JP2019073723A - Liquid anti-microbial laundry detergent composition - Google Patents

Abstract

A liquid antimicrobial laundry detergent composition that exhibits a good stability portfolio while maintaining cleaning performance. 0.001% to 3%, based on the weight of the composition, of a nonionic antibacterial agent represented by the following formula (wherein each Y is independently selected from chlorine, bromine or fluorine; each Z is independently selected from SO2H, NO2 or C1-C4 alkyl, 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); A liquid antibacterial laundry detergent composition. [Selection figure] None

Description

  The present invention relates to liquid antimicrobial laundry detergent compositions.

  Consumer products have been developed to address the user's need for antimicrobial efficacy in addition to the originally intended function. For example, antimicrobial laundry detergent products are desired by users because they provide an antimicrobial effect on the fabric while cleaning the fabric. At present, the typical approach to bring about an antimicrobial effect is to incorporate an antimicrobial agent into the formulation of consumer products. Such an antibacterial agent destroys the bacterial envelope and kills the bacteria, or denatures the bacterial envelope to prevent the growth or reproduction of the bacteria, thereby providing an antibacterial effect.

  Many known antimicrobial agents present stability issues when incorporated into liquid laundry detergent compositions. For example, lauryltrimethyl ammonium chloride, a conventional cationic antimicrobial agent, suffers from compatibility problems with anionic surfactants that are usually present in laundry detergent compositions. In order to solve this compatibility problem, the art teaches to formulate relatively high concentrations of solvents or stabilizers into the composition. This high concentration of solvent or stabilizer results in a reduction in the cleaning performance, since it dilutes the concentration of surfactant in the composition. In addition, increasing the concentration of the solvent or stabilizer leads to an undesirable increase in cost.

  Thus, there is a need for liquid antimicrobial laundry detergent compositions that exhibit a good stability portfolio while maintaining comparable cleaning performance.

  It is an advantage of the present invention to provide a stable liquid antimicrobial laundry detergent composition that can minimize the concentration of solvent or stabilizer. In particular, the present invention enables stable high concentration liquid antimicrobial laundry detergent compositions.

The present invention relates to a liquid antimicrobial laundry detergent composition, which comprises:
a) 0.001% to 3% non-ionic antibacterial agent with respect to the weight of the composition,
b) 0.1% to 2.5% organic solvent, based on the weight of the composition, which is a C ₁ -C ₆ alcohol.

Definitions As used herein, the term "laundry detergent composition" means a composition for the cleaning of fabrics. As used herein, the term "liquid laundry detergent composition" refers to a composition that is in a form selected from the group consisting of pourable liquids, gels, creams and combinations thereof. The liquid laundry detergent composition may be either aqueous or non-aqueous, anisotropic, isotropic or combinations thereof.

  As used herein, the term "antimicrobial agent" is a chemical compound whose main predetermined function is the killing of bacteria or the prevention of bacterial growth or reproduction. Conventional antimicrobial agents include cationic antimicrobial agents (eg, certain ammonium chlorides), nonionic antimicrobial agents, and the like. Preferred diphenyl ether compounds for use in the present invention are non-ionic antimicrobial agents.

  As used herein, the term "washing solution" refers to the normal volume of aqueous solution used in one wash wash cycle, preferably 1 L to 50 L, or 1 L to 20 L by hand, 20 L to wash by washing machine It is 50L.

  As used herein, the term "alkyl" means a hydrocarbyl moiety that is branched or unbranched, substituted or unsubstituted. The term "alkyl" includes the alkyl portion of an acyl group.

  As used herein, a composition is "substantially free" of a particular component if the composition contains less than a trace amount, or less than 0.1% by weight of the composition, or 0.01. It is meant to contain less than weight percent, or alternatively 0.001 weight percent of the specified ingredient.

  As used herein, articles including "a" and "an" are understood to mean one or more of the claims or set forth as used in the claims.

  As used herein, the terms "comprise, comprises, comprising", "includes, includes, including", "contains, contains, containing" are non-limiting. That is, other steps and other ingredients that do not affect the end result can be added. The above terms include the terms "consisting of and" consisting essentially of.

Liquid Antibacterial Laundry Detergent Composition The liquid antibacterial laundry detergent composition of the present invention comprises 0.1% to 2.5% of 0.001% to 3% of a nonionic antibacterial agent, based on the weight of the composition. It contains an organic solvent which is a C ₁ -C ₆ alcohol. It has surprisingly been found that by selecting a particular type of antimicrobial, the liquid composition of the present invention exhibits a good stability portfolio without the need to reduce its cleaning performance. Without being bound by theory, it is believed that the antimicrobial properties of the present invention allow for stable liquid antimicrobial laundry detergent compositions in the presence of relatively low concentrations of solvent due to their non-ionic nature . In contrast, in the context of low concentrations of solvents, conventional cationic antimicrobials are not compatible with the anionic surfactants present in the laundry detergent composition. Therefore, conventional cationic antibacterial agents can not achieve a stable liquid composition unless a relatively high concentration of solvent is used, which dilutes the concentration of the surfactant and causes a decrease in the cleaning performance. In other words, it is difficult to achieve both good stability and cleaning performance using conventional cationic antimicrobials.

  Preferably, the non-ionic antimicrobial agent is present in the liquid laundry detergent composition from 0.01% to 1%, more preferably 0.03% to 0.5%, by weight of the composition. The organic solvent is preferably present at 0.2% to 2%, more preferably 0.3% to 1.5%, based on the weight of the composition.

  The liquid laundry detergent composition can deliver the antimicrobial agent in the laundry wash liquor preferably at a concentration of 0.01 ppm to 5 ppm, more preferably 0.05 ppm to 3 ppm, more preferably 0.1 ppm to 1 ppm.

  The laundry detergent compositions herein provide an antimicrobial effect against both gram positive bacteria (eg, Staphylococcus aureus) and gram negative bacteria (eg, Klebsiella pneumoniae). The composition preferably provides a residual antimicrobial effect to the fabric treated with the composition, ie, the non-ionic antimicrobial agent in the composition is deposited on the fabric during the wash cycle and then deposited (ie, remains) 2.) The antimicrobial agent prevents bacteria from growing on the fabric during drying, storage or wearing. In one embodiment, the laundry detergent composition has a log reduction of at least 2.2, preferably 2 as compared to treated and non-treated fabrics, for both gram positive and gram negative bacteria. It results in bacteriostatic activity values with a log reduction of .5. Preferably, the composition has a log reduction of at least 2.2, preferably against Staphylococcus aureus and / or Klebsiella pneumoniae, after a contact time of 10 minutes in a 2069 ppm aqueous solution as defined in JIS L 1902 method (described below). Results in a 2.5 log reduction. More preferably, the composition provides at least a 3.0 log reduction, preferably a 3.5 log reduction, for S. aureus. It should be noted that fabrics, particularly those worn, are required to have antimicrobial activity, particularly against S. aureus, as S. aureus is frequently found on human skin.

  The laundry detergent compositions herein may be acidic or alkaline or pH neutral, depending on the ingredients to be incorporated into the composition. The pH range of the laundry detergent composition is preferably 6 to 12, more preferably 7 to 11, and even more preferably 8 to 10.

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

Nonionic Antimicrobial Agent The non-ionic antimicrobial agent of the present invention is preferably diphenyl ether, more preferably hydroxyl diphenyl ether. The nonionic antimicrobial agent herein may be either halogenated or non-halogenated, but is preferably a halogenated antimicrobial agent. Diphenyl ethers suitable for use herein are described in column 1, line 54 to column 5, line 12 of US Pat. No. 7,041,631 (B), which is incorporated by reference.

  In one embodiment, the non-ionic antimicrobial agent is a hydroxyl diphenyl ether of formula (I).

式中、
各Ｙは、独立して、塩素、臭素又はフッ素から選択され、好ましくは塩素又は臭素であり、より好ましくは塩素であり、
各Ｚは、独立して、ＳＯ_２Ｈ、ＮＯ_２又はＣ_１〜Ｃ_４アルキルから選択され、
ｒは、０、１、２又は３であり、好ましくは１又は２であり、
ｏは、０、１、２又は３であり、好ましくは０、１又は２であり、
ｐは、０、１又は２であり、好ましくは０であり、
ｍは、１又は２であり、好ましくは１であり、
ｎは、０又は１であり、好ましくは０である。

During the ceremony
Each Y is independently selected from chlorine, bromine or fluorine, preferably chlorine or bromine, more preferably chlorine
Each Z is independently selected from SO ₂ H, NO ₂ or C ₁ -C ₄ alkyl,
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.
n is 0 or 1, preferably 0.

  In the above definition of formula (I), 0 means absent. For example, when p is 0, Z in formula (I) does not exist. Each Y or each Z may be the same or different. In one embodiment, o is 1, r is 2 and Y is chlorine or bromine. In this embodiment, one chlorine atom is bonded to one benzene ring, and a bromine atom and another chlorine atom are bonded to the other benzene ring, or a bromine atom is bonded to one benzene ring, One chlorine atom may be bonded to the other benzene ring.

  Preferably, the non-ionic antimicrobial agent herein is 4-4'-dichloro-2-hydroxydiphenyl ether ("Diclosan"), 2,4,4'-trichloro-2'-hydroxydiphenyl ether ("Triclosan") And combinations thereof. Most preferably, the antimicrobial agent is 4-4'-dichloro-2-hydroxydiphenylether, which is commercially available from BASF under the tradename Tinosan® HP 100.

  In addition to diphenyl ether, other anti-microbial agents may be present, provided they are present at concentrations which do not cause instability in the formulation. Such useful further antimicrobial agents include chelating agents, which are particularly useful in reducing the resistance of gram negative bacteria in hard water. An acid biocide may be present.

Organic Solvent The organic solvent of the present invention is a C ₁ -C ₆ alcohol, preferably a C ₂ -C ₆ alcohol. The alcohols herein are preferably selected from the group consisting of diols, triols and combinations thereof. In one embodiment, the alcohol is an alkanolamine including methanolamine, ethanolamine, propanolamine and the like. Preferably, the organic solvent is selected from the group consisting of ethanol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, ethanolamine (such as mono-, di- and tri-ethanolamine) and combinations thereof. More preferably, the organic solvent is selected from the group consisting of diethylene glycol, propylene glycol, glycerol, monoethanolamine, triethanolamine and combinations thereof. Most preferably, the organic solvent is propylene glycol.

In addition to C ₁ -C ₆ alcohols, the liquid laundry detergent compositions herein may also comprise hydrotropic substances, which may likewise be regarded as solvents. It should be noted that the concentration of 0.1% to 2.5% required for the C ₁ -C ₆ alcohol organic solvent does not include the concentration of hydrotropic material that may also be present in the composition. The hydrotropic material is preferably selected from the group consisting of sodium cumene sulfonate (SCS), sodium toluene sulfonate (NaTS), sodium xylene sulfonate (SXS) and combinations thereof. More preferably, the hydrotropic substance is SCS.

In a preferred embodiment, the liquid antimicrobial laundry detergent composition comprises
a) 0.03% to 0.5%, based on the weight of the composition, of a nonionic antimicrobial agent which is 4-4'-dichloro-2-hydroxydiphenyl ether;
b) 0.3% to 1.5% by weight of the composition, including an organic solvent which is propylene glycol.

Auxiliary Components The liquid antimicrobial laundry detergent compositions herein may include auxiliary components. Suitable auxiliary substances include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, builders, chelating agents, rheology modifiers, dye transfer inhibitors, dispersants, enzymes and Enzyme Stabilizer, Catalyst Material, Bleach Activator, Hydrogen Peroxide, Hydrogen Peroxide Source, Preformed Peracid, Polymer Dispersant, Clay Soil Remover / Anti-redeposition Agent, Brightener, Foam Inhibitor, Dye, These include, but are not limited to, photobleaching agents, perfumes, perfume microcapsules, structural stretch agents, softeners, carriers, processing aids, hueing agents, structurants and / or pigments. In addition to the disclosure below, preferred examples and concentrations of such other adjuvants can be found in U.S. Patent Nos. 5,576,282, 6,306,812 (B1) and 6,326. , 348 (B1), which are incorporated by reference. The exact nature of these ancillary ingredients in the laundry detergent composition and the concentration thereof depend on the physical form of the composition and the nature of the washing procedure in which the composition is used.

  In one embodiment, the liquid laundry detergent composition herein is selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and combinations thereof. Further comprises a surfactant. Preferably, the composition is 3% to 50% anionic surfactant based on the weight of the composition and 0.1% to 10% nonionic surfactant based on the weight of the composition And.

In one embodiment, the composition comprises an anionic surfactant. Nonlimiting examples of anionic surfactants include linear alkyl benzene sulfonates (LAS) (preferably C ₁₀ -C ₁₆ LAS), C ₁₀ -C ₂₀ primary branched and random alkyl sulfates (AS) , C ₁₀ -C ₁₈ secondary (2, 3) alkyl sulfates, sulfated fatty alcohol ethoxylate (AES) (preferably C ₁₀ -C ₁₈ alkyl alkoxy sulfate (AE _x S), wherein in the formula, preferably x is 1 to 30, more preferably x is 1 to 3)), C ₁₀ -C ₁₈ alkyl alkoxy carboxylates (preferably containing 1 to 5 ethoxy units), US Pat. No. 6,020,303 and Medium chain branched alkyl sulfates as discussed in U.S. Pat. No. 6,060,443, U.S. Pat. No. 6,008,181. And medium-chain branched alkyl alkoxy sulfates as discussed in U.S. Pat. No. 6,020,303; discussed in WO 99/05243, WO 99/05242 and WO 99/05244. And modified alkyl benzene sulfonate (MLAS), methyl ester sulfonate (MES), as well as alpha-olefin sulfonate (AOS). Preferably, the composition is an anionic surfactant selected from the group consisting of LAS, AES, AS and combinations thereof, more preferably an anionic surfactant selected from the group consisting of LAS, AES and combinations thereof Containing agents. The total concentration of anionic surfactant may be from 3% to 50% by weight of the liquid detergent composition, preferably 5% to 40% in the composition by weight of the composition More preferably 10% to 30%. For implementations where both AES and LAS are present in the composition, the weight ratio of AES to LAS is 0.1: 1 to 10: 1, preferably 0.5: 1 to 5: 1, more preferably 0. .7: 1 to 2: 1.

In the present invention, the composition herein is incorporated into a relatively high concentration of anionic surfactant (ie, high concentration composition) without concern about stability, as the concentration of organic solvent is relatively low. be able to. In one embodiment, the composition is
a) 0.001% to 0.3% of a non-ionic antibacterial agent with respect to the weight of the composition,
b) 0.3% to 1.5% of an organic solvent which is a C ₁ -C ₆ alcohol, relative to the weight of the composition,
c) 20% to 50% of an anionic surfactant selected from the group consisting of AES, LAS and combinations thereof, based on the weight of the composition.

In one embodiment, the composition herein comprises a non-ionic surfactant, preferably an alkoxylated non-ionic surfactant. Non-limiting examples of alkoxylated nonionic surfactants suitable for use herein include C ₁₂ -C such as Neodol® nonionic surfactants available from Shell ₁₈ alkyl ethoxylates, C ₆ -C ₁₂ alkyl phenol alkoxylates (where the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units), ethylene oxide / propylene oxide such as Pluronic® available from BASF C ₁₂ -C ₁₈ alcohol condensates and C ₆ -C ₁₂ alkylphenol condensates with block alkylpolyamine ethoxylates, US Pat. Nos. 6,153,577, 6,020,303 and 6,093, As discussed in issue 856 ₁₄ -C ₂₂ chain branched alkyl alkoxylates, BAEx (wherein x is 1 to 30), U.S. Pat. No. 4,565,647 (Llenado) alkylpolysaccharides such as those discussed in, particularly, the United States Alkyl polyglycosides as discussed in patents 4,483,780 and 4,483,779, polyhydroxy fatty acid amides as discussed in US Patent 5,332,528, and US Ether-capped poly (oxyalkylated) alcohol surfactants such as those described in Patents 6,482,994 and WO 01/42408. Also useful as non-ionic surfactants herein are alkoxylated ester surfactants such as those having the formula R ¹ C (O) O (R ₂ O) n R ³ (where , R ₁ is selected from linear and branched C ₆ -C ₂₂ alkyl or alkylene moieties, R ² is selected from C ₂ H ₄ and C ₃ H ₆ moieties, R ³ is H, CH ₃ , Selected from C ₂ H ₅ and C ₃ H ₇ moieties, n has a value of 1 to 20). Such alkoxylated ester surfactants include fatty acid methyl ester ethoxylates (MEE) and are known in the art. For example, U.S. Patent Nos. 6,071,873, 6,319,887, 6,384,009, and 5,753,606, WO 01/10391, and 96. See / 23049.

In one embodiment, the alkoxylated nonionic surfactants _herein, C 6 _{-C 22} alkoxylated alcohols, preferably _C 8 _{-C 18} alkoxylated alcohols, more preferably _C 12 _{-C 16} alkoxylated It is alcohol. Preferably, the C ₆ -C ₂₂ alkoxylated alcohol is an alkyl alkoxylated alcohol having an average degree of alkoxylation of 1 to 50, preferably 3 to 30, more preferably 5 to 20, even more preferably 5 to 9 . The alkoxylation in the present specification may be ethoxylation, propoxylation or a mixture thereof, but is preferably ethoxylation. In one embodiment, the alkoxylated nonionic surfactant is a C ₆ -C ₂₂ ethoxylated alcohol, preferably a C ₈ -C ₁₈ alcohol ethoxylated with an average of 5 to 20 moles of ethylene oxide, more preferably an average of 5 in to 9 moles of ethylene oxide are ethoxylated _C 12 _{-C 16} alcohol. The most preferred alkoxylated nonionic surfactant is a C ₁₂ -C ₁₅ alcohol ethoxylated with an average of 7 moles of ethylene oxide, such as Neodol® 25-7, which is commercially available from Shell.

  In one embodiment, the compositions herein comprise a cationic surfactant. Nonlimiting examples of cationic surfactants include quaternary ammonium surfactants which may have up to 26 carbon atoms and are alkoxylates as discussed in US Pat. No. 6,136,769. Quaternary ammonium (AQA) surfactants, including dimethylhydroxyethyl quaternary ammonium, dimethylhydroxyethyl lauryl ammonium chloride as discussed in US Pat. No. 6,004,922, WO 98/35002, Polyamine cationic surfactants as discussed in U.S. Pat. Nos. 98/35003, 98/35004, 98/35005 and 98/35006, U.S. Pat. No. 4,228,042 , 4,239,660, 4,260,529, and 6,022,844. Cationic ester surfactants, as well as amino surfactants such as those discussed in US Pat. Nos. 6,221,825 and WO 00/47708, specifically amidopropyldimethylamine APA).

  In one embodiment, the composition herein comprises an amphoteric surfactant. Nonlimiting examples of amphoteric surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or quaternary ammonium, quaternary phosphonium or tertiary Derivatives of sulfonium compounds are mentioned. Preferred examples are alkyldimethyl betaines and cocodimethylamidopropyl betaines, C8 to C18 (or C12 to C18) amine oxides and sulfobetaines and hydroxybetaines, such as N-alkyl-N, N-dimethylamino-1-propanesulfonates. And betaines including (the alkyl group may be C8 to C18, or C10 to C14) and the like.

  Preferably, the amphoteric surfactant herein is selected from water soluble amine oxide surfactants. Useful amine oxide surfactants are

であり、式中、Ｒ^３は、Ｃ_８〜２２アルキル基、Ｃ_８〜２２ヒドロキシアルキル基又はＣ_８〜２２アルキルフェニル基であり、各Ｒ^４は、Ｃ_２〜３アルキレン基又はＣ_２〜３２ヒドロキシアルキレン基であり、ｘは、０〜約３であり、各Ｒ^５は、Ｃ_１〜３アルキル、Ｃ_１〜３ヒドロキシアルキル又は約１〜約３のＥＯを含むポリエチレンオキシドである。好ましくは、アミンオキシド界面活性剤は、Ｃ_{１０〜１８}アルキルジメチルアミンオキシド又はＣ_８〜１２アルコキシエチルジヒドロキシエチルアミンオキシドであってもよい。

In the formula, R ³ is a C _8-22 alkyl group, a C _8-22 hydroxyalkyl group or a C _8-22 alkylphenyl group, and each R ⁴ is a C _2-3 alkylene group or C _{2 32} hydroxyalkylene groups, x is 0 to about 3, and each R ⁵ is a polyethylene oxide containing C _1-3 alkyl, C _1-3 hydroxyalkyl or about 1 to about 3 EO. Preferably, the amine oxide surfactant may be a _C10-18 alkyl dimethyl amine oxide or a _C8-12 alkoxy ethyl dihydroxy ethyl amine oxide.

In one embodiment, the compositions herein comprise a rheology modifier (also referred to in certain circumstances as a "structurant"), the function of which is to suspend and stabilize the microcapsules, by packaging assembly It is to adjust the viscosity of the composition to be suitable. The rheology modifiers herein are those such as those disclosed in U.S. Patent Application Nos. 2006/0205631 A1, 2005/0203213 A1 and U.S. Patent Nos. 7294611 and 6855680. It may be any known ingredient capable of suspending particles and / or adjusting to a rheology suitable for liquid compositions. Preferably, the rheology modifiers are hydroxy-containing crystalline substances, polyacrylates, polysaccharides, polycarboxylates, alkali metal salts, alkaline earth metal salts, ammonium salts, alkanol ammonium salts, C ₁₂ -C ₂₀ aliphatic alcohols, di- A cationic polymer comprising a benzylidene polyol acetal derivative (DBPA), a diamide gelling agent, a first structural unit derived from methacrylamide and a second structural unit derived from diallyldimethyl ammonium chloride, and a combination thereof Be done. Preferably, the rheology modifier is a hydroxy-containing crystalline material generally having crystalline character, 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).

In a highly preferred embodiment, the antimicrobial laundry detergent composition of the present invention comprises
a) 0.03% to 0.5%, based on the weight of the composition, of a nonionic antimicrobial agent which is 4-4'-dichloro-2-hydroxydiphenyl ether;
b) 0.3% to 1.5% of an organic solvent which is propylene glycol with respect to the weight of the composition,
c) 10% to 30% of an anionic surfactant selected from the group consisting of AES, LAS and a combination thereof with respect to the weight of the composition,
relative to the weight of d) the composition from 0.5% to 5% of a nonionic surfactant (non-ionic surfactants are _C 12 _{-C 16} alcohols ethoxylated with an average 5-9 moles of ethylene oxide And b).

Composition Preparation The liquid antimicrobial laundry detergent compositions of the present invention are generally prepared by conventional methods known in the art for the preparation of liquid laundry detergent compositions. Such methods typically include mixing the essential and optional components in any desired order to a relatively uniform state, with or without heating, cooling, application of vacuum, etc., and thereby Providing a laundry detergent composition containing the ingredients in the required concentration.

Water-soluble pouches In one embodiment, the liquid antimicrobial laundry detergent compositions herein are contained within a water-soluble film, thereby forming a water-soluble pouch. The pouch may be used by the user to change the amount used according to the required operation, eg a single dose of the composition herein suitable for a single wash, or for example the amount of laundry or the degree of soiling. It may be of convenient size to accommodate any of the partial amounts that can be made more flexible.

  The water-soluble film of the pouch is preferably made of a polymer. The film can be obtained by methods known in the art, for example, casting, blow molding, extrusion, injection molding of polymers. Nonlimiting examples of polymers for producing water-soluble films such as polyvinyl alcohol (PVA), polyvinyl pyrrolidone, polyalkylene oxide, (modified) cellulose, (modified) cellulose-ether or-ester or-amide, polyacrylate, etc. Copolymers of polycarboxylic acids and salts maleic acid / acrylic acid, polyamino acids or peptides, polyamides such as polyacrylamides, polysaccharides such as starch and gelatin, natural gums such as xanthan and carragum. Preferably, the water soluble film is a polyacrylate and a water soluble acrylate copolymer, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylate, polyvinyl alcohol, hydroxypropyl methylcellulose (HPMC), and It includes a polymer selected from the group consisting of these combinations. Most preferably, the water soluble film comprises polyvinyl alcohol, such as M8639 available from MonoSol. Suitable polymers for producing water-soluble films of pouches are described in US Pat. No. 6,995,126.

  The pouch herein may comprise a single compartment or a plurality of compartments, preferably comprising a plurality of compartments, for example two compartments or three compartments. When multiple compartments are applied, one or more of the multiple compartments contain the liquid antimicrobial laundry detergent composition described above. Preferably, the pouch comprises a plurality of films forming a plurality of compartments, ie the internal volume of the plurality of films is divided into a plurality of compartments. Examples of these multi-compartment pouches are described in U.S. Patent Nos. 4,973,416, 5,224,601, and 8,066,818.

  The pouch of the present invention can be made by any suitable process known in the art. Examples of the preparation process of the pouch are described in U.S. Patent Nos. 6,995,126, 7,127,874, 8,156,713, 7,386,971, and 7,439, No. 215, and U.S. Patent Application Publication No. 2009/199877.

Method of Use Another aspect of the present invention relates to a method of using a laundry detergent composition to treat a fabric with an antimicrobial effect. The method comprises the steps of charging 5 g to 120 g of the above-described laundry detergent composition to a laundry washer containing water to form a cleaning solution. The washing liquid in the washing and washing machine in the present specification preferably has a volume of 1 L to 50 L, or 1 L to 20 L by hand washing, and 20 L to 50 L of washing by a washing machine. Preferably, the antibacterial effect in the present specification is evaluated by the JISL 1902 method. The temperature of the washing solution is preferably in the range of 5 ° C to 60 ° C.

  The dosages in the methods herein may vary depending on the type of cleaning. In one embodiment, the method comprises the step of charging 5 g to 60 g of the laundry detergent composition into a hand-washer (e.g. 4 L). In an alternative embodiment, the method comprises the step of charging 60 g to 120 g of the laundry detergent composition into a washing machine (e.g. 30 L).

  Preferably, the method herein further comprises the step of contacting the fabric with a cleaning solution, the fabric requiring an antimicrobial treatment. For example, the presence of gram positive bacteria and / or gram negative bacteria is suspected on the fabric. The step of contacting the fabric with the cleaning solution is preferably after the step of loading the laundry detergent composition into the laundry washer. The method comprises the steps of contacting the fabric with the laundry detergent composition prior to the step of loading the laundry detergent composition into the laundry washer, ie, laundering the fabric for a certain period of time (preferably 1 minute to 10 minutes). It may further comprise the step of pretreating with a detergent composition.

Test Method The antibacterial effect of the laundry detergent composition is evaluated according to the method defined in JIS L 1902 described below.

1. Preparation of microorganisms:
A. An aliquot of normal broth medium is aseptically added to the lyophilized S. aureus or K. pneumoniae culture. The culture is dissolved and suspended in a normal broth medium to obtain a suspension. The suspension of one platinum ear is streaked out on nutrient agar plates and incubated at 37 ° C. for 24 hours to obtain a first generation passage of bacterial suspension. Transfer the first generation of subculture of 1 platinum loop of bacterial suspension to 20 mL of ordinary broth medium with shaking, and incubate at 37 ° C. for 24 hours to obtain a second generation of bacterial suspension. A culture broth is obtained. Transfer the second generation subculture of 0.4 mL of the bacterial suspension to another 20 mL of normal broth medium with shaking, and incubate at 37 ° C. for 3 hours to produce the third generation of bacterial suspension Obtain a subculture fluid of
B. Working broth is obtained by diluting the third generation subculture of the bacterial suspension to 1 × 10 5 cells / mL using common broth medium diluted 1/20.
C. Store working medium at 4 ° C. Working cultures can not be stored overnight.

2. Fabric cleaning:
A. Two pieces of fabric, each 5 cm wide x 2.5 m long (32 yarns / cm x 32 yarns / cm, 100% plain weave cotton) are boiled in 3 L of solution for 1 hour. The solution is prepared with 1.5 g of nonionic immersion agent, 1.5 g of sodium carbonate and 3000 ml of distilled water. A non-ionic dip is prepared with 5.0 g of alkylphenol ethoxylate, 5 g of sodium carbonate and 1000 mL of distilled water. The piece of fabric is rinsed with boiling deionized water for 5 minutes. The piece of fabric is placed in cold deionized water for 5 minutes and allowed to dry in the room. One piece of fabric was taken as the test fabric piece of steps 2B-2I below, and the other piece of fabric was used as a control (no implementation of steps 2B-2I).
B. One end of the test fabric piece obtained from step 2A is fixed on the stainless steel spindle at an outer position along the horizontal extension of the stainless steel spindle. The stainless steel spindle has three horizontal stands connected to one another. A piece of test cloth is wound on three horizontal stands of a stainless steel spindle with sufficient tension to obtain a cloth-wound spindle having a 12-turn wound cloth. The other end of the test fabric piece is pinned to the outside of the 12-fold wound fabric. The fabric-wound spindle is sterilized at 121 ° C. for 15 minutes at steam pressure.
C. 5. 903 g of calcium chloride dihydrate and 2.721 g of magnesium chloride hexahydrate are dissolved in 100 mL of distilled water and the mixture is then sterilized at 121 ° C. for 20 minutes at steam pressure. Add 1 mL of the mixture to 1 L of distilled water to obtain a hard aqueous solution.
D. A sufficient amount of sample is added to 1 L of the hard aqueous solution obtained from step 2C to obtain a solution having a concentration of 2069 ppm. The solution is mixed with a magnetic stirrer for 4 minutes. 250 mL of mixed solution is supplied to the exposure chamber to obtain a wash. The exposure chamber is placed in a water bath to achieve a test temperature of (25 ± 1) ° C. The exposure chamber is then sterilized at 121 ° C. for 15 minutes at steam pressure.
E. The fabric wound spindle obtained from step 2B is aseptically immersed in the wash solution in the exposure chamber and the exposure chamber is closed with a lid.
F. The exposure chamber is fixed on the tumbler. Rotate the tumbler for 10 minutes. The fabric wound spindle is then removed from the exposure chamber. Place the fabric wound spindle into the Haier iwash-1p top-loading washer and rinse for 2 minutes.
G. Discard the wash solution from the exposure chamber and then add 250 mL of sterile distilled water to the exposure chamber. The rinsed fabric wrapped spindle is immersed in freshly added distilled water in the exposure chamber. Rotate the tumbler for 3 minutes.
H. Repeat step 2G.
I. The fabric wrapped spindle is aseptically removed from the exposure chamber and the test fabric strip is removed from the spindle. The test fabric pieces are allowed to air dry overnight.

3. Cloth culture:
A. Cut the cleaned test cloth pieces obtained from step 2I into square pieces with a side length of 2 cm. Three sets of 0.4 g sections are taken as samples for the following steps.
B. Each set of samples is placed in a vial and the samples are then sterilized by vapor pressure at 121 ° C. for 15 minutes. After sterilization, the samples are allowed to dry for 1 hour without lid in a clean bench.
C. Inoculate each dried sample with 0.2 mL of working culture fluid obtained from step 1C. The vial containing the inoculated sample is incubated at 37 ° C. for 18 hours.
D. The viable bacteria on the inoculated sample are harvested, seeded on nutrient agar plates and cultured for 24 to 48 hours at 37 ° C. Count all colony forming units (CFU) of each set of samples to obtain 3 sets of averaged results. Take the common logarithm of the CFU value as Mb.
E. In steps 3A-3D, the piece of fabric obtained from step 2A is used as a control (steps 2B-2I are not performed). Take the common logarithm of the CFU value as Ma.

4. Calculation of bacteriostatic activity value:
Bacteriostatic activity value = Mb-Ma
A bacteriostatic activity value of greater than 2.2 indicates an acceptable level of antibacterial effect, a value of greater than 2.5 indicates a good antibacterial effect, and a value of greater than 3.0 indicates an excellent antibacterial effect. Thus, bacteriostatic activity values below 2.2 show less than acceptable antimicrobial efficacy.

  The examples set forth herein are meant to illustrate the present invention, but are not used to limit or otherwise define the scope of the present invention. Examples 1A-1C and 2A are examples according to the present invention, and Example 2B is a comparative example.

Examples 1A-1C: Formulation of Liquid Laundry Detergent Compositions The following liquid laundry detergent compositions shown in Table 1 are made containing the listed components in the listed ratios (% by weight).

ａ Ｎｅｏｄｏｌ（登録商標）２５−７は、非イオン性界面活性剤としての、Ｓｈｅｌｌから入手可能な平均７モルのエチレンオキシドでエトキシ化されたＣ_１２〜Ｃ_１５アルコール
ｂ キレート剤としての、ジエチレントリアミン五酢酸五ナトリウム塩
ｃ Ｔｉｎｏｓａｎ（登録商標）ＨＰ１００は、ＢＡＳＦから入手可能な４−４’−ジクロロ−２−ヒドロキシジフェニルエーテル

a Neodol® 25-7 is a non-ionic surfactant, diethylenetriaminepentaacetic acid as an average of 7 moles of ethylene oxide ethoxylated C ₁₂ -C ₁₅ alcohol b chelating agent available from Shell Pentasodium salt c Tinosan (R) HP 100 is a 4-4'-dichloro-2-hydroxydiphenyl ether available from BASF

Examples 2A-2B: Formulation of Liquid Laundry Detergent Compositions The following liquid laundry detergent compositions shown in Table 2 are made containing the listed components in the listed proportions (% by weight).

ａ Ｓｕｒｆｏｎｉｃ（登録商標）Ｌ２４−９は、非イオン性界面活性剤としての、Ｈｕｎｔｓｍａｎから入手可能な９モルのエチレンオキシドでエトキシ化されたＣ_１２〜Ｃ_１４アルコール
ｂ キレート剤としてのジエチレントリアミンペンタメチレンホスホン酸ナトリウム塩
ｃ Ｔｉｎｏｓａｎ（登録商標）ＨＰ１００は、ＢＡＳＦから入手可能な４−４’−ジクロロ−２−ヒドロキシジフェニルエーテル
ｄ 本明細書中で使用するカチオン性抗菌剤は、ラウリルトリメチルアンモニウムクロリドである。

a Surfonic® L 24-9 is a non-ionic surfactant, diethylenetriaminepentamethylene phosphonic acid as C ₁₂ -C ₁₄ alcohol ethoxylated with 9 moles of ethylene oxide available from Huntsman b Chelator Sodium salt c Tinosan® HP 100 is 4-4′-dichloro-2-hydroxydiphenyl ether available from BASF d The cationic antimicrobial agent used herein is lauryl trimethyl ammonium chloride.

Preparation of Liquid Laundry Detergent Compositions of Examples 1A-1C and 2A-2B The liquid laundry detergent compositions of Examples 1A-1C and 2A-2B are
a) mixing the combination of NaOH and water in a batch vessel by applying a shear force of 200 rpm,
b) the citric acid (some), and if there borate () and _C 11 was added to _~ 13 LAS batch vessel and continue to mix by adding shearing force 200rpm step,
c) cooling the temperature of the mixture obtained in step b) to 25 ° C .;
d) C _12-14 AE _1-3 S, Na-DTPA (if present), Na-DTPMP (if present), Neodol® 25-7 (if present), Surfonic® L 24-9 (if present) some _cases), C 12 _{-C 18} fatty acids, propylene glycol, if monoethanolamine (some), if the calcium chloride (some), if there sodium cumene sulfonate (), if there silicone emulsions (), sodium polyacrylate ( In some cases), add Tinosan® HP 100 (if any) and cationic antimicrobial agent (if any) into the batch container and mix by applying shear force at 250 rpm until the mixture is homogeneously mixed, pH Adjusting to 8;
e) Add brightener (if present), protease (if present), amylase (if present), dye (if present) and perfume oil (if present) into the batch container and mix by applying shear force of 250 rpm And thereby forming a liquid laundry detergent composition,
Each component in the composition is present in the amounts shown for Examples 1A-1C and 2A-2B in Tables 1 and 2.

Stability Assessment A comparative experiment is conducted to assess the physical stability of the liquid laundry detergent compositions of Example 2A and Comparative Example 2B. Specifically, visual assessment of any change is used to assess its stability 1) when the composition is freshly prepared at 25 ° C and 2) when the composition is subjected to freeze-thaw. The freeze-thaw cycle consists of a first step at 18 ° C. for 24 hours followed by a second step at 25 ° C. for 24 hours. The evaluation results of the composition are shown in Table 3.

  As shown in Table 3, a liquid laundry detergent composition comprising Tinosan® HP 100 (Example 2A) according to the present invention does not require a high concentration of organic solvent, and it has been physically prepared since its new preparation. It shows that the stability has improved. In contrast, the comparative composition (comparative example 2B), which instead contains a cationic antimicrobial, is unstable and is prominent after freeze-thaw cycles. Unlike the nonionic antimicrobials used in the present invention, such cationic antimicrobials generally require relatively high concentrations of organic solvents to maintain the desired stability.

  All percentages, ratios and proportions are calculated based on the weight of the total composition, unless otherwise indicated. All temperatures are degrees Celsius (° C.) unless otherwise stated. All measurements are performed at 25 ° C unless otherwise specified. All concentrations of components or compositions relate to the level of activity of the components or composition, excluding impurities such as residual solvents or byproducts that may be present in commercial sources.

  It is understood that all maximum numerical limitations given throughout the specification are to be construed as including all lower numerical limitations as if such lower numerical limitations were expressly written herein. Should. All minimum numerical limitations given throughout this specification are inclusive of all higher numerical limitations, as if higher numerical limitations were explicitly stated herein. Are all numerical ranges given throughout the present specification all narrow numerical ranges falling within such wider numerical ranges and are all such narrow numerical ranges explicitly described herein? As in

  The dimensions and values disclosed herein are not to be understood as being strictly limited to the precise numerical values set forth. 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, the dimensions disclosed as "40 mm" are intended to mean "about 40 mm".

  All documents cited herein, including all patents or patent applications cross referenced or related, and any patent applications or patents for which the present application claims priority or benefit thereof, are expressly It is incorporated herein by reference in its entirety, unless excluded or otherwise limited. The citation of any document is not an admission that such document is prior art to any invention disclosed or claimed herein, and such document, alone or in any other reference, is not. Neither is it to be taught, suggested, or disclosed any of such inventions in any combination with. Furthermore, if any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in the document incorporated by reference, then the meaning or definition given to that term in this document shall prevail. I assume.

  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 present invention. Accordingly, all such changes and modifications that are included within the scope of the present invention are intended to be covered by the appended claims.

Claims (10)

a) about 0.001% to about 3% non-ionic antimicrobial agent by weight of the composition,
b) A liquid antimicrobial laundry detergent composition comprising about 0.1% to about 2.5% of an organic solvent, based on the weight of the composition, wherein the organic solvent is a C ₁ -C ₆ alcohol.   The composition of claim 1, further comprising about 3% to about 50% anionic surfactant, based on the weight of the composition.   The composition according to claim 1, wherein the non-ionic antimicrobial agent is diphenyl ether. The non-ionic antimicrobial agent is of the formula (I):

(In the formula,
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 alkyl,
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;
n is 0 or 1)
The composition according to claim 3, which is a hydroxyl diphenyl ether compound of   5. The non-ionic antimicrobial agent is selected from the group consisting of 4-4'-dichloro-2-hydroxydiphenyl ether, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, and combinations thereof. Composition as described.   The composition according to claim 5, wherein the nonionic antibacterial agent is 4-4'-dichloro-2-hydroxydiphenyl ether.   The composition according to claim 1, wherein the organic solvent is selected from the group consisting of ethanol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, ethanolamine and combinations thereof.   The non-ionic antimicrobial agent is present from about 0.01% to about 1% by weight of the composition, and the organic solvent is from about 0.2% to about 2% by weight of the composition. The composition according to claim 1, wherein 2% is present. a) about 0.03% to about 0.5% of the non-ionic antibacterial agent which is 4-4′-dichloro-2-hydroxydiphenyl ether, relative to the weight of the composition,
b) about 0.3% to about 1.5% of the organic solvent which is propylene glycol, based on the weight of the composition;
c) An anionic interface selected from the group consisting of about 10% to about 40% of alkyl ethoxy sulfate (AES), linear alkyl benzene sulfonate (LAS), and a combination thereof, based on the weight of the composition An activator,
d) about 0.5% to about 5% of a non-ionic surfactant based on the weight of the composition, wherein the non-ionic surfactant is ethoxylated with an average of 5 to 9 moles of ethylene oxide is a _C 12 _{-C 16} alcohols, the composition of claim 1.   The composition according to claim 1, contained in a water-soluble film, preferably a water-soluble film comprising polyvinyl alcohol.