one of claims 1 to 8, wherein the polymer is PQ6 <100kDa, PQ6 200-300 kDa, or combinations thereof.

10. The disinfecting composition according to any one of claims 1 to 8, wherein the polymer is PQ6 400-500 kDa

11 . The disinfecting composition according to any one of claims 1 to 8, wherein the polymer is PQ16 5VP-95QVI.

12. The disinfecting composition according to any one of claims 1 to 8, wherein the polymer is PQ16 50VP-50QVI

13. The disinfecting composition according to any one of claims 1 to 8, wherein the polymer is PQ37

14. The disinfecting composition according to any one of claims 1 to 9, wherein the polymer is A1000, C113, or combinations thereof.

15. A method of increasing disinfection activity of a benzyl-substituted quaternary ammonium compound in a disinfecting composition by adding a polyquaternium polymer to the disinfecting composition, the polymer being selected from the group consisting of PQ6 <100kDa, PQ6 200-300kDa, PQ6 400-500 kDa, PQ16 5VP-95QVI, PQ16 50VP- 50QVI, PQ37, A1000, C113, and combinations thereof.