CN111315858B

CN111315858B - Particulate antimicrobial laundry detergent composition

Info

Publication number: CN111315858B
Application number: CN201780096449.4A
Authority: CN
Inventors: 高倩; 姜春鹏; 刘玉祥
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 2017-11-14
Filing date: 2017-11-14
Publication date: 2021-12-24
Anticipated expiration: 2037-11-14
Also published as: CN111315858A; WO2019095089A1

Abstract

A particulate laundry detergent composition comprising the antimicrobial agent 4-4' -dichloro-2-hydroxydiphenyl ether, and such particulate laundry detergent composition is characterized by a relatively low equilibrium pH, which is particularly useful for improving the antimicrobial efficacy of such antimicrobial agents.

Description

Particulate antimicrobial laundry detergent composition

Technical Field

The present invention relates to a particulate laundry detergent composition having an antimicrobial benefit.

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 an antimicrobial benefit on such fabrics while they clean the fabrics.

Currently, various antimicrobial agents (e.g., diphenyl ethers) are known for use in liquid laundry detergent formulations to deliver antimicrobial effects. However, it has been found that in the case of solid particulate laundry detergent products, such diphenyl ether antimicrobials, especially 4-4' -dichloro-2-hydroxydiphenyl ether (commonly known as "dichlorosan" (dichlorosan) or under its trade name "are provided when at the same concentration level as in liquid laundry detergent products"

HP 100 "available from BASF) they have poor to disappointing antimicrobial efficacy. To compensate for such poor antimicrobial efficacy, it is desirable to provide such antimicrobial agents in granular laundry detergent products at concentration levels significantly higher than liquid laundry detergent products, so that they become too costly to use to be practical.

Accordingly, there is a need to improve the antimicrobial efficacy of 4-4' -dichloro-2-hydroxydiphenyl ether antimicrobials in granular laundry detergent compositions.

Disclosure of Invention

The present invention has surprisingly and unexpectedly discovered that the antimicrobial efficacy of 4-4' -dichloro-2-hydroxydiphenyl ether antimicrobials can be significantly improved by adjusting the equilibrium pH of the particulate laundry detergent composition to be within a relatively low range (as compared to conventional particulate laundry detergent compositions), for example, from about 6.5 to about 10.5. Such adjustment of the equilibrium pH is preferably, but not necessarily, performed by using a pH buffer system comprising a water-soluble alkali metal carbonate and a water-soluble acid.

Accordingly, the present invention relates in one aspect to a particulate laundry detergent composition comprising:

(a) from about 5% to about 70%, by weight of such composition, of a surfactant;

(b) from about 0.001% to about 3%, by weight of such composition, of an antimicrobial agent which is 4-4' -dichloro-2-hydroxydiphenyl ether,

and said particulate laundry detergent composition is characterized by an equilibrium pH in the range of from about 6.5 to about 10.5.

The equilibrium pH of the above particulate laundry detergent composition is preferably in the range of from about 6.5 to about 10, preferably from about 7 to about 10, more preferably from about 7 to about 9.5, even more preferably from about 7 to about 9, most preferably from about 7 to about 8.5.

The antimicrobial agent may be present in an amount ranging from about 0.005% to about 2%, preferably from about 0.01% to about 1%, more preferably from about 0.02% to about 0.2%, by weight of the particulate laundry detergent composition.

The particulate laundry detergent composition may comprise a water-soluble alkali or alkaline earth metal sulfate, which may be selected from sodium sulfate, potassium sulfate, magnesium sulfate, and combinations thereof. The water-soluble alkali or alkaline earth metal sulfate is preferably sodium sulfate. The water-soluble alkali or alkaline earth metal sulfate may be present in an amount ranging from about 20% to about 90%, preferably from about 30% to about 80%, more preferably from about 40% to about 70%, by weight of the particulate laundry detergent composition.

The particulate laundry detergent composition may comprise a water soluble alkali metal carbonate which may be selected from sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, and combinations thereof. Such water-soluble alkali metal carbonate is preferably sodium carbonate. The water-soluble alkali metal carbonate may be present in an amount ranging from about 0.01% to about 20%, preferably from about 0.1% to about 15%, more preferably from about 0.5% to about 10%, most preferably from about 1% to about 5%, by weight of the particulate laundry detergent composition.

The particulate laundry detergent composition may comprise a water-soluble acid, preferably water-soluble C₁-C₆Organic acids such as citric acid, lactic acid, and combinations thereof. The water-soluble acid is preferably citric acid. The water-soluble organic acid may be present in an amount ranging from about 0.01% to about 20%, preferably from about 0.1% to about 15%, more preferably from about 0.5% to about 10%, most preferably from about 0.75% to about 5%, by weight of the particulate laundry detergent composition.

In a particularly preferred, but not essential, embodiment of the present invention, the surfactant in the particulate laundry detergent composition comprises an anionic surfactant selected from the group consisting of: c₆-C₂₀Alkyl Sulfates (AS), C₆-C₂₀Alkyl Alkoxy Sulfates (AAS), C₆-C₂₀Linear alkyl benzene sulphonate (LAS), C₆-C₂₀Methyl Ester Sulfonate (MES), C₆-C₂₀Alkyl Ether Carboxylates (AECs), and combinations thereof. Such anionic surfactants are preferably present at from about 10% to about 60%, preferably from about 12% to about 50%, more preferably from about 15% to aboutAn amount in the range of 40% is present. Furthermore, the particulate laundry detergent composition may comprise a surfactant selected from C₆-C₂₀Nonionic surfactant of an alkoxylated alcohol, wherein such nonionic surfactant is preferably present in an amount ranging from about 0.01% to about 10%, preferably from about 0.05% to about 5%, more preferably from about 0.1% to about 3%, by weight of the particulate composition.

Still further, the particulate laundry detergent composition may further comprise a cationic polymer, preferably a cationic polysaccharide, more preferably a cationic cellulose polymer, most preferably a cationic hydroxyethyl cellulose or a cationic hydroxypropyl cellulose or a combination thereof. Such cationic polymers may be present in an amount ranging from about 0.01% to about 5%, preferably from about 0.02% to about 1%, more preferably from about 0.05% to about 0.5%, by weight of the particulate laundry detergent composition.

In another aspect, the present invention relates to a particulate laundry detergent composition comprising:

(a) from about 10% to about 20% by weight of such composition of C₆-C₂₀Linear alkyl benzene sulphonate (LAS);

(b) from about 0.5% to about 2% by weight of such compositions of C₆-C₂₀Alkyl Ethoxy Sulfates (AES);

(c) from about 0.1% to about 1%, by weight of such composition, of C₆-C₂₀An alkoxylated alcohol;

(d) from about 0.02% to about 0.2%, by weight of such compositions, of 4-4' -dichloro-2-hydroxydiphenyl ether;

(e) from about 50% to about 85%, by weight of such composition, of sodium sulfate;

(f) from about 0% to about 10%, by weight of such composition, of sodium carbonate; and

(g) from 0% to about 5%, by weight of such compositions, of citric acid,

such granular laundry detergent compositions are characterized by an equilibrium pH in the range of from about 7 to about 10.

The granular laundry detergent composition as described above is preferably characterized by a reduction in the value of bacteriostatic activity against both gram positive and gram negative bacteria of at least log 1, preferably at least log 2, more preferably at least log 2.5.

In yet another aspect, the present invention relates to a method of improving the antimicrobial efficacy of 4-4' -dichloro-2-hydroxydiphenyl ether in particulate laundry detergent compositions by adjusting the equilibrium pH of such particulate laundry detergent compositions to be in the range of from about 6.5 to about 10.5.

Preferably, but not necessarily, the above-mentioned equilibrium pH adjustment is carried out by using a pH buffer system comprising a water-soluble alkali metal carbonate and a water-soluble acid. More preferably, the water-soluble alkali metal carbonate is sodium carbonate and the water-soluble acid is citric acid. Sodium carbonate may be present in an amount ranging from 0.01% to about 20%, preferably from about 0.1% to about 15%, more preferably from about 0.5% to about 10%, most preferably from about 1% to about 5%, by weight of the particulate laundry detergent composition. Citric acid may be present in an amount ranging from 0.01% to about 20%, preferably from about 0.1% to about 15%, more preferably from about 0.5% to about 10%, most preferably from about 0.75% to about 5%, by weight of the particulate laundry detergent composition.

Detailed Description

The features and advantages of various embodiments of the present invention will become apparent from the following description, which includes examples intended to give a broad representation of specific embodiments of the invention. Various modifications will be apparent to those skilled in the art from this description and from practice of the invention. The scope of the invention is not intended to be limited to the particular forms disclosed, and the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the claims.

Definition of

As used herein, articles including "a" and "an" when used in a claim should be understood to mean one or more of what is claimed or described.

As used herein, the meaning of the terms "comprising", "including", "containing" and "containing" is non-limiting, i.e. other steps and other ingredients can be added that do not affect the result. The above terms encompass the terms "consisting of … …" and "consisting essentially of … …".

As used herein, unless otherwise indicated, the term "granular laundry detergent composition" includes multipurpose or "heavy duty" laundry detergents in solid, powder form, as well as cleaning adjuncts such as bleaching agents, rinse aids, additives or pretreatment types. In a preferred aspect, the particulate laundry detergent composition is a free-flowing particulate laundry detergent composition.

As used herein, the term "laundry detergent composition" refers to compositions for cleaning contaminated materials, including fabrics. Such compositions may be used as laundry pre-treatment agents, laundry post-treatment agents, or may be added during the rinse cycle or wash cycle of a laundry washing operation.

As used herein, the term "fabric" is used non-specifically and can refer to any type of natural or synthetic fiber, 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.

As used herein, when a composition is "substantially free" or "substantially free of a particular ingredient, it is meant that the composition comprises the indicated material in an amount ranging from 0% to about 0.5%, preferably from 0% to about 0.1%, by total weight of such composition.

As used herein, the terms "substantially free of" or "substantially free of" mean that the indicated material is present in an amount of less than about 0.01%, preferably less than about 0.001%, by weight of the composition, and more preferably that the material is not present at analytically detectable levels.

As used herein, the term "antimicrobial agent" refers to a chemical compound whose primary intended function is to kill bacteria or prevent their growth or reproduction.

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 composition.

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 "water soluble" refers to a solubility of greater than about 30 grams per liter (g/L) of deionized water measured at 20 ℃ and atmospheric pressure.

As used herein, the term "equilibrium pH" refers to the pH value of a composition when measured at a dilution of about 1.529 wt% in water at a hardness level of about 342mg/L at 20 ℃. Such water may be obtained, for example, by adding 0.034g CaCl₂And 0.139g MgCl₂·6H₂O is formed by dissolving in one (1) liter of Deionized (DI) water.

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

As used herein, all concentrations and ratios are by weight unless otherwise specified. All temperatures herein are in degrees Celsius (. degree. C.) unless otherwise indicated. All conditions herein are at 20 ℃ and atmospheric pressure unless otherwise specifically indicated. All polymer molecular weights are determined as weight average molecular weights unless otherwise specifically indicated.

Antimicrobial agents

The antimicrobial particulate laundry detergent composition of the present invention comprises a diphenyl ether type antimicrobial agent as one of its key ingredients. More specifically, the diphenyl ether antimicrobial agent for use in the present invention is the nonionic compound 4-4' -dichloro-2-hydroxydiphenyl ether (also referred to as "dichlorosilane"), which is available under the trade name

HP 100 is commercially available from BASF and has the following chemical structure:

such antimicrobial agents may provide antimicrobial benefits against gram positive bacteria (e.g., Staphylococcus aureus) and gram negative bacteria (e.g., Klebsiella pneumoniae), and are therefore particularly useful in the practice of the present invention. Such antimicrobial agents are preferably present in the particulate laundry detergent composition in an amount ranging from about 0.001% to about 3%, more preferably from about 0.005% to about 2%, even more preferably from about 0.01% to about 1%, most preferably from about 0.02% to about 0.2% by weight of the particulate laundry detergent composition. Such particulate laundry detergent compositions are preferably capable of delivering a washing process (through-the-wash) (ttw) concentration level of from about 0.01ppm to about 5ppm, more preferably from about 0.1ppm to about 3ppm, most preferably from about 0.25ppm to about 1ppm of an antimicrobial agent in a laundry wash solution. The cost of incorporating the antimicrobial agent into the particulate laundry detergent composition at this amount and/or this TTW concentration level is still within a reasonable range.

Granular laundry detergent composition

Detergent compositions, preferably laundry detergent compositions, comprising the above-described antimicrobial agents can provide residual antimicrobial benefits to fabrics treated with such compositions, i.e., wherein the nonionic antimicrobial agent deposits onto the fabric during the wash cycle, and the subsequently deposited (i.e., residual) antimicrobial agent prevents bacterial growth on the fabric during drying or storage or wear. However, despite the popularity of 4-4' -dichloro-2-hydroxydiphenyl ether as an antimicrobial active in liquid laundry detergent products, it has not been successfully incorporated into granular laundry detergent products because of its relatively poor antimicrobial efficacy exhibited in conventional granular laundry detergent products.

As noted above, in order to provide the desired residual antimicrobial benefit to the treated fabric or other article, it is desirable that 4-4' -dichloro-2-hydroxydiphenyl ether be deposited on such treated fabric after washing. The deposition method requires 4-4' -dichloro-2-hydroxydiphenyl ether to remain as an insoluble solid in the wash solution; however, it can be rinsed off together with the washing solution.

Without being bound by any theory, it is believed that 4-4' -dichloro-2-hydroxydiphenyl ether, which is a weak acid, can deprotonate and thus become partially soluble, as described below:

thus, the higher the pH of the wash solution, the easier the 4-4' -dichloro-2-hydroxydiphenyl ether is to dissolve (due to kinetics, thermodynamics and equilibrium). Accordingly, the less 4-4' -dichloro-2-hydroxydiphenyl ether that is deposited on the treated fabric or other article and remains on the treated fabric or other article after washing.

Accordingly, by balancing the pH of the granular laundry detergent composition of the present invention (as measured at 1.529 wt% dilution at 20 ℃ in water having a water hardness level of about 342mg/L, which can be measured by adding 0.034g CaCl₂And 0.139g MgCl₂·6H₂O dissolution in one liter of deionized water) to a relatively low range (i.e., lower than conventional granular laundry detergent compositions), which in turn results in a relatively lower equilibrium pH of the wash solution, reduced deprotonation and dissolution of 4-4' -dichloro-2-hydroxydiphenyl ether during the wash process, and effectively improved deposition efficacy and corresponding antimicrobial efficacy. Specifically, it is desirable to adjust the equilibrium pH of the particulate laundry detergent composition of the present invention to a range of from about 6.5 to about 10.5, preferably from about 6.5 to about 10, more preferably from about 7 to about 10, even more preferably from about 7 to about 9.5, even more preferably from about 7 to about 9, and most preferably from about 7 to about 8.5.

There are a number of ways to adjust the equilibrium pH of the particulate laundry detergent composition of the present invention(ii) a pathway. For example, the present invention may employ a pH buffering system for pH adjustment, which system comprises, for example, a water-soluble alkali metal carbonate and/or a water-soluble acid. The water soluble alkali metal carbonate is preferably selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, and combinations thereof. The water-soluble alkali metal carbonate is more preferably sodium carbonate. The water soluble acid may be any suitable acid, either organic or inorganic. The water-soluble acid is preferably water-soluble C₁-C₆The organic acid is, for example, selected from citric acid, lactic acid, and combinations thereof, and the water-soluble acid is more preferably citric acid. Such water-soluble acids may be at least partially coated or even completely coated by a water-dispersible or water-soluble coating material. One suitable water-dispersible coating material is wax, and one suitable water-soluble coating material is citrate. The respective amounts of such water-soluble alkali metal carbonates and such water-soluble acids in the particulate laundry detergent compositions of the present invention can be adjusted so that the equilibrium pH of such compositions falls within the desired range disclosed above. For example, the water-soluble alkali metal carbonate may be present in an amount in the range of from 0% to about 20%, preferably from about 0.01% to about 20%, more preferably from about 0.1% to about 15%, even more preferably from about 0.5% to about 10%, most preferably from about 1% to about 5%, by weight of the particulate laundry detergent composition. In a particularly preferred embodiment of the present invention, the particulate laundry detergent composition is substantially free of water soluble alkali metal carbonate, and more preferably it is substantially free of sodium carbonate. As another example, the water-soluble acid may be present in an amount ranging from 0% to about 20%, preferably from about 0.01% to about 20%, more preferably from about 0.1% to about 15%, even more preferably from about 0.5% to about 10%, most preferably from about 0.75% to about 5%, by weight of the particulate laundry detergent composition.

Thus, it is especially desirable that the particulate laundry detergent composition provides a value of bacteriostatic activity against gram positive and gram negative bacteria to the treated fabric which is at least a Log 1 reduction (Δ Log > -1), preferably less a Log 2 reduction (Δ Log > -2), more preferably at least a Log 2.5 reduction (Δ Log > -2.5) compared to the untreated fabric. Preferably, the composition provides a bacteriostatic activity value against Staphylococcus aureus (Staphylococcus aureus) and/or Klebsiella pneumoniae (Klebsiella pneumoniae) of at least a log 2.2 reduction, preferably a log 2.5 reduction, after 10 minutes of contact in 1529ppm of aqueous solution, as determined by the antimicrobial test method described below.

Preferably, the granular laundry detergent composition of the present invention is a fully formulated, solid, free-flowing particulate laundry detergent composition, not just a portion thereof (such as spray-dried particles, extruded particles or agglomerate particles forming only a part of the laundry detergent composition). Typically, such granular laundry detergent compositions comprise a plurality of chemically distinct particles, such as spray-dried base detergent particles and/or agglomerated base detergent particles and/or extruded base detergent particles; one or more, typically two or more, or five or more, or even ten or more microparticles selected from: surfactant particulates including surfactant agglomerates, surfactant extrudates, surfactant needles, surfactant sheets; phosphate particles; zeolite particles; polymer particles such as carboxylate polymer particles, cellulosic polymer particles, starch particles, polyester particles, polyamine particles, terephthalic acid polymer particles, polyethylene glycol particles; aesthetic particles such as colored bars, needles, lamellar particles, and ring particles; enzyme granules, such as protease granules, amylase granules, lipase granules, cellulase granules, mannanase granules, pectate lyase granules, xyloglucanase granules, bleaching enzyme granules and co-granules of any of these enzymes, preferably the enzyme granules comprise sodium sulphate; bleach particles, such as percarbonate particles, in particular coated percarbonate particles, such as percarbonate coated with carbonate, sulphate, silicate, borosilicate, or any combination thereof, perborate particles, bleach activator particles such as tetraacetylethylenediamine particles and/or alkyloxybenzenesulfonate particles, bleach catalyst particles such as transition metal catalyst particles, and/or isoquinolinium bleach catalyst particles, preformed peracid particles, in particular coated preformed peracid particles; filler particles such as sulfate and chloride particles; clay particles such as montmorillonite particles and clay and silicone particles; flocculant particles, such as polyethylene oxide particles; wax particles, such as waxy agglomerates; silicone particles, brightener particles; dye transfer inhibitor particles; dye fixative particles; perfume particles, such as perfume microcapsules and starch encapsulated perfume accord particles, and pro-perfume particles, such as schiff base reaction product particles; a hueing dye particle; chelant particles, such as chelant agglomerates; and any combination thereof.

Typically, the particulate laundry detergent composition of the invention comprises (in addition to the anti-microbial agent, water-soluble alkali metal carbonate and water-soluble organic acid as described above): (a) from about 5% to about 70%, by weight of such composition, of a surfactant; (b) from about 20% to about 90%, by weight of such composition, of a water-soluble alkali or alkaline earth metal sulfate; (c) from 0% to about 8%, by weight of such composition, of a zeolite builder; (d) from 0% to about 4%, by weight of such composition, of a phosphate builder, and such composition is preferably substantially free of phosphate builder; and (e) from 0% to about 8%, by weight of such composition, of sodium silicate, and such composition is preferably substantially free of sodium silicate.

The water soluble alkali or alkaline earth metal sulfate salt described above is preferably selected from the group consisting of sodium sulfate, potassium sulfate, magnesium sulfate, and combinations thereof. The water-soluble alkali metal or alkaline earth metal sulfate is preferably sodium sulfate and/or magnesium sulfate, and more preferably sodium sulfate. Such water-soluble alkali or alkaline earth metal sulfates are present in an amount ranging from preferably from about 30% to about 80%, more preferably from about 40% to about 70%, by weight of the particulate laundry detergent composition.

The surfactant used in the particulate laundry detergent composition of the present invention may be any suitable surfactant, such as selected anionic surfactants, nonionic surfactants, amphoteric surfactants, and combinations thereof. The surfactant of the present invention preferably comprises an anion selected from the group consisting ofSurfactant (c): c₆-C₂₀Alkyl Sulfates (AS), C₆-C₂₀Alkyl Alkoxy Sulfates (AAS), C₆-C₂₀Linear alkyl benzene sulphonate (LAS), C₆-C₂₀Methyl Ester Sulfonate (MES), C₆-C₂₀Alkyl Ether Carboxylates (AECs), and combinations thereof. More preferably, such anionic surfactants are present in an amount ranging from about 10% to about 60%, preferably from about 12% to about 50%, more preferably from about 15% to about 40%, by weight of the composition. Even more preferably, the particulate laundry detergent composition of the present invention comprises two or more anionic surfactants, e.g. one anionic surfactant is used as the primary surfactant and one or more anionic surfactants are used as the secondary surfactants.

In a particularly preferred embodiment of the present invention, the granular detergent compositions comprise from about 10% to about 20% by weight of such compositions of C₆-C₂₀Linear alkyl benzene sulfonate (LAS), and more preferably from about 0.5% to about 2% C by weight of such compositions₆-C₂₀Alkyl Ethoxy Sulfates (AES), e.g., C having an average degree of ethoxylation of from about 0.5 to about 5, more preferably from about 1 to about 3₁₂-C₁₄AES. The LAS surfactant comprises at least 25 wt.% of the 2-phenyl isomer and the 3-phenyl isomer combined. Suitable LAS surfactants having this characteristic are obtained by DETAL synthesis.

Furthermore, the granular laundry detergent composition preferably comprises, in addition to the anionic surfactant described above, a surfactant selected from the group consisting of C₆-C₂₀Nonionic surfactants of alkyl ethoxylates, such as those from Shell (Shell)

A nonionic surfactant; c₆-C₁₂Alkylphenol alkoxylates, wherein preferably the alkoxylate units are ethyleneoxy units, propyleneoxy units, or mixtures thereof; c₁₂-C₁₈Alcohol and C₆-C₁₂Alkyl phenols withCondensates of ethylene oxide/propylene oxide block polymers, such as those from BASF

(ii) a Alkyl polysaccharides, preferably alkyl polyglycosides; a methyl ester ethoxylate; polyhydroxy fatty acid amides; ether-terminated poly (alkoxylated) alcohol surfactants; and mixtures thereof. Suitable nonionic detersive surfactants also include alkyl alkoxylated alcohols, preferably C_6-20Alkyl alkoxylated alcohols, preferably C_6-20The alkyl ethoxylated alcohol, preferably the alkyl alkoxylated alcohol, has an average degree of alkoxylation of from 1 to 50, preferably from 1 to 30, or from 1 to 20, or from 1 to 10, the alkyl alkoxylated alcohol preferably being C_6-20An alkyl ethoxylated alcohol having an average degree of ethoxylation of from 1 to 10, preferably from 1 to 7, more preferably from 1 to 5, and most preferably from 3 to 7. The alkyl alkoxylated alcohol may be linear or branched, and substituted or unsubstituted. The nonionic surfactant is preferably selected from C₆-C₂₀Alkoxylated alcohol, and may be present in an amount ranging from about 0.01% to about 10%, preferably from about 0.05% to about 5%, more preferably from about 0.1% to about 3%, by weight of such compositions. In a particularly preferred embodiment of the present invention, the granular laundry detergent composition comprises, in addition to anionic surfactant, from about 0.1% to about 1% by weight of such composition of C₆-C₂₀Alkoxylated alcohol, preferably C having about 7 to about 9 EO units₁₂-C₁₅An ethoxylated alcohol.

The granular laundry detergent compositions of the present invention may further comprise one or more suitable cationic surfactants such as alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl tertiary sulfonium compounds, and mixtures thereof.

The particulate laundry detergent compositions of the present invention may also comprise one or more zwitterionic surfactants, such as amine oxides and/or betaines. Such compositions preferably further comprise an alkylamine oxide.

The particulate laundry detergent compositions of the present invention may comprise from 0% to about 6%, preferably from 0% to about 4%, by weight of such compositions, of sodium bicarbonate. Such compositions are preferably substantially free of sodium bicarbonate.

The particulate laundry detergent composition of the present invention may comprise, in addition to the ingredients disclosed above, one or more polymers selected from the group consisting of: cationic polymers, carboxylate polymers, soil release polymers, anti-redeposition polymers, cellulosic polymers, care polymers, and any combination thereof.

For example, the particulate laundry detergent composition of the present invention may comprise from 0.01% to 5%, preferably from 0.02% to 1%, more preferably from 0.05% to 0.5% by weight of the composition of a cationic polymer. The cationic polymer preferably has a cationic charge density of from about 0.05 to about 23 milliequivalents/g, more preferably from about 0.01 to about 12 milliequivalents/g, and most preferably from about 0.1 to about 7 milliequivalents/g. The charge density is calculated by dividing the net charge per repeat unit by the molecular weight of the repeat unit. The positive charge may be located on the polymer backbone and/or on the polymer side chains. Non-limiting examples of suitable cationic polymers are cationic polysaccharides, cationic proteins, and cationic synthetic polymers. The cationic polysaccharide may include cationic cellulose polymers, cationic guar, cationic chitosan, cationic starch, and derivatives and combinations thereof. Suitable cationic polysaccharides include cationically modified celluloses, such as cationic hydroxyethyl cellulose and/or cationic hydroxypropyl cellulose. Preferred cationic celluloses for use herein include those which may or may not be hydrophobically modified, including those having a weight average molecular weight in the range of from about 50,000 daltons to about 2,000,000 daltons, preferably from about 100,000 daltons to about 1,000,000 daltons, more preferably from about 200,000 daltons to about 800,000 daltons.

For example, the particulate laundry detergent composition may comprise, by weight of such composition, from about 0.5% to about 5% of a carboxylate copolymer comprising: (i) from about 50% to less than about 98% by weight structural units derived from one or more carboxyl-containing monomers; (ii) from about 1% to less than about 49% by weight structural units derived from one or more monomers comprising a sulfonate moiety; and (iii) from about 1% to about 49% by weight of structural units derived from one or more types of monomers selected from ether linkage-containing monomers.

The particulate laundry detergent composition may further comprise a polyethylene glycol (PEG) polymer comprising a polyethylene glycol backbone and grafted polyvinyl acetate side chains.

The granular laundry detergent composition may also comprise a soil release polymer, such as a PEG-based polyester soil release polymer. The granular laundry detergent composition may comprise a combination of a nonionic soil release polymer and an anionic soil release polymer.

The particulate laundry detergent composition may further comprise carboxymethyl cellulose having a degree of substitution greater than 0.65 and a degree of blockiness greater than 0.45.

The composition may comprise an alkoxylated polyalkyleneimine, and such alkoxylated polyalkyleneimine has a polyalkyleneimine core and one or more side chains bonded to at least one nitrogen atom in the polyalkyleneimine core. For example, such alkoxylated polyalkyleneimines can have the empirical formula (I): (PEI)_a-(EO)_b-R₁Wherein a is the average number average Molecular Weight (MW) of the polyalkyleneimine core of the alkoxylated polyalkyleneimine_PEI) And in the range of 100 daltons to 100,000 daltons, wherein b is the average degree of ethoxylation in the one or more side chains of the alkoxylated polyalkyleneimine and is in the range of 5 to 40, and wherein R₁Independently selected from hydrogen, C₁-C₄Alkyl groups, and combinations thereof. As another example, the alkoxylated polyalkyleneimine can have the empirical formula (II): (PEI)_o-(EO)_m(PO)_n-R₂Or (PEI)_o-(PO)_n(EO)_m-R₂Wherein o is the average number average Molecular Weight (MW) of the polyalkyleneimine core of the alkoxylated polyalkyleneimine_PEI) And in the range of 100 daltons to 100,000 daltons, wherein m is in the alkoxylated polyalkyleneimineAn average degree of ethoxylation in the one or more side chains, the m is in the range of 10 to 50, wherein n is an average degree of propoxylation in the one or more side chains of the alkoxylated polyalkyleneimine, n is in the range of 1 to 50, and wherein R₂Independently selected from hydrogen, C₁-C₄Alkyl groups, and combinations thereof.

Suitable care polymers include cationically modified or hydrophobically modified cellulosic polymers. Such modified cellulosic polymers can provide anti-abrasion benefits and dye lock benefits to fabrics during the wash cycle. Suitable cellulosic polymers include cationically modified hydroxyethyl cellulose. Other suitable care polymers include dye-locking polymers such as condensation oligomers produced by condensation of imidazole and epichlorohydrin, preferably in a 1:4:1 ratio. Suitable commercially available dye-locking polymers are

FDI (cognis). Other suitable care polymers include amino-silicones, which can provide fabric feel benefits and fabric shape retention benefits.

The particulate laundry detergent composition of the present invention may further comprise one or more of the following ingredients:

suitable enzymes include lipases, proteases, cellulases, amylases, and any combination thereof.

Suitable proteases include metalloproteases and serine proteases. Examples of suitable neutral or alkaline proteases include: subtilisin (EC 3.4.21.62); trypsin-type or chymotrypsin-type proteases; and a metalloprotease. Suitable proteases include chemically or genetically modified mutants of the aforementioned proteases. Suitable commercially available proteases include those sold under the trade name Novozymes (Novozymes A/S) by Denmark Novozymes

And

those sold; under the trade name DuPont

A series of proteases (including

P2082-EE and

P2083-A/J)、

Purafect

Purafect

and Purafect

Those sold; commercially available from Sovienase (Solvay Enzymes)

And

those sold; those available from Henkel/Kemira; and KAP from Kao.

Suitable amylases are derived from the AA560 α amylase endogenously derived from bacillus sp DSM 12649. Suitable commercially available amylases include

Plus、Natalase、

Ultra、

SZ、

(both from Novozymes) and

AA、

a series of amylase,

And

Ox Am、

HT Plus (both from Du Pont).

Suitable cellulases include those derived from bacteria or fungi. Chemically modified or protein engineered mutants are also suitable. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas (Pseudomonas), Humicola (Humicola), Fusarium (Fusarium), Rhizopus (Thielavia), Acremonium (Acremonium), for example from Humicola insolens, Myceliophthora thermophila and SporotrichumFungal cellulases produced by Fusarium oxysporum. Commercially available cellulases include

And

Premium、

and

(Novozymes A/S)、

the series of enzymes (Du Pont), and

series of Enzymes (AB Enzymes). Suitable commercially available cellulases include

Premium、

Classic。

Suitable lipases include those of bacterial, fungal or synthetic origin, as well as variants thereof. Chemically modified or protein engineered mutants are also suitable. Examples of suitable lipases include lipases from humicola (the synonym Thermomyces), for example from humicola lanuginosa (h.lanuginosa) (Thermomyces lanuginosus) sp. Preferred lipases include those known under the trade name

And

those sold by Novozymes (Bagsvaerd, Denmark).

Other suitable enzymes are bleaching enzymes such as peroxidases/oxidases, including those of plant, bacterial or fungal origin and variants thereof. Commercially available peroxidases include

(Novozymes A/S). Other suitable enzymes include choline oxidase and perhydrolase, such as for Gentle Power Bleach^TMOf (a). Other suitable enzymes include those known under the trade name

(from Novozymes A/S, Bagsvaerd, Denmark) and

pectate lyases sold by DuPont and under the trade name

(Novozymes A/S, Bagsvaerd, Denmark) and

mannanase sold by (Du Pont).

Suitable bleaching agents include sources of hydrogen peroxide, bleach activators, bleach catalysts, preformed peracids, and any combination thereof. Particularly suitable bleaching agents include a hydrogen peroxide source in combination with a bleach activator and/or bleach catalyst. Suitable sources of hydrogen peroxide include sodium perborate and/or sodium percarbonate. Suitable bleach activators include tetraacetylethylenediamine and/or alkylphenol sulfonates. Suitable bleach catalysts include the peroxyimine cation bleach catalysts, transition metal bleach catalysts, especially manganese and iron bleach catalysts. Suitable preformed peracids include phthalimido-peroxycaproic acid. Preferably, however, the composition is substantially free of preformed peracid.

The particulate laundry detergent composition may further comprise a chelant selected from the group consisting of: diethylene triamine pentaacetate, diethylene triamine penta (methyl phosphonic acid), ethylene diamine-N' -disuccinic acid, ethylene diamine tetraacetate, ethylene diamine tetra (methylene phosphonic acid), and hydroxyethane di (methylene phosphonic acid). Preferred chelating agents are ethylenediamine-N' -disuccinic acid (EDDS) and/or hydroxyethane diphosphonic acid (HEDP). The composition preferably comprises ethylenediamine-N' -disuccinic acid or salts thereof. Preferably ethylenediamine-N 'N' -disuccinic acid is in the form of the S, S enantiomer. Preferably, the composition comprises 4, 5-dihydroxy-m-benzenedisulfonic acid disodium salt. Preferred chelating agents may also act as calcium carbonate crystal growth inhibitors, such as: 1-hydroxyethane diphosphoric acid (HEDP) and salts thereof; n, N-dicarboxymethyl-2-aminopentane-1, 5-dioic acid or its salt; 2-phosphonobutane-1, 2, 4-tricarboxylic acid and salts thereof; and combinations thereof.

Many toners suitable for use in the present invention are known and described in the art. Suitable hueing agents include small molecule dyes, typically of the acid, direct, basic, reactive (including their hydrolyzed forms) or solvent or disperse dye color index (c.i.) classes, such as dyes classified as blue, violet, red, green or black, and provide the desired hue, either alone or in combination. Preferred such hueing agents include acid violet 50, direct violet 9, 66 and 99, solvent violet 13, and any combination thereof. Suitable hueing agents also include phthalocyanine and azo dye conjugates, alkoxylated disazo dyes, alkoxylated thiophene azo dyes, and the like. The hueing agent may be incorporated into the detergent composition as part of the reaction mixture as a result of the organic synthesis of the dye molecule by one or more optional purification steps. Such reaction mixtures generally comprise the dye molecules themselves and may, in addition, comprise unreacted starting materials and/or by-products of organic synthesis pathways. Suitable hueing agents may also be incorporated into the hueing dye particles.

Suitable dye transfer inhibiting agents include polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone, polyvinyloxazolidone, polyvinylimidazole, and mixtures thereof. Preferred are poly (vinylpyrrolidone), poly (vinylpyridine betaine), poly (vinylpyridine)N-oxide), poly (vinylpyrrolidone-vinylimidazole), and mixtures thereof. Suitable commercially available dye transfer inhibitors include PVP-K15 and K30(Ashland),

HP165、HP50、HP53、HP59、HP56K、HP56、HP66(BASF)，

s-400, S403E, and S-100 (Ashland).

Suitable perfumes include perfume materials selected from the group consisting of: (a) a perfume material having a ClogP of less than 3.0 and a boiling point of less than 250 ℃ (quadrant 1 perfume material); (b) perfume materials having a ClogP of less than 3.0 and a boiling point of 250 ℃ or higher (quadrant 2 perfume materials); (c) a perfume material having a ClogP of 3.0 or greater and a boiling point of less than 250 ℃ (quadrant 3 perfume material); (d) a perfume material having a ClogP of 3.0 or greater and a boiling point of 250 ℃ or higher (quadrant 4 perfume material); and (e) mixtures thereof. It may be preferred for the perfume to be in the form of a perfume delivery technology. Such delivery techniques are also stable and enhance deposition and release of perfume materials from laundered fabrics. Such perfume delivery technologies can also be used to further increase the longevity of perfume release from laundered fabrics. Suitable perfume delivery technologies include: perfume microcapsules, pro-perfumes, polymer assisted delivery, molecular assisted delivery, fiber assisted delivery, amine assisted delivery, cyclodextrins, starch encapsulated accords, zeolites and other inorganic carriers, and any mixtures thereof.

Suitable silicones include polydimethylsiloxane and aminosilicone.

The particulate laundry detergent composition of the present invention may be prepared by any suitable process including, for example, spray drying, agglomeration, extrusion and any combination thereof.

For example, a suitable spray drying process includes the steps of forming an aqueous slurry mixture, transferring it to a pressure nozzle by at least one pump, preferably two pumps. For anionic surfactants, such as linear alkyl benzene sulphonate, it may be preferred to introduce into the spray drying process after the step of forming the aqueous slurry mixture: for example, after pumping, the acid precursor is introduced into the aqueous slurry mixture. For gases, such as air, it may be preferred to be introduced into the spray drying process after the step of forming the aqueous slurry. For any inorganic ingredients, such as sodium sulfate and sodium carbonate, it may be preferred that if present in the aqueous slurry mixture, be micronized to a small particle size.

As another example, the particulate laundry detergent composition of the present invention is formed using a suitable agglomeration process comprising the step of contacting a detersive ingredient, such as a detersive surfactant, for example linear alkyl benzene sulphonate (LAS) and/or alkyl alkoxylated sulphate, with an inorganic material, such as sodium carbonate and/or silica, in a mixer. The agglomeration process may also be an in-situ neutralisation agglomeration process, wherein an acid precursor of the detersive surfactant, such as LAS, is contacted with a basic material, such as carbonate and/or sodium hydroxide, in a mixer, and wherein the acid precursor of the detersive surfactant is neutralised by the basic material during the agglomeration process to form the detersive surfactant. Other suitable detergent ingredients that may be agglomerated include polymers, chelants, bleach activators, silicones, and any combination thereof. The agglomeration process may be a high, medium, or low shear agglomeration process, wherein a high shear, medium shear, or low shear mixer is used, respectively. The agglomeration process may be a multi-step agglomeration process in which two or more mixers are used, such as a high shear mixer in combination with a medium or low shear mixer. The agglomeration process may be a continuous process or a batch process. It may be preferred for the agglomerates to be subjected to a drying step, for example, a fluid bed drying step. It may also be preferred for the agglomerates to be subjected to a cooling step, for example, a fluidized bed cooling step. Typically, the agglomerates are subjected to particle size classification, e.g., fluidized bed elution and/or sieving, to obtain the desired particle size distribution. Preferably, the agglomerates have a particle size distribution such that the weight average particle size is in the range of 300 microns to 800 microns, and less than 10% by weight of the agglomerates have a particle size of less than 150 microns, and less than 10% by weight of the agglomerates have a particle size of greater than 1200 microns.

For ingredients such as polymer and/or nonionic detersive surfactant and/or perfume, it may be preferred to spray onto the base detergent particles, such as spray-dried base detergent particles and/or agglomerated base detergent particles. Typically, this spraying step is carried out in a tumble mixer.

Method for washing fabrics

The method of laundering fabrics with the particulate laundry detergent composition of the present invention comprises the steps of contacting the solid composition with water to form a wash liquor, and laundering fabrics in said wash liquor. Typically, the washing liquid has a temperature of from above 0 ℃ to 90 ℃, or to 60 ℃, or to 40 ℃, or to 30 ℃, or to 20 ℃. The fabric may be contacted with water before, after, or simultaneously with contacting the solid composition with water. Typically, the wash liquor is formed by contacting the laundry detergent with water in such an amount that the concentration of the laundry detergent composition in the wash liquor is from 0.2g/l to 20g/l, or from 0.5g/l to 10g/l, or to 5.0 g/l. The method of washing fabrics may be carried out in a front loading automatic washing machine, a top loading automatic washing machine, including high efficiency automatic washing machines, or a suitable hand washing receptacle. Typically, the wash liquor comprises 90 litres or less, or 60 litres or less, or 15 litres or less, or 10 litres or less of water. Typically, 200g or less, or 150g or less, or 100g or less, or 50g or less of the laundry detergent composition is contacted with water to form a wash liquor.

Test method

Test 1: antimicrobial testing

The antimicrobial efficacy of the sample particulate laundry detergent composition was measured as follows:

each defined sample of the granular laundry detergent composition to be tested (e.g., 15.29g) was dissolved in 1L of water having a water hardness level of 342 mg/L. Such water is obtained by passing 0.034g CaCl₂And 0.139g MgCl₂·6H₂O is formed by dissolving in 1L Deionized (DI) water. By passingThe solution was mixed by a magnetic stirrer for about 4 minutes and then 265ml of such solution was dispensed into the exposed chamber of the washing drum as described in the laundry detergent sterilization test method promulgated by the japanese detergent and soap equity exchange commission.

In addition, the stainless steel mandrel was made from a single continuous stainless steel wire having a diameter of about 1/16 inches, which was bent to form 3 horizontally extending segments each about 2 inches long, connected by 2 vertical segments about 2 inches long. The mandrel serves as a carrier for wrapping the fabric ballast.

Approximately 300 grams of cotton fabric was then scoured by boiling for one hour in 3L of distilled or DI water containing about 1.5 grams of sodium carbonate and about 1.5 grams of a non-ionic wetting agent. The fabric was then rinsed in boiling water and then in cold water until all visible traces of foam formed by the wetting agent were removed. The fabric was then drained and air dried at ambient temperature for at least 24 hours. The scoured and dried fabric was then cut into strips each having a width of about 2 inches and weighing about 15 ± 0.1 g. A piece of such cotton fabric strip is then taken and one of its ends is fixed to the outer horizontal extension of the stainless steel mandrel. This strip of cotton fabric is wrapped around the three horizontally extending sections of the mandrel with sufficient tension for about 12 to 13 turns until the entire strip of fabric is wrapped onto the mandrel. Staples or pins may be used to secure the loose ends of the fabric strip. The fabric wrapped mandrel may then be sterilized in a separate exposure chamber of the washing drum described above, or separately from the exposure chamber. The fabric wrapped around the mandrel and the exposure chamber should both be dry prior to placing the mandrel into the exposure chamber.

The fabric wrapped mandrel was then placed into the exposed chamber of a wash drum containing 265ml of the above wash solution. The exposed chamber was then stirred at about 60rpm for about 20 minutes. After stirring for 20 minutes, the fabric-wrapped mandrel was centrifuged for about 2 minutes and the wash solution was discarded. 265ml of fresh hard water as described above was then dispensed into the same exposed chamber of the mandrel used to rinse the fabric wrap. The exposed chamber was stirred at the same stirring speed for an additional 3 minutes, then the fabric-wrapped mandrel was again spin-dried for about 2 minutes, and then the rinse solution was discarded. The fabric wrapped mandrel was rinsed and again spin dried in the same manner as described above.

Next, the cotton fabric strips were removed from the mandrel and air dried overnight at ambient temperature. The dried strips of cotton fabric were then cut into 2cm x 2cm square pieces and 10 pieces of such cotton fabric were stacked together to form a test sample weighing about 0.40 ± 0.05 g.

Then, the test specimen was evaluated according to the method for evaluating bacteriostatic activity described in the L1902-2015 standard of section 8.1 of the Japanese Industrial Standard (JIS), but the number of bacteria was calculated according to section 8.1.4.5.2 (instead of calculating the amount of ATP as described in section 8.1.4.5.3).

Examples

Example 1: granular coating exhibiting an equilibrium pH value comprising 0.025% of 4-4' -dichloro-2-hydroxydiphenyl ether Comparative testing of the effectiveness of the antimicrobial efficacy of a composition of a laundry detergent

Four (4) exemplary solid, free-flowing particulate laundry detergent compositions were prepared as follows:

using the antimicrobial test described above, water having a hardness level of about 342mg/L was used (by adding 0.034g CaCl₂And 0.139g MgCl₂·6H₂O dissolved in 1 liter of deionized water to form such hard water) was measured at a dosage level of about 1529ppm for the antimicrobial efficacy of each of the above granular laundry detergent compositions. The following are the measurement results:

	A	B	C	D
					equilibrium pH	10	9.52	8.49	6.99
Logarithmic decrease of the value of the bacteriostatic activity (. DELTA.Log)	0.11	2.24	2.69	2.55

When the equilibrium pH of the above four granular laundry detergent compositions is about 9.5 or less, the logarithmic decrease in the bacteriostatic activity value (Δ Log) is greater than 1.

Example 2: granular coating exhibiting an equilibrium pH value comprising 0.05% of 4-4' -dichloro-2-hydroxydiphenyl ether Comparative testing of the effectiveness of the antimicrobial efficacy of a composition of a laundry detergent

Five (5) exemplary solid, free-flowing particulate laundry detergent compositions were prepared as follows:

using the antimicrobial test described above, water having a hardness level of about 342mg/L (pass through)0.034g of CaCl₂And 0.139g MgCl₂·6H₂O dissolved in 1 liter of deionized water to form such hard water) was measured at a dosage level of about 1529ppm for the antimicrobial efficacy of each of the above granular laundry detergent compositions. The following are the measurement results:

	E	F	G	I	H
						equilibrium pH	10.54	10.03	9.49	8.49	6.99
Logarithmic decrease of the value of the bacteriostatic activity (. DELTA.Log)	0.03	0.55	5.2	4.64	5.48

When the equilibrium pH of the five granular laundry detergent compositions is about 9.5 or less, the logarithmic decrease in the bacteriostatic activity value (Δ Log) is greater than 1.

Example 3: particulate garments exhibiting an equilibrium pH value comprising 0.1% of 4-4' -dichloro-2-hydroxydiphenyl ether Comparative testing of the effectiveness of detergent compositions for antimicrobial efficacy

	I	J	K	L
					equilibrium pH	10.7	10.51	10.04	9.51
Logarithmic decrease of the value of the bacteriostatic activity (. DELTA.Log)	-0.09	-0.15	2.52	3.11

When the equilibrium pH of the above 4 granular laundry detergent compositions was about 10 or less, the logarithmic decrease (Δ Log) of the bacteriostatic activity value was greater than 1.

Example 4: exemplary particulate laundry detergent compositions

The following are exemplary solid, free-flowing particulate laundry detergent compositions:

the dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Rather, unless otherwise specified, 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 "40 mm" is intended to mean "about 40 mm".

Each document cited herein, including any cross referenced or related patent or patent application and any patent application or patent to which this application claims priority or its benefits, 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 any disclosure of the invention or the claims herein or that it alone, or in combination with any one or more of the references, teaches, suggests or discloses any such invention. Further, 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 invention 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 invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

1. A particulate laundry detergent composition, the composition comprising:

(a) from 5% to 70%, by weight of the composition, of a surfactant; and

(b) from 0.01% to 3%, by weight of the composition, of an antimicrobial agent which is 4-4' -dichloro-2-hydroxydiphenyl ether,

wherein the particulate laundry detergent composition is characterized by an equilibrium pH in the range of 6.5 to 9.5, the term "equilibrium pH" referring to the pH value of the composition when measured at 1.529 wt% dilution at 20 ℃ in water having a hardness level of 342 mg/L.

2. The particulate laundry detergent composition according to claim 1, wherein the equilibrium pH of the particulate laundry detergent composition is in the range of from 7 to 9.5.

3. The particulate laundry detergent composition according to claim 2, wherein the equilibrium pH of the particulate laundry detergent composition is in the range of 7 to 9.

4. The particulate laundry detergent composition according to claim 3, wherein the equilibrium pH of the particulate laundry detergent composition is in the range of from 7 to 8.5.

5. The particulate laundry detergent composition according to claim 4, wherein the antimicrobial agent is present in an amount ranging from 0.01% to 1% by weight of the composition.

6. The particulate laundry detergent composition according to claim 5, wherein the antimicrobial agent is present in an amount ranging from 0.02% to 0.2% by weight of the composition.

7. The particulate laundry detergent composition according to claim 1, further comprising a water-soluble alkali or alkaline earth metal sulfate; wherein the water soluble alkali or alkaline earth metal sulfate is selected from the group consisting of sodium sulfate, potassium sulfate, magnesium sulfate, and combinations thereof; and wherein the water soluble alkali or alkaline earth metal sulfate is present in an amount ranging from 20% to 90% by weight of the composition.

8. The particulate laundry detergent composition according to claim 7, wherein the water-soluble alkali or alkaline earth metal sulfate is sodium sulfate.

9. The particulate laundry detergent composition according to claim 7, wherein the water-soluble alkali or alkaline earth metal sulphate is present in an amount in the range 30% to 80%, the sum of the component levels of the composition being 100%.

10. The particulate laundry detergent composition according to claim 9, wherein the water-soluble alkali or alkaline earth metal sulphate is present in an amount in the range of 40% to 70%, the sum of the component levels of the composition being 100%.

11. The particulate laundry detergent composition according to claim 1, further comprising a water-soluble alkali metal carbonate; wherein the water soluble alkali metal carbonate is selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, and combinations thereof; and wherein the water soluble alkali metal carbonate is present in an amount ranging from 0.01% to 20% by weight of the composition.

12. The particulate laundry detergent composition according to claim 11, wherein the water-soluble alkali metal carbonate is sodium carbonate.

13. The particulate laundry detergent composition according to claim 1, further comprising a water-soluble acid; and wherein the water soluble acid is present in an amount ranging from 0.01% to 20% by weight of the composition.

14. The particulate laundry detergent composition according to claim 13, wherein the water-soluble acid is water-soluble C₁-C₆An organic acid.

15. The particulate laundry detergent composition according to claim 14, wherein the water soluble acid is selected from citric acid, lactic acid, and combinations thereof.

16. The particulate laundry detergent composition according to claim 15, wherein the water-soluble acid is citric acid.

17. The particulate laundry detergent composition according to claim 1, wherein the surfactant comprises an anionic surfactant selected from the group consisting of: c₆-C₂₀Alkyl Sulfates (AS), C₆-C₂₀Alkyl Alkoxy Sulfates (AAS), C₆-C₂₀Linear alkyl benzene sulphonate (LAS), C₆-C₂₀Methyl ester sulfonic acidAcid salt (MES), C₆-C₂₀Alkyl Ether Carboxylates (AECs), and combinations thereof; wherein the anionic surfactant is present in an amount ranging from 10% to 60% by weight of the composition.

18. The particulate laundry detergent composition according to claim 17, wherein the surfactant further comprises a surfactant selected from C₆-C₂₀A nonionic surfactant of an alkoxylated alcohol, wherein the nonionic surfactant is present in an amount ranging from 0.01% to 10% by weight of the composition.

19. The particulate laundry detergent composition according to claim 1, further comprising a cationic polymer, said cationic polymer being a cationic polysaccharide; wherein the cationic polymer is present in an amount ranging from 0.01% to 5% by weight of the composition.

20. The particulate laundry detergent composition according to claim 19, wherein the cationic polymer is a cationic cellulose polymer.

21. The particulate laundry detergent composition according to claim 20, wherein the cationic polymer is cationic hydroxyethyl cellulose.

22. A particulate laundry detergent composition, the composition comprising:

(a) from 10% to 20% by weight of the composition of C₆-C₂₀Linear alkyl benzene sulphonate (LAS);

(b) from 0.5% to 2% by weight of the composition of C₆-C₂₀Alkyl Ethoxy Sulfates (AES);

(c) from 0.1% to 1% by weight of the composition of C₆-C₂₀An alkoxylated alcohol;

(d) from 0.02% to 0.2%, by weight of the composition, of 4-4' -dichloro-2-hydroxydiphenyl ether;

(e) from 50% to 85%, by weight of the composition, of sodium sulfate;

(f) from 0% to 10% by weight of the composition of sodium carbonate; and

(g) from 0% to 5% by weight of the composition of citric acid,

wherein the particulate laundry detergent composition is characterized by an equilibrium pH in the range of from 7 to 9.5, wherein the term "equilibrium pH" refers to the pH value of the composition when measured as an 1.529 wt% dilution in water at a hardness level of 342mg/L at 20 ℃.

23. The granular laundry detergent composition according to claim 1 or 22, characterized by a reduction in the bacteriostatic activity value for both gram-positive and gram-negative bacteria of at least log 1.

24. A method of improving the antimicrobial efficacy of 4-4 '-dichloro-2-hydroxydiphenyl ether in a particulate laundry detergent composition by adjusting the equilibrium pH of the particulate laundry detergent composition to be in the range of 6.5 to 9.5, wherein the term "equilibrium pH" refers to the pH value of the composition when measured at 1.529 wt% dilution in water at a hardness level of 342mg/L at 20 ℃, wherein the composition comprises from 0.01% to 3% of 4-4' -dichloro-2-hydroxydiphenyl ether by weight of the composition.

25. The method according to claim 24, wherein the equilibrium pH of the particulate laundry detergent composition is adjusted to be in the range of 7 to 9.5.

26. The method according to claim 25, wherein the equilibrium pH of the particulate laundry detergent composition is adjusted to be in the range of 7 to 9.

27. The method according to claim 26, wherein the equilibrium pH of the particulate laundry detergent composition is adjusted to be in the range of 7 to 8.5.

28. The method according to claim 24 or 25, wherein the pH adjustment is performed by using a pH buffering system comprising a water soluble alkali metal carbonate and/or a water soluble acid.

29. The method of claim 28, wherein the water soluble alkali metal carbonate is sodium carbonate, and wherein the water soluble acid is citric acid.

30. The method according to claim 29, wherein the sodium carbonate is present in an amount ranging from 0.01% to 20% by weight of the particulate laundry detergent composition; wherein the citric acid is present in an amount ranging from 0.01% to 20% by weight of the composition.