EP3221437A1 - Flüssige reinigungsmittelzusammensetzungen - Google Patents

Flüssige reinigungsmittelzusammensetzungen

Info

Publication number
EP3221437A1
EP3221437A1 EP15861846.2A EP15861846A EP3221437A1 EP 3221437 A1 EP3221437 A1 EP 3221437A1 EP 15861846 A EP15861846 A EP 15861846A EP 3221437 A1 EP3221437 A1 EP 3221437A1
Authority
EP
European Patent Office
Prior art keywords
composition
mixture
acid
ethoxylate
surfactants
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP15861846.2A
Other languages
English (en)
French (fr)
Other versions
EP3221437B1 (de
EP3221437A4 (de
Inventor
Thomas J. DURRSCHMIDT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ecolab USA Inc
Original Assignee
Ecolab USA Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ecolab USA Inc filed Critical Ecolab USA Inc
Publication of EP3221437A1 publication Critical patent/EP3221437A1/de
Publication of EP3221437A4 publication Critical patent/EP3221437A4/de
Application granted granted Critical
Publication of EP3221437B1 publication Critical patent/EP3221437B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the disclosure pertains to a liquid detergent concentrate composition, to a stable aqueous use solution comprising the liquid detergent concentrate composition and to a method for washing textiles.
  • a liquid detergent composition in the form of the concentrate or a use solution which is an emulsion of the type water-in-oil emulsion or oil-in-water emulsion dependent on the amounts of water and oil in the emulsion, and which contains soil-anti re-deposition agents.
  • Accepted washing performance measures of liquid detergents suitable for laundry use are the degree of whiteness of white textiles and anti-soil re-deposition capability of the detergent composition.
  • the delivery of effective cleaning performance of certain laundry items, such as work-wear is especially problematic due to a range of factors including: the wide range of anticipated soils, from greasy and oily stains such as commonly found on uniforms, overalls and wiping / cleaning rags used the automotive industry, to food and drink stains and deposits such as are commonly found on uniforms used in the food industry, as well as general soil and dirt as found on floor mats and mop heads; the relative high levels of staining anticipated; the need to deliver high cleaning performance levels for work-wear used in customer-facing environments such as for example uniforms for use in restaurants and hotels. Therefore, there exists a need for liquid laundry detergents capable of providing improved whiteness performance and anti-soil re-deposition capability across a range of soils.
  • liquid laundry detergents suitable for cleaning work- wear at reduced temperatures Due to the need for retention of high performance levels, and in particular the degree of whiteness for certain uniforms, the development of liquid laundry detergents suitable for cleaning work- wear at reduced temperatures remains a challenge. Therefore, it would be desirable to provide liquid laundry detergents capable of providing effective cleaning performance across a wide range of soils of varying degree and on a variety of fabric substrates at 60°C.
  • Liquid detergents are known in the state of the art. Such detergents are, for example, described in WO2014/154244 Al, WO2012/045364 A2, and WO 2007/101470 Al.
  • the document WO2007/101470 Al describes a liquid detergent composition which is storage- stable and shows a good washing performance.
  • the core of the composition is the combination of linear alkoxylated alcohol nonionic surfactants and cross-linked or partly cross-linked polyacrylic acids and/or polymethacrylic acids as solubilizers. These solubilizers, which are available under the trade name Carbopol® from the Lubrizol Corporation, were used to keep the components in solution and to maintain the storage stability of the resulting emulsion over longer periods. To produce stable emulsions using solublizers a pre-mixing step is required.
  • the document WO2012/045363 Al describes a liquid detergent composition suitable for low temperature washing and disinfection which is storage-stable, shows a good washing performance and contributes to a reduction in the germs count of the washing washed with it.
  • the core of the composition is the combination of a mixture of low and higher alkoylated non-ionic tensides (surfactants).
  • the document WO2014/154244 Al describes a stable liquid detergent concentrate composition having good washing performance.
  • the core of the composition is the combination of ethoxylates and/or propoxylated fatty alcohol non-ionic surfactants and a stabilising (solubilizing) system comprising a mixture of two acrylic polymers.
  • a stabilising (solubilizing) system comprising a mixture of two acrylic polymers.
  • the aim of the present invention is to provide a liquid detergent concentrate composition having improved whiteness and anti-re-deposition performance, which provides both effective removal of soils and/or stains, is also stable, does not damage either the integrity or colour of the item to be laundered, and which is effective at wash temperatures in the region of 60°C.
  • Liquid detergent concentrate compositions in the form of an emulsion having a water phase and an oil phase and comprising at least one nonionic surfactant, a source of alkalinity, a combination of carboxymethylcellulose and methyl cellulose, at least one complexing agent, at least one thickening and/or stabilizing agent and solvent to balance are provided.
  • Liquid detergent concentrate compositions which comprises an emulsion having a water phase and an oil phase, the composition comprising based on the whole concentrate:
  • CMC carboxymethylcellulose
  • MC methylcellulose
  • the weight percent (wt.%) is calculated on the total weight amount of the liquid detergent concentrate composition, also referred herein to as the first component. Further, the total weight amount of all component of the first component is selected such, that it does not exceed 100 wt.% and the total weight amount of all components of the first component is selected such, that it does not exceed 100 wt.%.
  • the ratio of components is parts by weight, if not otherwise stated.
  • the liquid detergent concentrate composition has a pH in the range of from about 11 to about 14.
  • the total level of CMC and MC is from about 0.2 wt.% to about 8 wt.%.
  • the one or more non-ionic surfactants comprise a combination of at least two nonionic surfactants wherein at least one of the nonionic surfactants is a synthetic or natural alcohol that is alkoxylated with ethylene and/or propylene and/or butylene oxide to yield a C 6 -C24 alcohol ethoxylate and/or propoxylate and/or butoxylate.
  • liquid detergent concentrate compositions herein include a mixture of nonionic surfactants wherein said mixture comprises a mixture of at least two nonionic surfactants and wherein at least one of said surfactants is an ethoxylate of alkyl polyethylene glycol ethers based on isotridecyl alcohol.
  • the liquid detergent concentrate compositions herein include a mixture of nonionic surfactants wherein said mixture comprises at least one 2 EO-ethoxylate and at least one 8 EO-ethoxylate of alkyl polyethylene glycol ethers based on isotridecyl alcohol and at least one amine-based non-ionic surfactant
  • the liquid detergent concentrate compositions herein are free of cationic surfactants.
  • liquid detergent concentrate compositions herein are free of both cationic surfactants and amphoteric surfactants.
  • liquid detergent concentrate compositions additionally comprise from 1 to 20 wt. % of one or more anionic surfactants, and optionally from 0.1 to 2 wt. % of one or more anti-foaming agents.
  • liquid detergent concentrate compositions include a mixture of organic complexing agents comprising at least one aminocarboxylic acid or alkali metal salt thereof and at least one aminophosphonate containing alkyl or alkenyl groups having less than 8 carbon atoms
  • the invention provides a system comprising a first component and a second component, wherein the first component is represented by the liquid detergent composition according to the invention and wherein the second component is a bleaching composition is also provided.
  • the liquid detergent concentrates according to the invention are emulsions having improved whiteness and anti-re-deposition performance, which provide both effective removal of soils and/or stains, are stable, and do not damage either the integrity or colour of the item to be laundered.
  • liquid detergent concentrate compositions useful for cleaning textiles and having improved whiteness and anti-re-deposition performance, which provide both effective removal of soils and/or stains, are also stable, do not damage either the integrity or colour of the item to be laundered, and which are effective at wash temperatures in the region of 60°C.
  • laundry item refers to an item made from or including textile, woven fabric, non-woven fabric, or knitted fabrics.
  • the laundry item can include natural or synthetic fibers such as silk fibers, linen fibers, cotton fibers, polyester fibers, polyamide fibers such as nylon, acrylic fibers, acetate fibers, and blends thereof including cotton and polyester blends.
  • the fibers can be treated or untreated. Exemplary treated fibers include those treated with flame retardant materials. It should be understood that the term “linen” is often used to describe certain types of laundry items including bed sheets, pillow cases, towels, table linen, table cloth, bar mops and uniforms.
  • the liquid detergent concentrate composition may comprise additional surfactants such as cationic surfactants, anionic surfactant, e.g., phosphate ester, alkyl amine oxide, or amphoteric so-called zwitterionic surfactants.
  • the liquid detergent concentrate compositions herein are free of cationic surfactants.
  • the liquid detergent concentrate compositions herein are free of both cationic surfactants and amphoteric surfactants.
  • the liquid detergent concentrate compositions additionally comprise from 1 to 20 wt. % of one or more anionic surfactants, and optionally from 0.1 to 2 wt. % of one or more anti-foaming agents.
  • the detergent composition of the first component of the invention may include additional ingredients or forms of ingredients such as are typically found in laundry detergents such as bleaching agents, perfume, optical brighteners, complexing agents, sequestering agents, chelants and/or thickening agents.
  • the composition of the invention can also be used for treating non-laundry articles and surfaces including hard surfaces such as dishes, glasses, and other ware.
  • the term "by weight” as used herein in respect of any component for use in the present compositions means the weight of that component expressed as a percentage weight relative to the weight of the total composition of the liquid detergent concentrate composition (wt. ).
  • a component present at a level of from 1 to 2% by weight means that in the manufacture of 100 grams of the liquid detergent concentrate composition, from 1 to 2 grams of that component will be required.
  • the liquid detergent concentrate composition of certain aspects is particularly effective in the provision of enhanced cleansing performance as measured by degrees of whiteness.
  • the liquid detergent concentrate composition of certain aspects is stable and is particularly effective in the provision of enhanced cleansing performance as measured by degrees of whiteness.
  • liquid laundry detergent concentrate compositions Prior to the present liquid laundry detergent concentrate compositions it has not been possible to provide liquid laundry detergent concentrate compositions in the form of stable emulsions having a water phase and an oil phase which contain carboxymethylcellulose (CMC) or derivative thereof.
  • CMC carboxymethylcellulose
  • liquid laundry detergent concentrate compositions in the form of stable emulsions having a water phase and an oil phase which contain carboxymethylcellulose (CMC) and methyl cellulose (MC) which are stable across a range of temperature conditions on storage and under freeze/thaw conditions, and which provide desirable levels of cleaning, degree of whiteness and anti-soil re-deposition performance.
  • CMC carboxymethylcellulose
  • MC methyl cellulose
  • Liquid detergent concentrate compositions according to the invention including from 0.1 to 10 wt. % in total of carboxymethylcellulose (CMC) and methylcellulose (MC) wherein the ratio of CMC : MC is from 2 : 1 to 1 : 4 have been demonstrated to provide improved whiteness and anti-re-deposition performance, which provide both effective removal of soils and/or stains, are stable across a range of conditions, and do not damage either the integrity or colour of the item to be laundered.
  • CMC carboxymethylcellulose
  • MC methylcellulose
  • the particular combination of CMC and MC facilitates the sustained suspension of soils which have been removed from a textile during the wash process, in the use solution and reduces the tendency of the soils to be re-deposited onto the textile.
  • the total level of CMC and MC present in the liquid detergent concentrate compositions is from about 0.1 wt. % to about 10 wt. %, from about 0.2 wt.% to about 8 wt.%, from about 0.3 wt. % to about 5 wt. %, from about 0.5 to about 2wt. %.
  • the ratio of CMC : MC is from 2 : 1 to 1 : 4, from 2 : 1 to 1 : 2, from 2 : 1 to 1 : 1, about 2 : 1.
  • liquid detergent concentrate compositions including from 0.1 to 10 wt. % in total of carboxymethylcellulose (CMC) and methylcellulose (MC) wherein the ratio of CMC : MC is independently selected from: 2 : 1 to 1 : 4; 2 : 1 to 1 : 2; 2 : 1 to 1 : 1; about 2 : 1.
  • CMC carboxymethylcellulose
  • MC methylcellulose
  • Carboxymethylcellulose is present in the liquid laundry detergent compositions herein at a level of from about 0.05 wt. % to up to about 7 wt. %, from about 0.2 wt.% to about 5 wt.%, at a level of about 0.5 wt.% to up to about 3 wt.%, about 0.5 wt.% to about 2 wt. %, about 0.75 wt. % to about 1.5 wt. % based on the weight of the liquid laundry detergent compositions herein, and as detailed hereinbefore.
  • Carboxymethylcellulose as defined herein is a cellulose ether produced by reacting alkali cellulose with sodium monochloroacetate.
  • Different CMCs can be produced by substituting different numbers of the hydrogens, on the three hydroxyl groups contained in each of the anhydroglucose units, also known as ⁇ -glucopyranose residues of the repeating cellobiose units of the cellulosic polymer chain. This substitution of these hydroxyl- hydrogens for carboxymethyl groups (i.e. for -CH 2 OCH 2 CC ⁇ Na in a sodium salt form of CMC) provides CMCs.
  • CMCs can be defined by their degree of substitution (DS) i.e. the average number of substituted hydroxyls per anhydroglucose unit.
  • CMCs can also be defined by their average chain length or their degree of polymerisation (DP), which together will dictate the molecular weight of the CMC polymer.
  • CMCs having a DS of from about 0.5 to about 1.5, or more particularly from about 0.5 to about 0.8, from about 0.5 to about 0.75, from about 0.5 to about 0.7 are suitable for use herein.
  • Carboxymethyl cellulose is commercially available in many forms, exemplary commercially available forms of carboxymethyl cellulose suitable for use in the compositions herein include: Finnfix® BDA, from CP Kelco; Finnfix® CMC from Noviant; Na-CMC from Sirius; the CMC-sodium salt range of CMCs available from Mikro-Technik GmbH & Co.
  • KG including the 75aH, DT, DT R, DTK subcategories, and in particular the low viscosity DTK NV; Cellufix; and the WALOCELTM " CRT” and “CRT PV” ranges of sodium carboxymethyl celluloses having different substitution levels available from The Dow Chemical Company; the AQUALON® CMC range of sodium carboxymethyl celluloses from Hercules Incorporated.
  • carboxy methyl cellulose is provided by another manufactures under a different name
  • that alternatively named form of carboxy methyl cellulose is also suitable for use in the compositions herein.
  • a specific commercial form will correspond to CMC having specific features of DS and chain length. Whilst CMCs having the same DS and polymer chain length may be presented in different physical formats such as for example as dilute solutions of different viscosity and the like, such variations in form retain the core features of the CMC and are also suitable for use herein.
  • Preferred carboxy methyl celluose for use herein are independently selected from: low viscosity CMC-Sodium Salt DTK NV from Mikrotechnik GmBH having a DS of 0.75 +/- 0.05, a minimum CMC content (dry basis) of 56 %, and a viscosity of from 4-6mPa/s; Finnfix® BDA, from CP Kelco.
  • Methyl cellulose as defined herein is a water-soluble polymer derived from cellulose. Any form of methyl cellulose, also known as methylcellulose, methylated cellulose or cellulose methyl ether may be utilised in the compositions herein.
  • Methyl cellulose having variable numbers of substituted hydroxyl groups, and expressed as the degree of substitution (DS) are suitable for use in the compositions herein.
  • Methyl cellulose is widely available in many forms, exemplary commercially available forms of methyl cellulose suitable for use in the compositions herein include:
  • methyl cellulose is provided by another manufactures under a different name
  • that alternatively named form of methyl cellulose is also suitable for use in the compositions herein.
  • a specific commercial form will correspond to MC having specific features of DS and chain length. Whilst MCs having the same DS and polymer chain length may be presented in different physical formats such as for example as dilute solutions of different viscosity and the like, such variations in form retain the core features of the MC and are also suitable for use herein.
  • Preferred methyl celluose for use herein is Zellura MC 60 / Aquence LAM 60S available from Henkel.
  • Methyl cellulose is present in the liquid laundry detergent compositions herein at a level of from about 0.05 wt. % to up to about 3 wt. %, from about 0.2 wt.% to about 2 wt.%, at a level of about 0.5 wt.% to up to about 1.5 wt.%, about 0.5 wt.% to about 1 wt. %, about 0.75 wt. % based on the weight of the liquid laundry detergent compositions herein, and as detailed hereinbefore.
  • the CMC has a DS of from about 0.5 to about 1.5 and the MC has a DS of from about 1.3 to about 2.6 and the total level of CMC and MC present in the liquid detergent concentrate compositions is from about 0.1 wt. % to about 10 wt. %, from about 0.2 wt. % to about 8 wt. %, from about 0.3 wt. % to about 5 wt. %, from about 0.5 to about 2.5 wt. %, from about 1 to about 2.5 wt%.
  • the ratio of CMC : MC is from 2 : 1 to 1 : 4, from 2 : 1 to 1 : 2, from 2 : 1 to 1 : 1, about 2 : 1.
  • the source of alkalinity can be any source of alkalinity that is compatible with the other components of the liquid laundry detergent composition.
  • exemplary sources of alkalinity include alkali metal hydroxides, alkali metal salts, phosphates, amines, and mixtures thereof.
  • the alkalinity of a liquid laundry detergent composition as defined herein can be adjusted by adding the source of alkalinity until a pH- value of: from about 11 to about 14; from about 12 to about 14; from about 12.5 to about 14 is achieved.
  • Exemplary alkali metal hydroxides include sodium hydroxide, potassium hydroxide, and lithium hydroxide. Most preferred is sodium hydroxide, particularly when utilized as a 50% aqueous solution (caustic soda).
  • Exemplary alkali metal salts include sodium carbonate, trisodium phosphate, potassium carbonate, and mixtures thereof.
  • Exemplary phosphates include sodium pyrophosphate, potassium pyrophosphate, and mixtures thereof.
  • Exemplary amines include alkanolamines selected from the group comprising triethanolamine (TEA), monoethanolamine (MEA), diethanolamine (DEA), and mixtures thereof.
  • the source of alkalinity may be added to the composition in a variety of forms, including for example in the form of solid beads, dissolved in an aqueous solution or as a combination thereof.
  • Alkali metal hydroxides are commercially available as pellets or beads having a mix of particle sizes ranging from 12- 100 U.S. mesh, or as an aqueous solution, such as for example, as an about 45 wt.%, as an about 50 wt.%, or as an about 73 wt.% solution.
  • the source of alkalinity may comprises one or more different sources of alkalinity with the provision that the total level of the source of alkalinity in the present composition is form about 1 wt.
  • Suitable solvents for use in the liquid detergent concentrate compositions herein include, but are not limited to, water, alcohols, glycols, glycol ethers, esters, and the like, or combinations thereof.
  • the liquid detergent concentrate compositions include water as the solvent.
  • Suitable alcohols include, but are not limited to, ethanol, isopropanol (propan-2-ol, isopropyl alcohol), 2-butoxy ethanol (butyl glycol), 1-decanol, benzyl alcohol, glycerin, monoethanolamine (MEA), and the like, or combinations thereof.
  • Suitable glycols include, but are not limited to, ethylene glycol (monoethylene glycol or MEG), diethylene glycol (propylene glycol/1, 2-propanediol or butoxy diglycol or DEG), Methylene glycol (TEG), tetraethylene glycol (TETRA EG), glycerin, propylene glycol, dipropylene glycol, hexylene glycol, and the like, or combinations thereof.
  • MEG monoethylene glycol
  • DEG 2-propanediol or butoxy diglycol or DEG
  • TEG Methylene glycol
  • TETRA EG tetraethylene glycol
  • glycerin propylene glycol, dipropylene glycol, hexylene glycol, and the like, or combinations thereof.
  • Water is especially preferred as solvent for use herein.
  • the solvent is added to the liquid laundry detergent composition to balance the composition.
  • solvent is present at a level of from: 1 wt.% to about 70 wt.%; from about 5 wt.% to about 60 wt.%; from about 10 wt.% to about 50 wt.%; from about 15 wt.% to about 40 wt.%, based on the total weight of the liquid laundry detergent composition, and as defined hereinbefore.
  • the liquid detergent concentrate compositions include one or more non-ionic surfactants at a total level of from 1 wt. % to about 70 wt. %, from about 2 wt. % to about 60 wt. %, from about 5 wt. % to about 40 wt. %, from about 10 wt. % to about 30 wt. %, about 15 to 25 wt. % of the liquid detergent concentrate composition.
  • liquid detergent concentrate compositions having a mixture of non-ionic surfactants.
  • the non-ionic surfactant usually is a compound which is selected from the group consisting of alcohol alkoxylates, alkyl phenol alkoxylates, alkyl thio alkoxylates, ethoxylate-propoxylate oligomers, alkoxylated esters, alkoxylated carboxylic acids, alkoxylated salts of carboxylic acids, ethers, amines, amine oxides, amides, and mixtures thereof.
  • the liquid detergent concentrate compositions include at least one nonionic surfactant which is a synthetic or natural alcohol that is alkoxylated with ethylene and/or propylene and/or butylene oxide to yield a C6-C24 alcohol ethoxylate and/or propoxylate and/or butoxylate, preferably C 6 -Ci4 alcohol ethoxylate and/or propoxylate and/or butoxylate having 1 to 20 alkylene oxide groups, preferably 2 to 20 alkylene oxide groups; C6-C24 alkylphenol ethoxylates, preferably Cs-Cio alkylphenol ethoxylates having 1 to 100 ethylene oxide groups, preferably about 12 to about 20 ethylene oxide groups; and C6-C24 alkylpolyglycosides, preferably C6-C2 0 alkylpolyglycosides having 1 to 20 glycoside groups, preferably 9 to 20 glycoside groups.
  • nonionic surfactant which is a synthetic or natural alcohol that is alkoxylated
  • the present invention includes at least one non-ionic surfactant which is a ethoxylated fatty alcohol of the formula (I) R 1 -(OC2H4) M -OH, wherein R 1 is a linear or branched C9-C16 alkyl or alkenyl group and m is 3 to 10.
  • non-ionic surfactant which is a ethoxylated fatty alcohol of the formula (I) R 1 -(OC2H4) M -OH, wherein R 1 is a linear or branched C9-C16 alkyl or alkenyl group and m is 3 to 10.
  • the present invention includes at least one, and preferably two non- ionic surfactants which are ethoxylated fatty alcohols of the formula (I) R 1 -(OC2H4) M -OH, wherein R 1 is a linear or branched C H-CK alkyl or alkenyl group and m is 5 to 10.
  • the present invention includes a combination of non-ionic surfactants which are alkoxylated alcohols of the formula (I) R 1 -(OC2H4) M -OH, wherein R 1 is an iso-tridecyl group and m is 6 to 12, preferably m is 6 to 10, most preferred m is 8.
  • non-ionic surfactants which are alkoxylated alcohols of the formula (I) R 1 -(OC2H4) M -OH, wherein R 1 is an iso-tridecyl group and m is 6 to 12, preferably m is 6 to 10, most preferred m is 8.
  • the non-ionic surfactant is at least one ethoxylated guerbet alcohol of the formula (I) R 1 -(OC2H4) M -OH, wherein R 1 is a branched C9-C2 0 alkyl group, preferably a branched C9-C 18 alkyl group, further preferred a branched C9-C15 alkyl group, more preferred a branched C9-C11 alkyl group, most preferred a branched C1 0 alkyl group and m is from 2 to 10, preferably 2 to 6.
  • the non-ionic surfactant is at least one alkoxylated fatty alcohol of the formula (II) R 2 -(OC 2 H4) x - (OC 3 H6)y-OH, wherein R 2 is a linear or branched C6-C24 alkyl or alkenyl group, x is 0 to 18 and y is 0 to 10 and the sum of x and y is at least 2 and one of x or y may be 0.
  • the non-ionic surfactant is at least one ethoxylated and/or propoxylated fatty alcohol of the formula (II) R 2 -(OC2H4) x -(OC 3 H6) Y -OH, wherein R 2 is a linear or branched Cs-Cis alkyl or alkenyl group, x is 0 to 10 and y is 0 to 10 and the sum of x and y is at least 2 and one of x or y may be O.
  • the non-ionic surfactant is at least one ethoxylated and/or propoxylated fatty alcohol of the formula (II) R 2 -(OC2H4) x - (OC 3 H6) Y -OH, wherein R 2 is a linear or branched C9-C16 alkyl or alkenyl group, x is 3 to 10 and y is 3 to 10 and the sum of x and y is at least 3 and one of x or y may be O.
  • Exemplary nonionic surfactants suitable for use herein are ethoxylates of alkyl polyethylene glycol ethers based on the ClO-Guerbet alcohol and/or isotridecanol. Commercially available forms of ethoxylates of alkyl polyethylene glycol ethers based on isotridecanol are available from BASF under the LUTENSOL® range as LUTENSOL® T08, LUTENSOL® T02.
  • a liquid detergent concentrate composition comprising a mixture of at least two nonionic surfactants wherein: at least one of said surfactants is an ethoxylate of alkyl polyethylene glycol ethers based on the ClO-Guerbet alcohol and/or isotridecanol; said mixture comprises at least one 2 EO-ethoxylate and at least one 8 EO-ethoxylate of alkyl polyethylene glycol ethers based on isotridecanol; at least one of said surfactants is an ethoxylate of alkyl polyethylene glycol ethers based on isotridecanol and at least one of said surfactants is an amine oxide-based nonionic.
  • a liquid detergent concentrate composition comprising a mixture of at least two nonionic surfactants wherein said mixture comprises at least one 2 EO-ethoxylate and at least one 8 EO-ethoxylate of alkyl polyethylene glycol ethers based on isotridecyl alcohol and wherein the ratio of the 2 EO-ethoxylate to 8 EO- ethoxylate is from: about 1 :2 to about 1 :8; from about 1 : 3; from about 1 : 3 to about 1 :5.
  • a liquid detergent concentrate composition comprising a mixture of at least two nonionic surfactants wherein said mixture comprises at least one 2 EO-ethoxylate and at least one 8 EO-ethoxylate of alkyl polyethylene glycol ethers based on isotridecyl alcohol and wherein the total level of the 2 EO-ethoxylate and the 8 EO-ethoxylate is from about: 5% to about 50 wt. , from about 15 to 30 wt. , from about 5 to 20 wt. %.
  • a liquid detergent concentrate composition comprising a mixture of at least two nonionic surfactants wherein said mixture comprises at least one 2 EO-ethoxylate and at least one 8 EO-ethoxylate of alkyl polyethylene glycol ethers based on isotridecyl alcohol and wherein the total level of the 2 EO-ethoxylate and the 8 EO-ethoxylate is from about: 5% to about 50 wt.%; from about 5 to 30 wt.%, from about 5 to 20 wt.
  • Exemplary 2 EO and 8 EO-ethoxylates for use in accordance with any of the aspects herein are ethoxylates of alkyl polyethylene glycol ethers based on isotridecanol are available from BASF under the LUTENSOL® range as poly(oxy-l,2- ethanediyl),LUTENSOL® T08 and isotridecanol, ethoxylated, LUTENSOL® T02.
  • LUTENSOL® XP30 is an alkyl polyethylene glycol ethers based on the ClO-Guerbet alcohol and ethylene oxide having a degree of ethoxylation of 3 and a hydroxyl number (in mg KOH/g) of 195.
  • non-ionic surfactants suitable for use herein include amine oxide-based non-ionics.
  • Commercially available amine oxide-based nonionics suitable for use herein include decamine oxides, such as the TEGOTENS® range available from Evonik Industries, and TEGOTENS® DO, 1-decamine, N, N-dimethyl-, N-oxide.
  • a liquid detergent concentrate composition comprising a mixture of nonionic surfactants wherein said mixture comprises at least one 2 EO-ethoxylate and at least one 8 EO-ethoxylate of alkyl polyethylene glycol ethers based on isotridecyl alcohol and at least one amine-based non-ionic surfactant.
  • a liquid detergent concentrate composition comprising a mixture of nonionic surfactants wherein said mixture comprises at least one 2 EO-ethoxylate and at least one 8 EO-ethoxylate of alkyl polyethylene glycol ethers based on isotridecyl alcohol and at least one amine-based non-ionic surfactant wherein the ratio of the combined 2 EO-ethoxylate and 8 EO-ethoxylate to the amine- based non-ionic surfactant is from: about 15 : 1; about 10 :1; about 8.5 : 1.
  • a liquid detergent concentrate composition comprising a mixture of nonionic surfactants wherein said mixture comprises at least one 2 EO-ethoxylate and at least one 8 EO-ethoxylate of alkyl polyethylene glycol ethers based on isotridecyl alcohol and at least one amine-based non-ionic surfactant wherein the total level of the mixture of nonionic surfactants is from about 5% to about 60 wt. , from about 5 to 35 wt.%, from about 5 to 25 wt. %.
  • An exemplary mixture of nonioninc surfactants for use herein is a mixture of ethoxylates of alkyl polyethylene glycol ethers based on isotridecanol as available from BASF under the LUTENSOL® range as LUTENSOL® T08, LUTENSOL® T02 and amine oxide- based nonionics including decamine oxides, such as the TEGOTENS® range available from Evonik Industries, and TEGOTENS® DO, 1 -decamine, N, N-dimethyl-, N-oxide.
  • non-ionic surfactants suitable for use herein include alkoxylated alcohols having the formula R-(OC 2 H 4 )x-(OC 3 H 6 )y, wherein R is a C6-C22 alkyl or alkenyl group, x is 0 to 18 and y is 0 to 10 and the sum of x and y is at least 5 and one of x or y may be 0.
  • R is a C6-C22 alkyl or alkenyl group
  • x is 0 to 18 and y is 0 to 10 and the sum of x and y is at least 5 and one of x or y may be 0.
  • suitable non -ionic surfactants are liquid alkoxylated preferably ethoxylated and/or propoxylated alcohols.
  • These include primary alcohols containing 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxides or propylene oxides per mole of alcohol in which the alcohol already may be linear or 2-methyl- branched or may contain linear and methyl-branched radicals in the form of the mixtures typically present in oxoalcohol radicals.
  • Examplary non-ionic surfactants of these types are alcohol ethoxylates containing linear radicals of alcohols with 8 to 18 carbon atoms, for example coconut fatty alcohol, tallow fatty alcohol or oleyl alcohol which may contain an average of 2 to 8 EO units per molecule.
  • Ethoxylated and/or propoxylated alcohol nonionic surfactants include for example C13-C15 alcohols containing 6 EO units, C12-C14 alcohols containing 5 EO (ethylene oxide) units and 4 PO (propylene oxide) units, CIO isoalcohols containing 3 EO units, C13-C15 alcohols containing 7 EO units, C13-C15 alcohols containing 3 EO units and/or 10 EO units or mixtures of these non-ionic surfactants.
  • Such non-ionic surfactants are available under the trade names
  • the non-ionic surfactants are used to provide the resulting use solution with desired detersive properties.
  • the non-ionic surfactant components can include a mixture of non- ionic surfactants.
  • the liquid detergent concentrate composition additionally comprises one or more thickening and/or stablizing agents at a total level of from 0.01 to 10 wt.%.
  • Suitable thickening and/or stabilizing agents for use herein include one or more crosslinked or partly crosslinked polyacrylic acids and/or polymethacrylic acids.
  • polyacrylic acid or polymethacrylic acid is crosslinked or partly crosslinked with a polyalkenyl polyether compound as crosslinker is used as thickener and stabiliser for a liquid detergent concentrate composition in the form of an emulsion.
  • Polyacrylic acids (acrylic acid polymers) or polymethacrylic acids crosslinked or partly crosslinked with a polyalkenyl polyether compound as crosslinker are commercially available under the trade name Carbopol® from Noveon.
  • suitable materials for use herein include: Carbopol® EDT 2691.
  • the thickening and/or stabilizing agent is at least one crosslinked or partly crosslinked polyacrylic acids and/or polymethacrylic acids and is present at 0.05 to 9 wt. , 0.1 to 8 wt. , or 0.2 to 0.7 wt. .
  • Liquid detergent concentrate compositions according to the invention have viscosities in the range of from 400 to 3000, between 400 to 2000 mPas, at 20°C measured at 20 revolutions per minute on a Brookfield RVT viscosimeter with spindle no. 2.
  • the liquid detergent concentrate composition of the first component according to the invention can include from 1 to 20 wt. % of one or more anionic surfactants, and optionally from 0.1 to 10 wt. % of one or more anti-foaming agents.
  • anionic surfactants that can be used include organic carboxylates, organic sulfonates, organic sulfates, organic phosphates and the like, particularly linear alkylaryl sulfonates, such as alkylarylcarboxylates, alkylarylsulfonates, alkylarylphosphates, and the like.
  • anionic surfactants are known within the surfactant art as linear alkyl benzyl sulfonates (LABS), alpha olefin sulfonates (AOS), alkyl sulfates, and secondary alkane sulfonates.
  • the anionic surfactants can be provided in the composition in an amount of from: 0 wt.% to about 20 wt.%; from about 1 wt.% to about 20 wt.%; from about 5 wt.% to about 15 wt.%; from about 5 wt.% to about 10 wt. %, based on the weight of the total liquid detergent concentrate composition, as defined hereinbefore. Where one or more amphoteric surfactants are additionally present the total level of the amphoteric and anionic surfactants should not exceed 10 wt.%.
  • composition comprises one or more anionic surfactants
  • cationic surfactant is included.
  • the liquid detergent concentrate composition of the first component according to the invention can include from 0.1 to 10 wt. % of one or more cationic surfactants. Where the composition includes one or more cationic surfactants the level of one or more cationic surfactants is from 0.1 to 10 wt. %, 0 to 5 wt. %, 0.1 to 1 wt. %, 0.5 to 1 wt. %.
  • Suitable cationic surfactants include quaternary ammonium compounds having the formula of RR'R"R"N + X " , where R, R, R" and R" are each a Ci-C 24 alkyl, aryl or arylalkyl group that can optionally contain one or more P, O, S or N heteroatoms, and X is F, CI, Br, I or an alkyl sulfate.
  • Each of R, R, R" and R'" can independently include, individually or in combination, substituents including 6 to 24 carbon atoms, preferably 14 to 24 carbon atoms, and more preferably, 16 to 24 carbon atoms.
  • Each of R, R', R" and R'" can independently be linear, cyclic, branched, saturated, or unsaturated, and can include heteroatoms such as oxygen, phosphorous, sulfur, or nitrogen. Any two of R, R, R" and R'” can form a cyclic group. Any one of three of R, R, R" and R'” can independently be hydrogen.
  • X is preferably a counter ion and preferably a non- fluoride counter ion. Exemplary counter ions include chloride, bromide, methosulfate, ethosulfate, sulfate, and phosphate.
  • the quaternary ammonium compound includes alkyl ethoxylated and/or propoxylated quaternary ammonium salts (or amines).
  • Preferred alkyl groups contain between about 6 and about 22 carbon atoms and can be saturated and/or unsaturated.
  • the degree of ethoxylation is preferably between about 2 and about 20, and/or the degree of propoxylation is preferably between about 0 and about 30.
  • the quaternary ammonium compound includes an alkyl group with about 6 to about 22 carbon atoms and a degree of ethoxylation between about 2 and about 20.
  • An exemplary cationic surfactant is commercially available under the name Berol 563 from Akzo-Nobel. Additional cationic surfactants suitable for use include ethoxylated and/or propoxylated alkyl amines, diamines, or triamines.
  • amphoteric surfactants are additionally present the total level of the amphoteric and cationic surfactants should not exceed 10 wt.%.
  • the liquid detergent concentrate composition of the first component according to the invention can include from 0.1 to 10 wt. % of one or more amphoteric surfactants.
  • suitable amphoteric surfactants include capryloamphopropionate, disodium lauryl B-iminodipropionate, cocoamphocarboxypropionate, and disodium octylimino dipropionate.
  • amphoteric surfactants can be provided in the composition in an amount of about 0 wt.% to about 10 wt.%; from 1 to 10 wt. %, 1 to 5 wt. %; 2 to 5 wt. %, based on the weight of the total liquid detergent concentrate composition.
  • the liquid detergent concentrate composition may optionally additionally include from lwt % to 20wt % in total of one or more hydrotrope components. It is anticipated, that where present, the one or more hydrotrope components will provide added stability to the liquid detergent concentrate, primarily by stabilizing the nonionic surfactant component.
  • hydrotropes examples include the sodium, potassium, ammonium and alkanol ammonium salts of xylene, toluene, ethylbenzoate, isopropylbenzene, naphthalene, alkyl naphthalene sulfonates, phosphate esters of alkoxylated alkyl phenols, phosphate esters of alkoxylated alcohols, short chain (C8 or less) alkyl polyglycoside, sodium, potassium and ammonium salts of the allcyl sarcosinates, salts of cumene sulfonates, amino propionates, diphenyl oxides, and disulfonates.
  • Hydrotropes are useful in maintaining the dispersion of organic materials, including the surfactant, in the aqueous emulsion.
  • the hydrotrope component When used, it can be provided in an amount of about 1 wt.% to about 20 wt.%, preferably about 2 wt.% to about 15 wt.%, further preferred about 3 wt.% to about 15 wt.%, based on the weight of the liquid detergent concentrate composition.
  • the liquid detergent concentrate compositions herein may optionally include one or more anti-foaming agent, so-called foam inhibitors or defoamers, particularly where one or more anionic surfactants is present in the composition.
  • these are non-surface-active agents and include: silica and silicones; aliphatic acids or esters; alcohols; sulphates or sulfonates; amines or amides; haloxygenated compounds such as fluorochlorohydrocarbons; vegetable oils, organopolysiloxanes and mixtures thereof with microfine, optionally silanised silica, paraffins, waxes, mineral oils as well as their sulfonated or sulfated derivatives; fatty acids and/or their soaps such as alkali, alkaline earth metal soaps; and phosphates and phosphate esters such as alkali and alkaline diphosphates, and tributyl phospates, micro-crystalline waxes and mixtures
  • silicones for example mixtures of silicones, paraffins or waxes
  • One of the more effective antifoaming agents includes silicones. Silicones such as dimethyl silicone, glycol polysiloxane, methylphenol polysiloxane, trialkyl or tetralkyi silanes, hydrophobic silica defoamers and mixtures thereof can all be used in defoaming applications.
  • defoamers commonly available include silicones such as Ardefoam® from Armour Industrial Chemical Company which is a silicone bound in an organic emulsion; Foam Kill® or Kresseo® available from Krusable Chemical Company which are silicone and non-silicone type defoamers as well as silicone esters; and Anti- Foam A® and DC-200 from Dow Corning Corporation.
  • Other defoamers that can be used in preferred embodiments of the invention include organic amides such as Antimussol® from Clariant or oil and/or polyalkylene based compounds such as Agitan® from Munzing or branched fatty alcohols such as Isofol® from Sasol.
  • compositions of the present invention may further include antifoaming agents or defoaming agents which are based on alcohol alkoxylates that are stable in alkaline environments and are oxidatively stable.
  • antifoaming agents or defoaming agents which are based on alcohol alkoxylates that are stable in alkaline environments and are oxidatively stable.
  • one of the more effective antifoaming agents are the alcohol alkoxylates having an alcohol chain length of about C-C 12 , and more specifically C9-CI 0 , and having poly- propylene oxide alkoxylate in whole or part of the alkylene oxide portion.
  • Commercial defoamers commonly available of this type include alkoxylates such as the BASF Degressal's; especially Degressal SD20.
  • cloud point defoamers typically non-ionic surfactants consisting of ethoxylated/propoxylated alcohols
  • Plurafac® types from BASF
  • Dehypon® types from Cognis.
  • the total amount of the one or more anti-foaming agents can be about 0.1 wt.% to about 10 wt.%, preferably about 0.2 wt.% to about 5 wt.%, further preferred about 0.5 wt.% to about 4 wt.%, and more preferred about 1 wt.% to about 3 wt.%, based on the weight of the liquid detergent concentrate composition.
  • liquid detergent concentrate compositions according to the present invention include, but are not limited to, acidulants, pigments and/or dyes, dye transfer/color transfer inhibitors or color protection agents, additional solvents, optical brighteners, stabilizing agents e.g.
  • chelating agents or sequestrates builders, buffering or water conditioning or water softening agents, wetting agents, thickeners, foaming agents, solidification agents, oil and water repellant agents, insect repellency agents, anti-pilling agents, color fastness agents, starch/sizing agents, fabric softening agents, anti-static agents, anti-wrinkling agents, souring agents, mildew removing agents, iron controlling agents, antimicrobials, fungicides, UV absorbers / UV light protection agents, sanitizing agents, disinfecting agents ,allergicide agents, aesthetic enhancing agents such as colorants, odor removal and/or odor capturing agents, perfumes or fragrances, and the like.
  • the liquid detergent concentrate composition additionally comprises one or more additives selected from the group consisting of: dye transfer/color transfer inhibitors or color protection agents, additional solvents, optical brighteners, stabilizing agents e.g. chelating agents or sequestrates, builders, odor removal and/or odor capturing agents, perfumes or fragrances, and combinations and mixtures thereof.
  • additional solvents include alcohols, such as C 2 -C6 alcohols, N-alkyl pyrrolidones, such as a Cs-Cis alkyl pyrrolidone, e.g.
  • N-octyl pyrrolidone N-lauryl pyrrolidone, and the like.
  • Lauryl (or n-dodecyl) pyrrolidone is commercially available, for example, as sold by ISF Chemicals under the brand name Surfadone, such as Surfadone LP-300.
  • Solvents of similar structure can also be used.
  • Such solvents include lactones, such as decano lactone.
  • Other suitable solvents include diacetone alcohol, long chain, e.g. greater than C6-alkyl ethers, cyclic alkyl ketones, a 1 ,2 alkane diol having 5 to 10 carbon atoms such as 1 ,2 hexanediol, a Cs-Cio alkene carbonate, a pyrrol (such as N-capryl pyrrol, N- lauryl pyrrol, and the like), and mixtures thereof.
  • a pyrrol such as N-capryl pyrrol, N- lauryl pyrrol, and the like
  • the liquid detergent concentrate composition according to the invention may additionally comprise one or more enzyme materials.
  • the enzyme material can be selected from proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof.
  • the additional, optional enzyme material can be present in said composition at a level of from about 0.001 wt. to about 3 wt. , based on the weight of the liquid detergent concentrate composition. Dyes/Odorants
  • Dyes may be included to alter the appearance of the composition, as for example, Direct Blue 86 (Miles), Fastusol Blue (Mobay Chemical Corp.), Acid Orange 7 (American Cyanamid), Basic Violet 10 (Sandoz), Acid Yellow 23 (GAF), Acid Yellow 17 (Sigma Chemical), Sap Green (Keyston Analine and Chemical), Metanil Yellow (Keystone Analine and Chemical), Acid Blue 9 (Hilton Davis), Sandolan Blue/ Acid Blue 182 (Sandoz), Hisol Fast Red (Capitol Color and Chemical), Fluorescein (Capitol Color and Chemical), Acid Green 25 (Ciba-Geigy), and the like.
  • Direct Blue 86 Miles
  • Fastusol Blue Mobay Chemical Corp.
  • Acid Orange 7 American Cyanamid
  • Basic Violet 10 Sandoz
  • Acid Yellow 23 GAF
  • Acid Yellow 17 Sigma Chemical
  • Sap Green Keyston Analine and Chemical
  • Metanil Yellow Keystone Analine and Chemical
  • Acid Blue 9 Hilton Davis
  • Fragrances or perfumes that may be included in the compositions include, for example, terpenoids such as citronellol, aldehydes such as amyl cinnamaldehyde, a jasmine such as CIS-jasmine or jasmal, vanillin, and the like.
  • preferred dyes and odorants include one or more blue dyes, which can be employed at concentrations up to about 1 wt. %.
  • Optical brighteners also known as optical brightening agents (OBAs) as defined herein include fluorescent whitening agents (FBAs) and fluorescent brightening agents (FBAs), and provide color brightening, or optical compensation for the yellow cast in textile substrates (color masking).
  • FBAs fluorescent whitening agents
  • FBAs fluorescent brightening agents
  • color masking color masking
  • yellowing is replaced by light emitted from optical brighteners present in the area commensurate in scope with yellow color.
  • the violet to blue light supplied by the optical brighteners combines with other light reflected from the location to provide a substantially complete or enhanced bright white appearance.
  • the brightener through fluorescence produces this additional light.
  • Optical brighteners can absorb light in the ultraviolet range (e.g., 275-400 nm) and can emit light in the ultraviolet blue spectrum (e.g., 400-500 nm).
  • Fluorescent compounds belonging to the optical brightener family are typically aromatic or aromatic heterocyclic materials often containing condensed ring system.
  • An important feature of these compounds is the presence of an uninterrupted chain of conjugated double bonds associated with an aromatic ring. The number of such conjugated double bonds is dependent on substituents as well as the planarity of the fluorescent part of the molecule.
  • optical brightener compounds are derivatives of triazine-stilbenes including di-, tetra- or hexa-sulphonated stilbenres, 4,4'-diamino stilbene, biphenyl-stilbenes, five membered heterocycles (triazoles, oxazoles, imidazoles, etc.) or six membered heterocycles (cumarins, naphthalamides, triazines, etc.).
  • one or more optical brighteners for use in the liquid laundry detergent compositions herein will depend upon a number of factors, such as the type of detergent, the nature of other components present in the composition, the temperature of the wash water, the degree of agitation, and the ratio of the material washed to the tub size.
  • the brightener selection is also dependent upon the type of material to be cleaned, e.g., cottons, synthetics, etc. Since the present liquid laundry detergent compositions are suitable for use in products used to clean a variety laundry items, having a variety of fabrics, and for work-wear cleaning in particular, the compositions should contain a mixture of brighteners, which are effective for a variety of fabrics. It is of course necessary that the individual components of such a brightener mixture be compatible.
  • Preferred mixtures of optical brighteners for use herein include one or more compounds which has optimal absorption at wash temperatures of greater than about 55°C or at about 60°C, such as Tinopal® DMA-X, and one or more compounds which has optimal absorption at wash temperatures in the range of from about 30°C to about 40°C, such as Tinopal® CBS-X.
  • optical brighteners useful in the present invention are commercially available and will be appreciated by those skilled in the art. At least some commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, carboxylic acid, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles and other miscellaneous agents.
  • Stilbene derivatives which may be useful in the present invention include, but are not necessarily limited to, derivatives of bis(triazinyl)amino-stilbene; bisacylamino derivatives of stilbene; triazole derivatives of stilbene; oxadiazole derivatives of stilbene; oxazole derivatives of stilbene; and styryl derivatives of stilbene.
  • optical brighteners examples include: 4,4'-bis-(2- sulfostyryl)biphenyl disodium salt, available from BASF under the trade name Tinopal® CBS-X; benzensulfonic acid, 2,2'-(l,2-ethenediyl)bis[5-[[4-(4-morpholinyl)-6- (phenylamino)-l,3,5-triazin-2-yl]amino]-disodium salt, also available from BASF under the trade name Tinopal® DMA-X; Tinopal® 5 BM-GX; Tinopal® CBS-CL; Tinopal® DMS-X; Tinopal® AMS-GX; Leucophor® brighteners from Archrom
  • Optical brighteners particularly suitable for use include: 4,4'-bis-(2-sulostyryl)biphenyl disodium salt, available from BASF under the trade name Tinopal® CBS-X; and/or benzensulfonic acid, 2,2'-(l,2-ethenediyl)bis[5-[[4-(4-morpholinyl)-6-(phenylamino)- l,3,5-triazin-2-yl]amino]-disodium salt, also available from BASF under the trade name Tinopal® DMA-X, and from 3V under the trade name Optiblank® 2M/G LT Extra.
  • the total amount of one or more optical brighteners, and more particularly a mixture of optical brighteners as defined herein can be present at a level of from about 0.1 wt. % to up to about 2 wt.%, from about 0.2 wt.% to about 1 wt.%, at a level of from about 0.6 wt.% to up to about 0.9 wt.%, from about 0.2 wt.% to about 1 wt.% based on the weight of the liquid laundry detergent compositions herein, and as detailed hereinbefore. Accordingly there is provided a liquid laundry detergent having a total amount of one or more optical brighteners, and more particularly a mixture of optical brighteners at a level of from about 0.1 wt.
  • liquid laundry detergent having a total amount of a mixture of 4,4'-bis-(2-sulfostyryl)biphenyl disodium salt, available from BASF under the trade name Tinopal® CBS-X and benzensulfonic acid, 2,2'-(l,2-ethenediyl)bis[5-[[4-(4-morpholinyl)- 6-(phenylamino)-l,3,5-triazin-2-yl]amino]-disodium salt, also available from BASF under the trade name Tinopal® DMA-X optical brighteners at a level of from about 0.1 wt.
  • the liquid laundry detergent compositions herein can include one or more complexing agents, also known as sequestrants, chelating agents or binding agents, or builders.
  • a complexing agent, or a sequestrant is a molecule capable of coordinating (i.e., binding) the metal ions commonly found in natural water to prevent those metal ions from interfering with the action of other detersive ingredients in a cleaning composition.
  • Some complexing agents can also function as a threshold agent when included in an effective amount.
  • Suitable complexing agents include, but are not limited to organic chelating compounds which sequester metal ions in solution, particularly transition metal ions.
  • suitable complexing agents can be used in the liquid laundry detergent compositions herein including, for example, organic amino- or hyroxy-polyphosphonic acid complexing agents (either in acid or soluble salt forms), carboxylic acids (e.g. polymeric polycarbonate), hydroxycarboxylic acids, aminocarboxylic acids, or heterocyclic carboxylic acids e.g. , pyridine-2-6-dicarboxylic acid (dipicolinic acid), condensed phosphates, inorganic builders, polymeric polycarboxylates, and the like, and combinations or mixtures thereof.
  • Such complexing agents are commercially available.
  • Suitable condensed phosphates for use herein include sodium and potassium orthophosphate, sodium and potassium pyrophosphate, sodium and potassium tripolyphosphate, sodium hexametaphosphate.
  • Suitable organic phosphonate complexing agents for use herein include organic - phosphonic acids and alkali metal salts thereof.
  • CioH( 2 8-x)N 2 K x Oi 2 P 4 (x 6); bis(hexamethylene)triamine(pentamethylenephosphonic acid) : (H0 2 )POCH 2 N[(CH 2 )6N[CH 2 PO(OH) 2 ] 2 ] 2 ; and phosphorus acid H 3 P0 3; and other similar organic phosphonates, and mixtures thereof.
  • Exemplary commercially available complexing agents include: phosphonates sold under the trade name DEQUEST® from Italmatch or Cublen® from Zschimmer & Schwarz or Briquest® from Rhodia including, for example, 1-hydroxyethylidine- 1,1 -diphosphonic acid (CH 3 C(P0 3 H 2 ) 2 OH) (HEDP) DEQUEST® 2010; amino(tri(methylenephosphonic acid)), (N[CH 2 P0 3 H2]3), available as DEQUEST® 2000, or as Cublen® AP5 from Zschimmer & Schwarz, or as Briquest® 301-50A from Rhodia; ethylenediamine[tetra(methylenephoshonic acid)], (DTMP), available from Itsalmatch as DEQUEST® 2041 ; diethylene triamine penta(methylene phosphonic acid), (DTPMP), available from Thermphos as DEQUEST® 2066, or as Cublen® D 3217S from Zschimmer & Schwarz; 2-phosphonobutane-
  • liquid detergent concentrate compositions herein include a mixture of complexing agents wherein at least one of the complexing agents is a phosphonate-based complexing agent.
  • the mixture of complexing agents includes at least one phosphonate-based complexing agent and at least one non-phosphonate-based complexing agent wherein the ratio of total level of complexing agents is from about: 5 to 30 wt. %, from about 10 to 20 wt. and wherein the ratio of phosphonate-based agent to non- phosponate agent is from about 1 : 1 to about 1 : 4; from about 1 : 1 to about 1 : 3; from about 1 : 2 to about 1 : 3.
  • the mixture of complexing agents in the liquid detergent concentrate compositions herein includes diethylene triamine penta(methylene phosphonic acid), (DTPMP) and sodium methylglycinediacetate.
  • DTPMP diethylene triamine penta(methylene phosphonic acid),
  • sodium methylglycinediacetate the present compositions preferable contain 0.5 wt. % or less of phosphate.
  • the liquid laundry detergent composition of the invention includes a mixture of organic complexing agents which may be polymeric and small molecule complexing agents.
  • Organic small molecule complexing agents are typically organocarboxylate compounds or organophosphate complexing agents.
  • Poylmeric complexing agents commonly include polyanionic compositions such as polyacrylic acid compounds.
  • a mixture of organic complexing agents wherein at least one complexing agent is an aminophosphonate containing alkyl or alkenyl groups having less than 8 carbon atoms and at least one other complexing agent is an aminocarboxylic acid or alkali metal salt thereof.
  • the mixture of organic complexing agents in the liquid laundry detergent composition of the invention includes sodium methylglycinediacetate, Trilon® M and diethylene triamine penta(methylene phosphonic acid), DEQUEST® 2066 at a relative ratio of from 3:1 to 2.5 : 1; about 2.6 :1, and wherein their combined level in the composition is from 18 wt. % to 25 wt. , from 20 wt. % to 24 wt , about 22 wt. %.
  • the liquid laundry detergent composition of the invention includes a mixture of organic complexing agents independently selected from: sodium methylglycinediacetate, Trilon® M and diethylene triamine penta(methylene phosphonic acid), DEQUEST® 2066 at a relative ratio of from 3 :1 to 1 : 1, from 3 : 1 to 2 : 1 and wherein their combined level in the composition is from 15 wt % to 25 wt %, from 18 wt % to 24 wt , about 22 wt. .
  • the complexing agent can include an organic phosphonate, such as an organic-phosphonic acid and alkali metal salts thereof.
  • organic phosphonate such as an organic-phosphonic acid and alkali metal salts thereof.
  • exemplary suitable organic phosphonates for use herein include:
  • the small molecule organic complexing agent can be, or the mixture of complexing agents can include aminocarboxylic acid type sequestrants. Suitable aminocarboxylic acid type sequestrants include the acids or alkali metal salts thereof, e.g., amino acetates and salts thereof. Some examples include N-hydroxyethylaminodiacetic acid; hydro
  • NT A nitrilotriacetic acid
  • MGDA methylglycinediacetic acid
  • HEIDA 2-hydroxyethyliminodiacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • HEDTA N-hydroxyethyl-ethylenediaminetriacetic acid
  • DTP A diethylenetriammepentaacetic acid
  • TTHSA ethyloenediamine-tetrapropionic acid triethylentetraaminehexaacetic acid
  • GLDA N,N- diacetic acid
  • MGDA methylglycinediacetic acid
  • IDS iminodisuccinate
  • Preferred small molecule organic complexing agents include: ⁇ , ⁇ -diacetic acid (GLDA); methylglycinediacetic acid (MGDA); iminodisuccinic acid (IDS); the sodium salt of iminodisuccinic acid; and mixtures and combinations thereof.
  • GLDA ⁇ , ⁇ -diacetic acid
  • MGDA methylglycinediacetic acid
  • IDS iminodisuccinic acid
  • the sodium salt of iminodisuccinic acid and mixtures and combinations thereof.
  • Such agents, and mixtures and combinations of such agents are desirable because they are generally considered to be more environmentally friendly, particularly when compared with other agents such as for example EDTA.
  • Polymeric complexing agents suitable for use herein include homopolymeric and copolymeric agents.
  • Exemplary commercially available polymeric complexing agents include: homopolymers of acrylic acid, sold under the trade name AcusolTM 445 from Dow; maleic acid/acrylic acid co-polymers sold under the trade name Sokalan® CP 5 from BASF. It should be understood that the one or more complexing agents are optional components.
  • the total level of complexing agent(s) present is from about: 1 wt. % to about 30 wt.
  • the level of any one agent should not exceed 29 wt. % and ideally should not exceed 20 wt. %.
  • liquid detergent concentrate compositions comprising an emulsion having a water phase and an oil phase, the composition comprising based on the whole concentrate:
  • Color stabilizing agents also known as floor fastness agents or dye transfer inhibition or color protection agents, can be used in the liquid laundry detergent compositions herein.
  • Color transfer inhibitors are polymers of vinyl pyrrolidone, vinyl imidazole, vinyl pyridine-N-oxide or copolymers thereof. Polymers of vinyl imidazole, vinyl pyrrolidone and copolymers thereof are particularly suitable.
  • Exemplary color stabilizing agents that can be used include polyvinyl pyrrolidones and quaternary amines. It should be understood that the use of one or more color stabilizing agents are optional, but when one or more of such agents are utilized, the total level of color stabilizing agents in the compositions herein is an amount of: between about 0.1 wt. % and about 10 wt. ; from about 0.2 wt. to about 5 wt. ; from about 0.3 wt. to about 3 wt.%; from about 0.5 wt.% to about 1 wt.%, based on the weight of the total composition, and as defined hereinbefore. For the avoidance of doubt, where a mixture of color stabilizing agents is present the level of any one agent should not exceed 9.9 wt. % and ideally should not exceed 5 wt. %.
  • Softening agents can be included in the liquid laundry detergent compositions herein.
  • Exemplary softening agents include quaternary ammonium compounds such as alkylated quaternary ammonium compounds, ring or cyclic quaternary ammonium compounds, aromatic quaternary ammonium compounds, di-quaternary ammonium compounds, alkoxylated quaternary ammonium compounds, amidoamine quaternary ammonium compounds, ester quaternary ammonium compounds, and mixtures thereof.
  • Exemplary alkylated quaternary ammonium compounds include ammonium compounds having an alkyl group containing between 6 and 24 carbon atoms.
  • alkylated quaternary ammonium compounds include monoalkyl trimethyl quaternary ammonium compounds, monomethyl trialkyl quaternary ammonium compounds, and dialkyl dimethyl quaternary ammonium compounds.
  • alkylated quaternary ammonium compounds are available commercially under the names Adogen (Registered Trademark), Arosurf (Registered trademark), Variquat (Registered trademark), and Varisoft (Registered trademark).
  • the alkyl group can be a Cs- C22 group or a Cs-Cis group or a C12-C22 group that is aliphatic and saturated or unsaturated, or straight or branched, an alkyl group, a benzyl group, an alkyl ether propyl group, a hydro generated-tallow group, a coco group, a stearyl group, a palmityl group, or a soya group.
  • Exemplary ring or cyclic quaternary ammonium compounds include imidazolinium quaternary ammonium compounds and are also available under the name Varisoft (Registered trademark).
  • Exemplary imidazolinium quaternary ammonium compounds include methyl- 1-hydroxyl tallow amidoethyl-2-hydroxyl tallow imidazolinium-methyl sulfate, methyl- 1 -tallow amido ethyl-2-tallow imidazolinium-methyl sulfate, methyl- 1-oleyl amido ethyl-2-oleyl imidazolinium-methyl sulfate, and 1 -ethylene bis(2 -tallow, 1 -methyl, imidazolinium- methyl sulfate).
  • Exemplary aromatic quaternary ammonium compounds include those compounds that have at least one benzene ring in the structure.
  • Exemplary aromatic quaternary ammonium compounds include dimethyl alkyl benzyl quaternary ammonium compounds, monomethyl dialkyl benzyl quaternary ammonium compounds, tri-methyl benzyl quaternary ammonium compounds, and tri- alkyl benzyl quaternary ammonium compounds.
  • the alkyl group can contain between 6 and 24 carbon atoms, and can contain between 10 and 18 carbon atoms, and can be a stearyl group or a hydrogenated tallow group.
  • Exemplary aromatic quaternary ammonium compounds are available under the names Variquat (Registered trademark) and Varisoft (Registered trademark).
  • the aromatic quaternary ammonium compounds can include multiple benzyl groups.
  • Di- quaternary ammonium compounds include those compounds that have at least two quaternary ammonium groups.
  • An exemplary di-quaternary ammonium compound is N- tallow pentamethyl propane diammonium dichloride and is available under the name Adogen 477.
  • Exemplary alkoxylated quaternary ammonium compounds include methyl di-alkoxy alkyl quaternary ammonium compounds, tri-alkoxy alkyl quaternary ammonium compounds, tri-alkoxy methyl quaternary ammonium compounds, dimethyl alkoxy alkyl quaternary ammonium compounds, and tri-methyl alkoxy quaternary ammonium compounds.
  • the alkyl group can contain between 6 and 24 carbon atoms and the alkoxy groups can contain between 1 and 50 alkoxy groups units wherein each alkoxy unit contains between 2 and 3 carbon atoms.
  • Exemplary alkoxylated quaternary ammonium compounds are available under the names Variquat (Registered trademark), Varstat (Registered trademark), and Variquat (Registered trademark).
  • Exemplary amido amine quaternary ammonium compounds include diamidoamine quaternary ammonium compounds.
  • Exemplary diamidoamine quaternary ammonium compounds are available under the name Varisoft (Registered trademark).
  • Exemplary amido amine quaternary ammonium compounds that can be used herein are methyl- bis(tallow amido ethyl)-2-hydroxyethyl ammonium methyl sulfate, methyl bis(oleylamidoethyl)-2-hydroxyethyl ammonium methyl sulfate, and methyl bis (hydr.tallowamidoethyl)-2-hydroxyethyl ammonium methyl sulfate.
  • Exemplary ester quaternary compounds are available under the name Stephantex (Registered Trademark).
  • the quaternary ammonium compounds can include any counter ion that allows the component to be used in a manner that imparts fabric-softening properties.
  • exemplary counter ions include chloride, methyl sulfate, ethyl sulfate, and sulfate.
  • the softening agents are optional components and need not be present in the liquid laundry detergent compositions herein. When one or more fabric softening agents are incorporated into the liquid laundry detergent compositions herein, the total level of agent(s) is: from about 1 wt.% to about 20 wt.
  • pH Adjusting Agent The pH value of the liquid laundry detergent composition herein can be adjusted by adding a pH adjusting agent.
  • the pH can be adjusted by the introduction of a pH adjusting agent that can be an acid or a base. Adjusting the pH includes adjusting a concentrated solution and/or a use solution thereof.
  • a "use solution” as defined herein is a stable aqueous diluted solution of the liquid detergent concentrate composition, typically at from 0.5g/l to lOg/1 in water, which is suitable for washing textiles as discussed hereinafter.
  • the pH adjusting agent can be added to the use composition when it is desired to provide a shift in the pH level.
  • the pH adjusting agent can be provided as part of the liquid laundry detergent composition and can be provided in a form that allows it to take effect at a certain point in time during the wash cycle / use.
  • the pH adjusting agent can be coated in a manner that provides for release of the pH adjusting agent after a length of time.
  • the pH- adjusting agent can be a component that is generated as a result of a reaction.
  • the pH-adjusting agent can provide the desired pH shift to a second pH after the composition has been provided at the first pH for a desired length of time.
  • the pH adjusting agent can be referred to as an alkaline agent.
  • Exemplary alkaline agents that can be used has been already mentioned above and referred to as "source of alkalinity".
  • Sodium hydroxide, NaOH is a preferred source of alkalinity herein, particularly when provided as a 50% aqueous solution, alternatively KOH in an aqueous solution, or KOH or NaOH in a variety of solid forms in varying particle sizes can be used.
  • an acidifying agent When the pH adjusting agent is used to lower the pH, it can be referred to as an acidifying agent.
  • exemplary acidifying agents include inorganic acids, organic acids, and mixtures of inorganic acids and organic acids.
  • Exemplary inorganic acids that can be used include mineral acids such as sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid.
  • Exemplary organic acids that can be used include carboxylic acids including monocarboxylic acids and polycarboxcylic acids such as dicarboxcylic acids.
  • Exemplary carboxylic acids include aliphatic and aromatic carboxylic acids.
  • Exemplary aliphatic carboxylic acids include acetic acid, formic acid, halogen-containing carboxylic acids such as chloroacetic carboxylic acid, and modified carboxylic acids containing side groups such - OH, - R, - OR, -(EO) x , - (PO) x , - NH 2 , and- N0 2 wherein R is a Ci to Cio alkyl group.
  • Exemplary aromatic carboxylic acids include benzoic carboxylic acid, salicylic carboxylic acid, and aromatic carboxylic acid modified to include as a side group at least one of halogen, - OH, - R, - OR, -(EO) x , - (PO) x , - NH 2 , and- N0 2 wherein R is a Ci to Cio alkyl group.
  • Additional exemplary organic acids include oxalic acid, phthlaic acid, sebacic acid, adipic acid, citric acid, maleic acid, and modified forms thereof containing side groups including halogen, - OH, - R, - OR, -(EO) x , - (PO) x , - NH 2 , and- N0 2 wherein R is a Ci to Cio alkyl group. It should be understood that the subscript X refers to repeating units. Additional exemplary organic acids include fatty acids such as aliphatic fatty acids and aromatic fatty acids.
  • Exemplary aliphatic fatty acids include oleic acid, palmitic acid, stearic acid, C3-C26 fatty acids that may be saturated or unsaturated, and sulfonated forms of fatty acids.
  • An exemplary aromatic fatty acid includes phenylstearic acid. Additional acids that can be used include peroxycarboxylic acid such as peroxyacetic acid, and phthalimidopercarboxylic acids. Additional acidic pH adjusting agents include carbon dioxide and ozone.
  • the pH can be adjusted by adding the pH adjusting agent and/or by allowing the pH adjusting agent to cause a pH shift.
  • the pH adjusting agent can be formed in situ by reaction and/or the pH adjusting agent can be coated and, once the coating is degraded, the pH adjusting agent can become exposed to the liquid laundry detergent composition.
  • the liquid detergent concentrate composition is preferably used as a detergent for institutional and industrial washing as discussed hereinbefore, the liquid detergent concentrate composition does not contain any bleaching agents. In institutional and industrial washing processes the bleaching agent is normally dosed separately from the detergent.
  • a system comprising a first component and a second component, wherein the first component is represented by the liquid detergent composition according to the invention and wherein the second component is a bleaching composition.
  • the bleaching compositions include at least one oxidizing agent.
  • the bleaching composition can include any of a variety of oxidizing agents, for example, hydrogen peroxide and/or any inorganic or organic peroxide or peracid.
  • the oxidizing agent can be present at an amount effective to convert a carboxylic acid to a peroxycarboxylic acid.
  • the oxidizing agent can also have antimicrobial activity.
  • the oxidizing agent is present in an amount insufficient to exhibit antimicrobial activity.
  • the bleaching compositions include about 0.001 wt.- oxidizing agent to 60 wt.- oxidizing agent.
  • the compositions of the invention include about 10 wt.-% to about 30 wt.-% oxidizing agent.
  • inorganic oxidizing agents include the following types of compounds or sources of these compounds, or alkali metal salts including these types of compounds, or forming an adduct therewith: hydrogen peroxide, urea-hydrogen peroxide complexes or hydrogen peroxide donors of: group 1 (I A) oxidizing agents, for example lithium peroxide, sodium peroxide; group 2 (IIA) oxidizing agents, for example magnesium peroxide, calcium peroxide, strontium peroxide, barium peroxide; group 12 (MB) oxidizing agents, for example zinc peroxide; group 13 (111 A) oxidizing agents, for example boron compounds, such as perborates, for example sodium perborate hexahydrate of the formula Na2[B2(02)2(OH)4].6H20 (also called sodium perborate tetrahydrate); sodium peroxyborate tetrahydrate of the formula Na2B2(02)2[(OH)4].4H20 (also called sodium perborate trihydrate);
  • active inorganic oxygen compounds can include transition metal peroxides; and other such peroxygen compounds, and mixtures thereof.
  • organic oxidizing agents include, but are not limited to, perbenzoic acid, derivatives of perbenzoic acid, t-butyl benzoyl hydroperoxide, benzoyl hydroperoxide, or any other organic based peroxide and mixtures thereof, as well as sources of these compounds.
  • compositions of the present invention may employ one or more of the inorganic oxidizing agents listed above.
  • Suitable inorganic oxidizing agents include ozone, hydrogen peroxide, hydrogen peroxide adduct, group IIIA oxidizing agent, or hydrogen peroxide donors of group VIA oxidizing agent, group VA oxidizing agent, group VI IA oxidizing agent, or mixtures thereof.
  • Suitable examples of such inorganic oxidizing agents include percarbonate, perborate, persulfate, perphosphate, persilicate, or mixtures thereof.
  • the bleaching compositions of the present invention may include at least one carboxylic and/or percarboxylic acid.
  • the compositions of the present invention include at least two or more carboxylic and/or percarboxylic acids.
  • the carboxylic acid for use with the compositions of the present invention includes a Ci to C22 carboxylic acid.
  • the carboxylic acid for use with the compositions of the present invention is a Ci to C 12 carboxylic acid.
  • the carboxylic acid for use with the compositions of the present invention in particular may be a C5 to C12 carboxylic acid.
  • the carboxylic acid for use with the compositions of the present invention is a Q to C 4 carboxylic acid.
  • suitable carboxylic acids include, but are not limited to, formic, acetic, propionic, butanoic, pentanoic, hexanoic, heptanoic, octanoic, nonanoic, decanoic, undecanoic, dodecanoic, as well as their branched isomers, lactic, maleic, ascorbic, citric, hydroxyacetic, neopentanoic, neoheptanoic, neodecanoic, oxalic, malonic, succinic, glutaric, adipic, pimelic subric acid, and mixtures thereof.
  • the bleaching compositions of the present invention preferably include about 0.1 wt.
  • compositions of the present invention include about 1 wt- % to about 60 wt.- of a carboxylic acid. In yet other embodiments, the compositions of the present invention include about 20 wt. %, about 30 wt. %, or about 40 wt. % of a carboxylic acid. In further preferred embodiments, the compositions of the present invention include about 5 wt. % to about 10 wt. % of acetic acid. In other embodiments, the compositions of the present invention include about 5 wt. % to about 10 wt. % of octanoic acid.
  • the bleaching compositions of the present invention include a combination of octanoic acid and acetic acid.
  • the bleaching compositions of the present invention preferably include at least one peroxycarboxylic acid.
  • Peroxycarboxylic acids useful in the bleaching compositions include peroxyformic, peroxyacetic, peroxypropionic, peroxybutanoic, peroxypentanoic, peroxyhexanoic, peroxyheptanoic, peroxyoctanoic, peroxynonanoic, peroxydecanoic, peroxyundecanoic, peroxydodecanoic, or the peroxyacids of their branched chain isomers, peroxylactic, peroxymaleic, peroxy ascorbic, peroxyhydroxy acetic, peroxyoxalic, peroxymalonic, peroxysuccinic, peroxyglutaric, peroxyadipic, peroxypimelic and peroxysubric acid and mixtures thereof.
  • the bleaching compositions may utilize a combination of several different peroxycarboxylic acids.
  • the composition includes one or more Ci to C 4 peroxycarboxylic acids and one or more C5 to C 12 peroxycarboxylic acids.
  • the Ci to C 4 peroxycarboxylic acid is peroxyacetic acid and the C5 to C 12 acid is peroxyoctanoic acid.
  • the bleaching compositions include peroxyacetic acid.
  • Peroxyacetic (or peracetic) acid is a peroxycarboxylic acid having the formula: CH 3 COOOH.
  • peroxyacetic acid is a liquid having an acrid odor at higher concentrations and is freely soluble in water, alcohol, ether, and sulfuric acid.
  • Peroxyacetic acid can be prepared through any number of methods known to those of skill in the art including preparation from acetaldehyde and oxygen in the presence of cobalt acetate.
  • a solution of peroxyacetic acid can be obtained by combining acetic acid with hydrogen peroxide.
  • a 50% solution of peroxyacetic acid can be obtained by combining acetic anhydride, hydrogen peroxide and sulfuric acid.
  • the bleaching compositions include peroxyoctanoic acid, peroxynonanoic acid, or peroxyheptanoic acid.
  • the bleaching compositions include peroxyoctanoic acid.
  • Peroxyoctanoic (or peroctanoic) acid is a peroxycarboxylic acid having the formula, for example, of n-peroxyoctanoic acid: CH 3 (CH 2 ) 6 COOOH.
  • Peroxyoctanoic acid can be an acid with a straight chain alkyl moiety, an acid with a branched alkyl moiety, or a mixture thereof.
  • Peroxyoctanoic acid can be prepared through any number of methods known to those of skill in the art.
  • a solution of peroxyoctanoic acid can be obtained by combining octanoic acid and hydrogen peroxide and a hydrotrope, solvent or carrier.
  • the bleaching compositions include about 0.1 wt. % to about 90 wt. % of one or more peroxycarboxylic acids. In other embodiments, the bleaching compositions include about 1 wt. % to about 25 wt. % of one or more peroxycarboxylic acids. In yet other embodiments, the bleaching compositions include about 5 wt. % to about 10 wt. % of one or more peroxycarboxylic acids. In some embodiments, the bleaching compositions include about 1 wt. % to about 25 wt.
  • the bleaching compositions include about 0.1 wt. % to about 10 wt. % of peroxyoctanoic acid. In still yet other embodiments, the bleaching compositions include a mixture of about 5 wt. % peroxyacetic acid, and about 1.5 wt. % peroxyoctanoic acid.
  • the bleaching composition comprises a peracid selected from: a) peracids corresponding to general formula (VI) R 7 -C>2C-(CH2) p -CC>3H, wherein R 7 is hydrogen or an alkyl group containing 1 to 4 carbon atoms and p is an integer from 1 to 4, or salts thereof; b) phthalimidopercarboxylic acids (VII) wherein the percarboxylic acid contains 1 to 18 carbon atoms, or salts thereof; c) compounds corresponding to formula (VIII) R 8 CC>3H, wherein R 8 is an alkyl or alkenyl group containing 1 to 18 carbon atoms.
  • a peracids corresponding to general formula (VI) R 7 -C>2C-(CH2) p -CC>3H, wherein R 7 is hydrogen or an alkyl group containing 1 to 4 carbon atoms and p is an integer from 1 to 4, or salts thereof; b) phthalimidopercar
  • the bleaching composition comprises a peracid selected from: a) peracids corresponding to general formula (VI) R 7 C>2C-(CH2) p -CC>3H, wherein R 7 hydrogen or methyl group and p is an integer from 1 to 4, or salts thereof;
  • the peracid is selected from peracetic acid, perpropionic acid, peroctanoic acid, phthalimidoperhexanoic acid, phthalimidoperoctanoic acid, persuccinic acid, persuccinic acid monomethyl ester, perglutaric acid, perglutaric acid monomethyl ester, peradipic acid, peradipic acid monomethyl ester, persuccinic acid, and persuccinic acid monomethyl ester.
  • the bleaching composition comprises 1 to 30 wt. % of peracid.
  • the bleaching composition additionally contains 0.01 to 35 wt. % of hydrogen peroxide. Still further preferred, the bleaching composition comprises at least a mixture of hydrogen peroxide, peracid and the corresponding acid. Most preferred, the bleaching composition comprises at least hydrogen peroxide, peroxyacetic acid and acetic acid.
  • the liquid detergent concentrate composition according to the invention is used for washing textiles.
  • the method for washing textiles comprises providing the liquid detergent concentrate composition, diluting the liquid detergent concentrate composition to a stable aqueous use solution in a concentration of 0.5 to 25 wt. %, or about 1 to 10 wt. % based on the whole use solutions, optionally adding a bleaching composition to the liquid detergent concentrate composition or to the use solution, and washing the textiles in an institutional or household washing machine in the use solution.
  • liquid detergent concentrate composition of the invention and method for washing textiles with the composition is further described in the following examples which are mean to exemplify the present invention without restricting its scope.
  • test textiles were washed either 5 or 25 times at 60°C in the presence of a work wear soil suspension.
  • the test detergent emulsion composition was dosed at 5g/l together with a suitable bleaching agent, such as peracetic acid at a level of 0.7ml/l, and a source of alkalinity to adjust the pH to 10.
  • the soil suspension was composed of a mixture of motor oil, starch, protein and pigments.
  • the soil suspension, the bleaching agent and the test detergent emulsion composition were dosed via the in-rinsing chamber of an industrial, programmable wash machine (12.5kg wash load capacity).
  • test textile samples were three test fabrics commercially available from WFK: 100% pure (natural) cotton; and 50/50 and 65/35 cotton/polyester; in addition, 100% cotton towels from two different suppliers (Dyckhoff and Floringo) were used. Following the final wash, the test textiles were dried and the whiteness degree of the test textiles was measured using a spectrophotometer from Konica-Minolta.
  • Test samples were placed in 100 ml glass jars and placed in 5°C and 40°C storage chambers as well as on a shelf at room temperature (RT). After one week and on every subsequent week thereafter, until the conclusion of testing (after 12 weeks) the height of the separated layer was measured (in millimeters) from the bottom of each of the glass jars. This is an effective measure of phase stability because separation takes place at the bottom of the samples. To provide a relative measure of the differences in the separation observed both from sample to sample, and over time for any given sample, the height of the separated layer was divided by the total height of the sample to obtain a percent separation.
  • Freeze/thaw stability of test samples was measures by placing test samples in 100ml glass jars which were placed in a 40°C storage chamber for 24 hours and thereafter in a -5°C storage chamber, again for 24 hours. This cycle was repeated twice to provide a total of 3 freeze / thaw cycles. After each cycle, the samples were checked visually for separation and consistency.
  • Sample Manufacturing Method All samples have been prepared in the following way: the ingredients are added step-by- step and mixed together using a standard liquid mixing device to provide a test sample.
  • the stabilizing agent, Carbopol was pre-dispersed in one of the nonionic surfactants.
  • the premix was added to a mixture of the remaining ingredients as the final step.
  • the so- completed mixture was then agitated for 30 minutes followed by shearing with a high shear mill.
  • Any suitable commercially available equipment may be utilised for the agitation and shear milling steps, such as for example a High Shear Mill from IKA with 3 sets of generators, and use at a shear rate of about 3000rpm.
  • Example 1 Example Compositions and Comparative Test Compositions The improved cleaning performance of liquid detergent concentrate compositions in accordance with the invention [Compositions A and B] was demonstrated versus a baseline composition [C] and comparator test text compositions [D and E]. The relative levels of the components in compositions A, B, C, D and E in parts per hundred of each composition (wt. ) are shown in Table 1. TABLE 1
  • Tetogen 1 -Decanamine Surfactant 2.00 2.00 2.00 2.00 s DO N,Ndimethyl-,N- oxide
  • Dequest 2066 contains 32% active DTPMP.
  • the molecular weight of DTPMP is 727 and P is 31.
  • the molecule contains 5 P atoms.
  • To calculate the percentage P content in compositions A, B, C and D, (5*31)7727 * 0.32 * 6% 0.41%.
  • the objective of the secondary wash test is two-fold. It evaluates the both the cleaning performance of a composition, as measured by the degree of whiteness of a textile washed therewith, and also the substrate compatibility of the composition, as a composite of the chemical damage to the textile, the ash content of the textile and the tensile strength of the textile before and after the test.
  • test compositions were dosed with bleach (as detailed in the test methodology hereinbefore).
  • Table 4 illustrates storage stability data after storage of Composition A-E for 6 weeks at various temperatures. The data confirms the improved stability of compositions A and B when compared to Compositions C, D or E.
  • Table 5 illustrates freeze/thaw stability data for Composition A-E for 3 freeze/thaw cycles. Except for Composition D all samples are freeze/thaw stable. TABLE 5

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BR112021014315A2 (pt) 2019-01-22 2021-09-21 Ecolab Usa Inc. Composição de detergente líquido, e, métodos de lavagem de têxteis e de dispensa de uma composição de detergente líquido para lavar têxteis
WO2024100226A1 (en) * 2022-11-11 2024-05-16 Nouryon Chemicals International B.V. Cleaning composition

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL222100A (de) * 1956-11-02
US4886615A (en) * 1985-08-05 1989-12-12 Colgate-Palmolive Company Hydroxy polycarboxylic acid built non-aqueous liquid cleaning composition and method for use, and package therefor
IN165978B (de) * 1985-08-20 1990-02-17 Colgate Palmolive Co
US4797225A (en) * 1986-09-08 1989-01-10 Colgate-Palmolive Company Nonaqueous liquid nonionic laundry detergent composition containing an alkali metal dithionite or sulfite reduction bleaching agent and method of use
US6242406B1 (en) * 1997-10-10 2001-06-05 The Procter & Gamble Company Mid-chain branched surfactants with cellulose derivatives
GB0428202D0 (en) * 2004-12-23 2005-01-26 Fabric Care Res Ass Ltd A method of disinfecting textile articles during laundering and a laundry preparation for use in said method
WO2007101470A1 (en) * 2006-03-06 2007-09-13 Ecolab Inc. Liquid membrane-compatible detergent composition
ES2658650T3 (es) * 2010-10-08 2018-03-12 Ecolab Usa Inc. Composición detergente de lavandería para lavado y desinfección a baja temperatura
US9752109B2 (en) * 2013-03-25 2017-09-05 Ecolab Usa Inc. Liquid detergent composition

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WO2016081132A1 (en) 2016-05-26
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EP3221437A4 (de) 2018-06-20

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