CN116601277A

CN116601277A - Method for removing microorganisms from clothes after washing

Info

Publication number: CN116601277A
Application number: CN202080107567.2A
Authority: CN
Inventors: 李飞; 刘玉祥
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 2020-12-01
Filing date: 2020-12-01
Publication date: 2023-08-15
Also published as: WO2022115988A1; JP2023548699A

Abstract

There is provided a method for removing microorganisms from clothes after washing, wherein the method comprises the steps of: a) Providing a laundry article in a washing machine; and b) contacting the laundry article during a wash sub-cycle of the washing machine with a liquid detergent composition comprising a surfactant system and an antimicrobial agent selected from diphenyl ethers, wherein the surfactant system comprises C ₆ ‑C ₂₀ Linear Alkylbenzene Sulfonate (LAS) as the primary surfactant.

Description

Method for removing microorganisms from clothes after washing

Technical Field

The application relates to a method for removing microorganisms from laundry after washing, comprising the following steps: a) Providing a laundry article in a washing machine; and b) contacting the laundry article during a wash sub-cycle of the washing machine with a liquid detergent composition comprising a surfactant system and an antimicrobial agent selected from diphenyl ethers, wherein the surfactant system comprises C ₆ -C ₂₀ Linear Alkylbenzene Sulfonate (LAS) as the primary surfactant.

Background

In addition to the original intended function, consumer products have evolved to address the needs of users for antimicrobial benefits. For example, users desire antimicrobial laundry detergent products that have antimicrobial benefits on fabrics while cleaning the fabrics. Currently, various antimicrobial agents (e.g., bleach, chloroxylenol (PCMX), benzalkonium chloride (BKC), diphenyl ether) are known to be useful in consumer product formulations to provide antimicrobial effects. Antimicrobial agents include two main types, one of which is used as an agent (e.g., bleach, PCMX, BKC) for removing microorganisms during washing and the other is used (e.g., diphenyl ether) during storage or use.

However, achieving the desired antimicrobial efficacy remains challenging. In particular, no known antimicrobial detergent products are capable of delivering post-wash microbial removal during storage or use of the garment. In particular, for those antimicrobial agents which are used as agents for removing microorganisms, they can only function during washing because they cannot be deposited on clothes. On the other hand, diphenyl ether can be used as a preventive means for the growth of microorganisms during the use of clothes after being deposited on the clothes by washing, but cannot effectively remove microorganisms already present on the clothes. However, consumers desire to provide antimicrobial detergent products that are capable of delivering not only the benefits of post-wash microbial prevention, but also the benefits of post-wash microbial removal.

Accordingly, there is a continuing need for laundry detergent compositions that are capable of delivering effective benefits for post-wash removal of microorganisms from clothes.

Disclosure of Invention

One surprising and unexpected discovery of the present application is: comprising C ₆ -C ₂₀ The combination of a surfactant system with Linear Alkylbenzene Sulfonate (LAS) as the primary surfactant and an antimicrobial agent selected from biphenyl in a liquid detergent formulation can provide effective benefits for the removal of microorganisms from clothes after washing.

In particular, the present application provides a liquid detergent composition comprising from 2% to 60% by weight of the composition of a surfactant system and from 0.01% to 1% by weight of the composition of an antimicrobial agent which is a hydroxydiphenyl ether of formula (I):

wherein:

each Y is independently selected from chlorine, bromine or fluorine,

each Z is independently selected from SO ₂ H、NO ₂ Or C ₁ -C ₄ An alkyl group, a hydroxyl group,

r is 0, 1, 2 or 3,

o is 0, 1, 2 or 3,

p is 0, 1 or 2,

m is 1 or 2, and

n is 0 or 1

Wherein the surfactant system comprises C ₆ -C ₂₀ Linear Alkylbenzene Sulfonate (LAS) as the primary surfactant.

Accordingly, the present application relates in one aspect to a method of removing microorganisms from a laundry article after washing, the method comprising the steps of:

a) Providing a laundry article in a washing machine; and

b) Contacting the laundry article with a liquid detergent composition according to the present disclosure during a wash sub-cycle of the washing machine.

In another aspect, the present application relates to the use of a liquid detergent composition according to the present disclosure for removing microorganisms from laundry articles after washing.

Preferably, the composition comprises from 4% to 50%, preferably from 6% to 40%, more preferably from 10% to 30% by weight of the composition of the surfactant system.

Preferably, the surfactant system comprises a surfactant selected from C ₆ -C ₂₀ Alkyl Sulfate (AS), C ₆ -C ₂₀ Alkyl Alkoxy Sulphates (AAS), C ₆ -C ₂₀ Methyl Ester Sulfonate (MES), C ₆ -C ₂₀ Alkyl Ether Carboxylates (AEC) and any combination thereof, and/or a nonionic surfactant selected from alkyl alkoxylated alcohols, alkyl alkoxylated phenols, alkyl polysaccharides, polyhydroxy fatty acid amides, alkoxylated fatty acid esters, sucrose esters, sorbitan esters and alkoxylated derivatives of sorbitan esters, and any combination thereof.

Preferably C ₆ -C ₂₀ Linear Alkylbenzene Sulfonate (LAS) is present in the composition as the primary surfactant.

Preferably, the surfactant system comprises:

1) 50.1% to 90%, preferably 51% to 70%, more preferably 52% to 60%, for example 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 65% or any range of C therebetween, by weight of the surfactant system ₆ -C ₂₀ Linear Alkylbenzene Sulfonate (LAS),

2) 10% to 49.9%, preferably 30% to 49%, more preferably 40% to 45%, for example 35%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48% or any range of C therebetween, by weight of the surfactant system ₆ -C ₂₀ Alkyl Alkoxy Sulfate (AAS), and

3) From 0.5% to 10%, preferably from 1% to 8%, more preferably from 2% to 6, for example 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or any range of C therebetween, by weight of the surfactant system ₁₀ -C ₁₈ Alkyl ethoxylates.

Preferably, the composition comprises from 0.01% to 0.1%, preferably from 0.01% to 0.05%, more preferably from 0.01% to 0.04%, most preferably from 0.02% to 0.03%, by weight of the composition, of the antimicrobial agent, preferably selected from 4-4 '-dichloro-2-hydroxydiphenyl ether, 2, 4' -trichloro-2 '-hydroxydiphenyl ether, and combinations thereof, and wherein more preferably the antimicrobial agent is 4-4' -dichloro-2-hydroxydiphenyl ether.

Preferably, the composition further comprises from 0.1% to 10%, preferably from 0.2% to 5%, more preferably from 0.3% to 2% by weight of the composition of a polyamine, preferably a polyethyleneimine, more preferably an alkoxylated polyethyleneimine.

In some preferred embodiments, the composition comprises:

PA231101C

a) 15% to 30% by weight of the composition of a surfactant system comprising 52% to 60% by weight of the surfactant system of C ₆ -C ₂₀ Linear Alkylbenzene Sulfonate (LAS), 40% to 45% C by weight of surfactant system ₆ -C ₂₀ Alkyl Alkoxy Sulfate (AAS) and 2% to 6% C by weight of the surfactant system ₁₀ -C ₁₈ Alkyl ethoxylates;

b) 0.01% to 0.04% by weight of the composition of 4-4' -dichloro-2-hydroxydiphenyl ether; and

c) From 0.3% to 2% by weight of the composition of an alkoxylated polyethyleneimine.

In another aspect, the present application relates to a liquid detergent composition as mentioned above, its use for removing microorganisms from clothes after washing.

One advantage of the liquid detergent composition according to the present disclosure is that it may improve microbial removal. In particular, liquid detergent compositions according to the present disclosure can significantly reduce the amount of microorganisms on fabrics during post-wash use and/or storage. In the context of the present disclosure, removal of microorganisms is intended to mean a reduction in the amount of viable microorganisms, including, but not limited to, killing, inactivating, and/or eliminating microorganisms. In particular, post-wash removal of microorganisms is intended to mean a reduction in the amount of viable microorganisms during use and/or storage of the post-wash garment.

Detailed Description

Definition of the definition

As used herein, the articles "a" and "an" when used in the claims should be understood to mean one or more of the substance that is claimed or described.

As used herein, the terms "comprise/include", "include/include", "contain/contain" and "contain/contain" are not limiting, i.e. other steps and other ingredients may be added that do not affect the result. The above terms encompass the terms "consisting of … …" and "consisting essentially of … …".

As used herein, when the composition is "substantially free" of a particular ingredient, it means that the composition comprises less than trace amounts, alternatively less than 0.1%, alternatively less than 0.01%, alternatively less than 0.001% of the particular ingredient by weight of the composition.

As used herein, the term "laundry detergent composition" refers to a composition for cleaning soiled materials, including fabrics. Such compositions may be used as laundry pretreatments, laundry post-treatments, or may be added during the rinse cycle or wash cycle of a laundry operation. The laundry detergent composition may have a form selected from the group consisting of: liquid, powder, single or multi-phase unit doses, sachets, tablets, gels, pastes, sticks or wafers. Preferably, the laundry detergent composition is a liquid. The term "liquid laundry detergent composition" refers herein to a composition in a form selected from the group consisting of: pourable liquids, gels, creams and combinations thereof. The liquid laundry detergent composition may be aqueous or non-aqueous, and may be anisotropic, isotropic, or a combination thereof.

As used herein, the term "antimicrobial agent" refers to a chemical compound that primarily functions as intended to kill bacteria and/or prevent their growth or reproduction. Traditional antimicrobial agents include cationic antimicrobial agents (e.g., certain ammonium chlorides), nonionic antimicrobial agents, and the like. The diphenyl ether compounds used in the present application are nonionic antimicrobial agents.

As used herein, the term "primary surfactant" refers to a surfactant that is present in a composition in an amount greater than any other surfactant comprised by such a composition.

As used herein, the term "majority surfactant" refers to surfactants present in such compositions at a total surfactant content of at least 50 wt%.

As used herein, the term "alkyl" refers to a branched or unbranched, substituted or unsubstituted hydrocarbyl moiety. Included within the term "alkyl" are the alkyl portions of acyl groups.

As used herein, the term "wash solution" refers to a typical amount of aqueous solution for one laundry wash cycle, preferably 1L to 50L, or 1L to 20L for hand washing, and 20L to 50L for machine washing.

As used herein, the term "stained fabric" is used non-specifically and may refer to any type of fabric made from natural or synthetic fibers, including natural, synthetic, and synthetic fibers, such as, but not limited to, cotton, linen, wool, polyester, nylon, silk, acrylic, and the like, as well as various blends and combinations.

Liquid detergent composition

The liquid detergent composition of the present application comprises from 2% to 60% by weight of the composition of a surfactant system and from 0.01% to 1% by weight of the composition of an antimicrobial agent which is a hydroxydiphenyl ether of formula (I):

wherein:

each Y is independently selected from chlorine, bromine or fluorine,

r is 0, 1, 2 or 3,

o is 0, 1, 2 or 3,

p is 0, 1 or 2,

m is 1 or 2, and

n is 0 or 1

Wherein the surfactant system comprises C ₆ -C ₂₀ Linear Alkylbenzene Sulfonate (LAS) as the primaryA surfactant is required.

It has surprisingly been found that by combining a surfactant system comprising LAS as the primary surfactant with diphenyl ether, excellent efficacy of post-wash microorganism removal can be achieved. This effect is unexpected because it has not previously been found in liquid detergent compositions.

The laundry detergent compositions herein provide efficacy in removing gram positive bacteria (e.g., staphylococcus aureus (Staphylococcus aureus)). In one embodiment, the laundry detergent composition provides at least a log 1.0 reduction, preferably a log 1.5 reduction, more preferably a log 2.0 reduction, even more preferably a log2.5 reduction, most preferably a log 3.0 reduction of microbial removal values for gram positive bacteria at 18 hours post-inoculation as compared to the inoculation time. Preferably, the composition provides at least a log 2.2 reduction, preferably a log2.5 reduction, against staphylococcus aureus at 18 hours post-inoculation, as determined by test 1 as described below. More preferably, the composition provides at least a log 3.0 log reduction against staphylococcus aureus. It is notable that staphylococcus aureus is frequently found on human skin, and thus fabrics (especially worn fabrics) particularly require antimicrobial effects against staphylococcus aureus.

The laundry detergent composition may have any suitable viscosity, depending on factors such as the formulation ingredients and the purpose of the composition. In one embodiment, the composition has a high shear viscosity value of about 200cP to about 3,000cP, or about 300cP to about 2,000cP, or about 500cP to about 1,000cP, at a shear rate of 20/sec and a temperature of 21 ℃, and a low shear viscosity value of about 500cP to about 100,000cP, or about 1000cP to about 10,000cP, or about 1,500cP to about 5,000cP, at a shear rate of 1/sec and a temperature of 21 ℃.

Surfactant system

Preferably, the composition comprises from 4% to 50%, preferably from 6% to 40%, more preferably from 10% to 30% by weight of the composition of the surfactant system. In particular, the surfactant system may comprise additional anionic and nonionic surfactants in addition to LAS.

Anionic surfactants suitable for the compositions of the present application may be selected from C ₆ -C ₂₀ Linear Alkylbenzene Sulfonate (LAS), C ₆ -C ₂₀ Alkyl Sulfate (AS), C ₆ -C ₂₀ Alkyl Alkoxy Sulphates (AAS), C ₆ -C ₂₀ Methyl Ester Sulfonate (MES), C ₆ -C ₂₀ Alkyl Ether Carboxylates (AEC), and any combination thereof. For example, the laundry detergent composition may comprise C ₆ -C ₂₀ Alkyl alkoxy sulphates (AA) _x S), wherein x is from about 1 to about 30, preferably from about 1 to about 15, more preferably from about 1 to about 10, and most preferably x is from about 1 to about 3. Such AA _x The alkyl chain in S may be straight or branched, with mid-chain branched AA _x S surfactants are particularly preferred. Preferred AA _x Group S includes C wherein x is from about 1 to about 3 ₁₂ -C ₁₄ Alkyl alkoxy sulfates.

Nonionic surfactants suitable for the compositions of the present application may be selected from the group consisting of alkyl alkoxylated alcohols, alkyl alkoxylated phenols, alkyl polysaccharides, polyhydroxy radicalsFatty acid amides, alkoxylated fatty acid esters, sucrose esters, sorbitan esters and alkoxylated derivatives of sorbitan esters, and any combinations thereof. Non-limiting examples of nonionic surfactants suitable for use herein include: c (C) ₁₂ -C ₁₈ Alkyl ethoxylates, e.g. available from ShellA nonionic surfactant; c (C) ₆ -C ₁₂ Alkylphenol alkoxylates in which the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c (C) ₁₂ -C ₁₈ Alcohol and C ₆ -C ₁₂ Condensates of alkylphenols with ethylene oxide/propylene oxide block alkyl polyamine ethoxylates, such as +.>C ₁₄ -C ₂₂ A mid-chain branched alkyl alkoxylate, BAEx, wherein x is from about 1 to about 30; alkyl polysaccharides, in particular alkyl polyglycosides; polyhydroxy fatty acid amides; and an ether-terminated poly (alkoxylated) alcohol surfactant. Also useful herein as nonionic surfactants are alkoxylated ester surfactants, such as those of formula R ¹ C(O)O(R ₂ O)nR ³ Those of (C), wherein R ¹ Selected from linear or branched C ₆ -C ₂₂ An alkyl or alkylene moiety; r is R ² Selected from C ₂ H ₄ And C ₃ H ₆ Part, and R ³ Selected from H, CH ₃ 、C ₂ H ₅ And C ₃ H ₇ A portion; and n has a value between about 1 and about 20. Such alkoxylated ester surfactants include aliphatic Methyl Ester Ethoxylates (MEEs) and are well known in the art. In some embodiments, the alkoxylated nonionic surfactant comprised by the laundry detergent compositions of the present application is C ₆ -C ₂₀ Alkoxylated alcohols, preferably C ₈ -C ₁₈ Alkoxylated alcohols, more preferably C ₁₀ -C ₁₆ An alkoxylated alcohol. C (C) ₆ -C ₂₀ The alkoxylated alcohol is preferably an alkyl alkoxylated alcohol having an average degree of alkoxylation of from about 1 to about 50, preferably from about 3 to about 30, more preferably from about 5 to about 20, even more preferably from about 5 to about 9.

In some embodiments, the composition comprises C ₆ -C ₂₀ Linear alkylbenzene sulfonate surfactant (LAS), preferably C ₁₀ -C ₁₆ LAS, and more preferably C ₁₂ -C ₁₄ LAS。

Preferably, the surfactant system comprises:

1) 50.1% to 90%, preferably 51% to 70%, more preferably 52% to 60% C by weight of the surfactant system ₆ -C ₂₀ Linear Alkylbenzene Sulfonate (LAS),

2) 10% to 49.9%, preferably 30% to 49%, more preferably 40% to 45% C by weight of the surfactant system ₆ -C ₂₀ Alkyl Alkoxy Sulfate (AAS), and

3) From 0.5% to 10%, preferably from 1% to 8%, more preferably from 2% to 6% C by weight of the surfactant system ₁₀ -C ₁₈ Alkyl ethoxylates.

The laundry detergent compositions of the present application may also comprise cationic surfactants. Non-limiting examples of cationic surfactants include: quaternary ammonium surfactants, which may have up to 26 carbon atoms, include: an Alkoxylated Quaternary Ammonium (AQA) surfactant; dimethyl hydroxyethyl quaternary ammonium; dimethyl hydroxyethyl lauryl ammonium chloride; a polyamine cationic surfactant; and amino surfactants, in particular amidopropyl dimethylamine (APA).

Antimicrobial agents based on diphenyl ether

The diphenyl ether-based antimicrobial agent of the present application is a nonionic compound. In the present application, it has been found that the antimicrobial agent of the present application allows the formation of stable liquid detergent compositions due to its nonionic nature.

Preferably, the antimicrobial agent is hydroxydiphenyl ether. The antimicrobial agents herein may be halogenated or non-halogenated, but are preferably halogenated. In one embodiment, the antimicrobial agent is a hydroxydiphenyl ether of formula (I):

wherein:

each Y is independently selected from chlorine, bromine or fluorine, preferably chlorine or bromine, more preferably chlorine,

r is 0, 1, 2 or 3, preferably 1 or 2,

o is 0, 1, 2 or 3, preferably 0, 1 or 2,

p is 0, 1 or 2, preferably 0,

m is 1 or 2, preferably 1, and

n is 0 or 1, preferably 0.

In the definition of formula (I) above, 0 means absent. For example, when p is 0, then Z is absent in formula (I). Each Y and each Z may be the same or different. In one embodiment, o is 1, r is 2, and Y is chloro or bromo. This embodiment may be: one chlorine atom is bonded to the benzene ring, whereas bromine atoms and other chlorine atoms are bonded to other benzene rings; or a bromine atom is bonded to a benzene ring, whereas two chlorine atoms are bonded to other benzene rings.

More preferably, the antimicrobial agent is selected from the group consisting of 4-4' -dichloro-2-hydroxydiphenyl ether ("sethoxydim"), 2, 4' -trichloro-2 ' -hydroxydiphenyl ether ("triclosan"), and combinations thereof. Most preferably, the antimicrobial agent is 4-4' -dichloro-2-hydroxydiphenyl ether, available from BASF under the trade nameHP100 is commercially available.

In addition to diphenyl ether, other antimicrobial agents may be present, provided that the antimicrobial agents are present in amounts that do not cause instability of the formulation. Among such antimicrobial agents that are also useful are chelating agents, which are particularly useful for reducing the resistance to gram negative bacteria in hard water. Acidic biocides may also be present.

Polyamines as a base material

The laundry detergent compositions herein may further comprise from 0.1% to 10%, preferably from 0.2% to 5%, more preferably from 0.3% to 2% by weight of the composition of a polyamine, preferably a polyethyleneimine, more preferably an alkoxylated polyethyleneimine.

Polyamines suitable for use in the laundry detergent compositions herein may have a Mw of greater than 400 g/mol. One preferred class of polyamines are Polyethylenimine (PEI) and derivatives thereof such as ethoxylated PEI polymers, propoxylated PEI polymers, polyamines, polyquaterniums, polyglycerol quaterniums and other PEI derivatives, salts or mixtures thereof. In some preferred embodiments, the PEI is a branched, spherical polyamine and the molecular weight of the PEI or PEI salt used is from about 800 daltons to about 2,000,000 daltons. Furthermore, in some preferred embodiments, the PEI or PEI salt used has a charge density of about 15meq/g to about 25meq/g, more preferably about 16meq/g to about 20meq/g. Examples of such preferred PEI's include the BASF products LUPASOL WF (25 kDa;16-20 meq/g) andFG (800 daltons; 16-20 meq/g), available from BASFPolymer families, e.g.)>HP20 and->HP22 G。

Auxiliary ingredient

The laundry detergent compositions herein may comprise adjunct ingredients. Suitable adjunct materials include, but are not limited to: builders, chelating agents, rheology modifiers, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, photobleaches, perfumes, perfume microcapsules, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, solvents, toners, structurants and/or pigments. The exact nature of these adjunct ingredients and their content in the laundry detergent composition will depend on the physical form of the composition and the nature of the cleaning operation to be performed using it.

In one embodiment, the compositions herein comprise rheology modifiers (also referred to as "structurants" in some instances) that are used to adjust the viscosity of the composition, and thus are more suitable for use in packaging components. The rheology modifier herein may be any ingredient known to be capable of suspending particles and/or adjusting the rheology of a liquid composition. Preferably, the rheology modifier is selected from the group consisting of hydroxyl-containing crystalline materials, polyacrylates, polysaccharides, polycarboxylates, alkali metal salts, alkaline earth metal salts, ammonium salts, alkanolammonium salts, C ₁₂ -C ₂₀ Fatty alcohols, dibenzylidene polyol acetal Derivatives (DBPA), diamidogainst (galbant), cationic polymers comprising a first structural unit derived from methacrylamide and a second structural unit derived from diallyldimethyl ammonium chloride, and combinations thereof. Preferably, the rheology modifier is a crystalline hydroxyl-containing material generally characterized as crystalline, hydroxyl-containing fatty acids, fatty acid esters, and fatty waxes, such as castor oil and castor oil derivatives. More preferably the rheology modifier is Hydrogenated Castor Oil (HCO).

Preparation of the composition

The laundry detergent compositions of the present application are typically prepared by conventional methods, such as methods of preparing laundry detergent compositions known in the art. Such methods generally involve mixing the essential and optional ingredients in any desired order to a relatively homogeneous state, with or without heating, cooling, application of vacuum, and the like, to provide a laundry detergent composition comprising the ingredients in the requisite concentrations.

Application method

Another aspect of the application relates to a method of treating fabrics with a laundry detergent composition having a microbial removal benefit and optionally a microbial prevention benefit. The method comprises the step of applying 5g to 120g of the laundry detergent composition described above to a laundry tub comprising water to form a wash solution. The wash solution in the laundry wash basin herein preferably has a volume of 1L to 50L, or 1L to 20L for hand washing and 20L to 50L for machine washing. Preferably, the post-wash microbial removal benefit herein is determined by the method as described in test 1 (i.e. GB/T20944.2-2007 adsorption method). The temperature of the laundry solution is preferably in the range 5 ℃ to 60 ℃.

The dosage in the methods herein may vary depending on the type of wash. In one embodiment, the method comprises applying from about 5g to about 60g of the laundry detergent composition to a hand basin (e.g., about 2-4L). In alternative embodiments, the method comprises applying from about 5g to about 100g, preferably from about 10g to about 65g, of the laundry detergent composition to a washing machine (e.g., about 30-45L).

Preferably, the method herein further comprises the step of contacting the stained fabric with a wash solution. For example, the fabric is suspected of having gram positive and/or gram negative bacteria. The step of contacting the stained fabric with the wash solution preferably follows the step of applying the laundry detergent composition into the laundry tub. The method may further comprise the step of contacting the fabric with a laundry detergent composition, i.e. pre-treating the fabric with the laundry detergent composition for a specific time, preferably from 1 to 10 minutes, before the step of applying the laundry detergent composition into the laundry tub.

Test method

Test 1: efficacy of microorganism removal after washing (GB/T20944.2 2007 adsorption method)

The efficacy of post-wash microbial removal of laundry detergent compositions is determined by the method as defined in GB/T20944.2-2007 adsorption method and as described below.

1. Microbial preparation：

A. A quantity of the nutrient broth is aseptically added to a lyophilized culture of staphylococcus aureus, escherichia coli, or klebsiella pneumoniae. The culture is dissolved and suspended in the nutrient broth to obtain a suspension. One loop of the suspension was streaked onto nutrient agar plates and incubated at 37℃for 24 hours to obtain a first generation subculture of bacterial suspension. The first generation subculture of a loop of bacterial suspension was transferred to 20mL of the nutrient broth and cultured with shaking at 37 ℃ for 24 hours to obtain the second generation subculture of bacterial suspension. The second generation subculture of 0.4mL of the bacterial suspension was transferred to another 20mL of the nutrient broth, and shake-cultured at 37 ℃ for 3±1 hour to obtain the third generation subculture of the bacterial suspension.

B. Third generation subcultures of bacterial suspensions were diluted 1X 10 with 1/20 of the diluted nutrient broth ⁵ CFU/mL to 3X 10 ⁵ CFU/mL to obtain working cultures.

C. The working cultures were stored at 4 ℃. The working cultures were not allowed to store overnight.

2. Fabric washing：

A. Two fabric strips, each having a width of 1m and a length of 3m (32 yarns/cm x 32 yarns/cm, 100% plain weave cotton), were boiled in 5L of solution for 1 hour. A solution was prepared from 2.5g of nonionic impregnant, 2.5g of sodium carbonate and 5000mL of distilled water. The nonionic impregnant was prepared from 5.0g of alkylphenol ethoxylate, 5g of sodium carbonate and 1000mL of distilled water. The fabric strips were rinsed in boiling deionized water for 5 minutes. The fabric strips were placed in cooled deionized water for 5 minutes and dried in a room. One strip was used as a test strip for the following steps 2B-2I and the other strip was used as a control (without going through steps 2B-2I).

B. One end of the test fabric strip obtained from step 2A was fixed to the stainless steel mandrel at a position outward in the horizontal extension direction of the stainless steel mandrel. The stainless steel mandrel has 3 horizontal stands connected to each other. The test fabric strips were wrapped around 3 horizontal stands of stainless steel mandrel with sufficient tension to obtain a fabric wrapped mandrel with 12 stacks of fabric. The other end of the test fabric strip was pinned to the outer ply of the 12 plies of fabric. The fabric wrapped mandrel was sterilized with high pressure steam at 121 ℃ for 15 minutes.

C. 5.903g of calcium chloride dihydrate and 2.721g of magnesium chloride hexahydrate were dissolved in 100mL of distilled water and the mixture was subsequently sterilized with high pressure steam at 121 ℃ for 20 minutes. 1mL of the mixture was added to 1L of distilled water to obtain a hard aqueous solution.

D. Sufficient sample was added to the 1L of hard aqueous solution obtained from step 2C to obtain a solution having a concentration of 1055 ppm. The solution was mixed with a magnetic stirrer for 4 minutes. 250mL of the mixed solution was dispensed into the contactor to obtain a wash solution. The contact chamber was placed in a water bath and brought to a test temperature of (25.+ -. 1). Degree.C.

E. The fabric-wrapped mandrel from step 2B was aseptically immersed into the wash solution within the contacting chamber and the contacting chamber was closed with a cover.

F. The contacting chamber is secured to the tumbler. The tumbler was rotated for 10 minutes. The fabric-wrapped mandrel is then removed from the contacting chamber. The fabric wrapped mandrel was placed in a Haier iwash-1p top load washer and spin dried for 2 minutes.

G. The wash solution from the contactor is discarded and then 250mL of sterile distilled water is added to the contactor. The spin-dried fabric-wrapped mandrel is immersed in freshly added distilled water in the contacting chamber. The tumbler was rotated for 3 minutes and then dried for 2 minutes.

H. And (5) repeating the step 2G.

I. The fabric-wrapped mandrel is aseptically removed from the contactor and the test fabric strip is removed from the mandrel. The test strips were air dried overnight.

3. Fabric incubation：

A. The laundered test fabric strips obtained from step 2I were cut into square pieces, each piece having a side length of 2 cm. Three (3) sets of 0.4g of tablets were used as samples for the following steps.

B. Each set of samples was placed in a vial and the samples were then autoclaved at 121 ℃ for 15 minutes. After sterilization, the samples were dried in a clean bench without lid for 1 hour.

C. 0.2mL of the working culture from step 1C was inoculated onto each dried sample. Vials containing inoculated samples were incubated at 37℃for 18 hours.

D. Viable microorganisms on the incubated samples were extracted, inoculated onto nutrient agar plates, and incubated at 37℃for 24-48 hours. The total Colony Forming Units (CFU) for each group of samples were counted and the average results for 3 groups were obtained. The log10 value of the CFU value is taken as Mb.

E. In steps 3A-3D, the fabric strip obtained from step 2A (which did not go through steps 2B-2I) was used as a control. The log10 value of the CFU value was taken as Ma.

F. In step 3C, parallel vials of each inoculated sample were removed immediately after inoculation for cell concentration determination. Viable microorganisms on the incubated samples were extracted, inoculated onto nutrient agar plates, and incubated at 37℃for 24-48 hours. The total Colony Forming Units (CFU) for each group of samples were counted and the average results for 3 groups were obtained. The log10 value of the CFU value was taken as Mc.

4. Calculation of bacteriostatic Activity value and microbial removal Activity value after washing：

Bacteriostatic activity value = Ma-Mb

Microbial removal Activity value after washing = Mc-Mb

A bacteriostatic activity value of not less than 2.0 indicates an acceptable microbial preventive effect, not less than 2.5 indicates a good microbial preventive effect, and not less than 3.0 indicates an excellent microbial preventive effect. And bacteriostatic activity values below 2.0 indicate unacceptable poor microbial prevention efficacy.

A bacteriostatic activity value of at least 1.0 indicates acceptable post-wash microorganism removal efficacy, a bacteriostatic activity value of at least 2.0 indicates good post-wash microorganism removal efficacy, and a bacteriostatic activity value of at least 3.0 indicates excellent post-wash microorganism removal efficacy.

Test 2: fabric deposition test of antimicrobial agent

The antimicrobial agent is extracted from the treated fabric by using the methanol-based Accelerated Solvent Extraction (ASE) method described below. The resulting extract was then subjected to gradient reverse phase High Performance Liquid Chromatography (HPLC) separation on a C18 column and quantified by tandem mass spectrometry (MS/MS) operating under Multiple Reaction Monitoring (MRM) conditions in negative mode.

As a first step, about three (3) grams of treated fabric were accurately weighed and then filled into steel ASE tubes. The extraction protocol was run for about five (5) minutes at an elevated temperature of about 100 ℃ and a pressure of about 2000 pounds per square inch (psi) using methanol as the extraction solvent. The resulting extract was collected and transferred to a 25ml flask, which was then filled to its full volume with methanol. The resulting solution was then diluted approximately twenty-five (25) fold by using a 50:50 ratio of methanol and water mixture, which was used as an injection sample for subsequent LC-MS/MS analysis.

Next, about five (5) ul of the above-described injection samples were injected and separated on a Waters Acquity UPLC C column, with a gradient of about 70% mobile phase a (1% formic acid in water)/30% mobile phase B (0.1% formic acid in methanol) to 5% mobile phase a/95% mobile phase B over about three (3) minutes, and the final gradient was maintained for an additional three (3) minutes. Detection of antimicrobial agents in negative MRM mode, e.gHP100。m/z 253>142 are used as quantitative conversions, however m/z 253>125 ion pairs were used for identification.

Subsequently, a standard of a labeled matrix in the range of 0.5mg/ml to 500ng/ml was injected to generate a calibration curve. Using weighting of the calibration curve (1/x ² ) Quadratic regression is extrapolated to determine antimicrobial agent in injected samples (e.gHP 100).

Examples

Example 1: exhibiting effective removal by liquid detergent compositions containing surfactant systems and diphenyl ether Comparative test of microorganisms after removal of the wash

A liquid laundry detergent composition was prepared containing the ingredients shown in table 1 below, wherein inventive sample 1 contained a surfactant system containing LAS as the primary surfactant and diphenyl ether, while comparative sample 2 contained a surfactant system containing NI as the primary surfactant and diphenyl ether.

TABLE 1

a C _11-13 LAS

b C _12-14 AE _1-3S Purchased from Shell

c25-7, which is C ethoxylated with an average of 7 moles of ethylene oxide ₁₂ -C ₁₅ Alcohols, which are commercially available as nonionic surfactants _Shell

dHP100 is 4-4' -dichloro-2-hydroxydiphenyl ether available from BASF

e ethoxylated or ethoxylated and propoxylated Polyethylenimine (PEI) polymers from BASF

Then, according to test 1 where staphylococcus aureus was used, ATCC 6538: efficacy of post-wash microorganism removal the efficacy of post-wash microorganism removal of the above sample was determined at a 1000ppm finished dose. The results are shown below.

TABLE 2

As the data presented above, it is surprising and entirely unexpected that the combination of a surfactant system comprising LAS as the primary surfactant with diphenyl ether is capable of delivering very strong post-wash microorganism removal efficacy (i.e., log 3 reduction exceeded). In other words, sample 1 of the present application removed more than 99.9% of the microorganisms in the microorganism removal test. In contrast, the combination of the different surfactant systems with diphenyl ether (comparative sample 2) did not show any significant efficacy (i.e., even less than log 0 reduction) of microbial removal after washing.

Example 2: exemplary formulations of liquid laundry detergent compositions

The following liquid laundry detergent compositions shown in table 3 were prepared, comprising the listed ingredients in the listed proportions (wt.%).

TABLE 3 Table 3

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Rather, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40mm" is intended to mean "about 40mm".

Each of the documents cited herein, including any cross-referenced or related patent or patent application, and any patent application or patent for which the present application claims priority or benefit from, is hereby incorporated by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to the present application, or that it is not entitled to any disclosed or claimed herein, or that it is prior art with respect to itself or any combination of one or more of these references. Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

While particular embodiments of the present application have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the application. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this application.

Claims

1. A method of removing microorganisms from a laundry article after washing, the method comprising the steps of:

a) Providing a laundry article in a washing machine; and

b) Contacting the laundry article during a wash sub-cycle of the washing machine with a liquid detergent composition comprising from 2% to 60% by weight of the composition of a surfactant system and from 0.01% to 1% by weight of the composition of an antimicrobial agent which is a hydroxydiphenyl ether of formula (I):

wherein:

each Y is independently selected from chlorine, bromine or fluorine,

r is 0, 1, 2 or 3,

o is 0, 1, 2 or 3,

p is 0, 1 or 2,

m is 1 or 2, and

n is 0 or 1

2. The method according to claim 1, wherein the composition comprises from 4% to 50%, preferably from 6% to 40%, more preferably from 10% to 30% of the surfactant system by weight of the composition,

preferably wherein the surfactant system comprises a surfactant selected from C ₆ -C ₂₀ Alkyl Sulfate (AS), C ₆ -C ₂₀ Alkyl Alkoxy Sulphates (AAS), C ₆ -C ₂₀ Methyl Ester Sulfonate (MES), C ₆ -C ₂₀ Alkyl Ether Carboxylates (AEC) and any combination thereof, and/or a nonionic surfactant selected from alkyl alkoxylated alcohols, alkyl alkoxylated phenols, alkyl polysaccharides, polyhydroxy fatty acid amides, alkoxylated fatty acid esters, sucrose esters, sorbitan esters and alkoxylated derivatives of sorbitan esters, and any combination thereof.

3. The method of any one of the preceding claims, wherein the C ₆ -C ₂₀ Linear Alkylbenzene Sulfonate (LAS) is present in the composition as the primary surfactant.

4. The method of any of the preceding claims, wherein the surfactant system comprises:

2) From 10% to 49.9%, preferably from 30% to 49%, more preferably from 40% to 45% C by weight of the surfactant system ₆ -C ₂₀ Alkyl Alkoxy Sulfate (AAS), and

3) From 0.5% to 10%, preferably 1% by weight of the surfactant systemTo 8%, more preferably 2% to 6% C ₁₀ -C ₁₈ Alkyl ethoxylates.

5. The method of any of the preceding claims, wherein the composition comprises from 0.01% to 0.1%, preferably from 0.01% to 0.05%, more preferably from 0.01% to 0.04%, most preferably from 0.02% to 0.03%, by weight of the composition, of the antimicrobial agent, preferably selected from 4-4 '-dichloro-2-hydroxydiphenyl ether, 2, 4' -trichloro-2 '-hydroxydiphenyl ether, and combinations thereof, and wherein more preferably the antimicrobial agent is 4-4' -dichloro-2-hydroxydiphenyl ether.

6. The method of any of the preceding claims, wherein the composition further comprises from 0.1% to 10%, preferably from 0.2% to 5%, more preferably from 0.3% to 2% of a polyamine, preferably a polyethyleneimine, more preferably an alkoxylated polyethyleneimine, by weight of the composition.

7. The method of claim 1, wherein the composition comprises:

a) 15% to 30% by weight of the composition of the surfactant system comprising 52% to 60% by weight of the surfactant system of C ₆ -C ₂₀ Linear Alkylbenzene Sulfonate (LAS), 40% to 45% C by weight of the surfactant system ₆ -C ₂₀ Alkyl Alkoxy Sulfate (AAS) and 2% to 6% C by weight of the surfactant system ₁₀ -C ₁₈ Alkyl ethoxylates;

b) 0.01% to 0.04%, by weight of the composition, of 4-4' -dichloro-2-hydroxydiphenyl ether; and

c) From 0.3% to 2% by weight of the composition of an alkoxylated polyethylenimine.