WO2020052743A1 - Phase stable and low foaming aqueous detergent compositions having a long time enzyme activity - Google Patents

Phase stable and low foaming aqueous detergent compositions having a long time enzyme activity Download PDF

Info

Publication number
WO2020052743A1
WO2020052743A1 PCT/EP2018/074488 EP2018074488W WO2020052743A1 WO 2020052743 A1 WO2020052743 A1 WO 2020052743A1 EP 2018074488 W EP2018074488 W EP 2018074488W WO 2020052743 A1 WO2020052743 A1 WO 2020052743A1
Authority
WO
WIPO (PCT)
Prior art keywords
detergent composition
alkyl
aqueous detergent
ether
preferred
Prior art date
Application number
PCT/EP2018/074488
Other languages
French (fr)
Inventor
Isabelle FRIEDRICH
Silke Denzin
Sabine Swoboda
Nadine Göhring
Peter Forth
Original Assignee
Ecolab Usa Inc.
Popovic, Zoran
Jaeger, Stefan
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., Popovic, Zoran, Jaeger, Stefan filed Critical Ecolab Usa Inc.
Priority to EP18778381.6A priority Critical patent/EP3850068A1/en
Priority to PCT/EP2018/074488 priority patent/WO2020052743A1/en
Publication of WO2020052743A1 publication Critical patent/WO2020052743A1/en

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
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • 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
    • 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
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2044—Dihydric alcohols linear
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only
    • 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
    • C11D3/43—Solvents
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines

Definitions

  • the present invention relates to aqueous cleaning compositions that are phase stable and having a long time enzyme activity, to a method of manufacture and the use thereof
  • soils such as carbohydrate, proteins, blood and water hardness soils, food oil soils, fat soils and other soils.
  • soils can arise from the manufacture of both liquid and solid residences/contaminants.
  • Grease soils and residue soils such as proteins, fats, blood and oils, especially when dried, can be hard to remove soil.
  • carbohydrate soils such as cellulosic, monosaccharides, disaccharides, oligosaccharides, starches, gums and other complex materials, when dried, can form tough, hard to remove soils, particularly when combined with other soil components such as proteins, blood, fats, oils, minerals, and others. The removal of such soils and residues, can be a significant problem.
  • Clean out of place systems (COP) cleaning techniques are a specific cleaning regimen adapted for removing soils from exterior surfaces of a wide variety of parts, such as ceramic surfaces, metallic surfaces, walls, wash tanks, soaking vessels, mop buckets, holding tanks, scrub sinks, vehicle parts washers, non-continuous batch washers and systems, ceilings, external parts of production machinery and the like.
  • parts such as ceramic surfaces, metallic surfaces, walls, wash tanks, soaking vessels, mop buckets, holding tanks, scrub sinks, vehicle parts washers, non-continuous batch washers and systems, ceilings, external parts of production machinery and the like.
  • Often clean out of place methods can involve a first rinse, the application of the cleaning solutions, and a second rinse with potable water followed by resumed operations.
  • the process can also include any other contacting step in which a rinse, acidic or basic functional fluid, solvent or other cleaning component such as hot water, cold water, etc. can be contacted with the equipment at any step during the process.
  • a rinse, acidic or basic functional fluid, solvent or other cleaning component such as hot water, cold water, etc.
  • Conventional clean in place as well as clean out of place methods require high temperatures, up to about 80° C. In production rooms, the elevated water temperature currently used for that kind of cleaning processes is in the range of about 40° C to about 60° C.
  • Conventional clean out of place techniques (COP) thus require the consumption of large amounts of energy.
  • manual or automatic instrument reprocessing requires a specific cleaning regimen and cleaning compositions adapted for removing soils from surfaces.
  • Cleaning processes at elevated temperatures in the range of about 40° C to about 60° C requires cleaning composition that are not corrosive to the metallic surface to be cleaned as well as doesn’t affect or being aggressive to plastic parts, like plastic seals.
  • the object addressed by the present invention is to provide an aqueous detergent composition for removing soils such as proteins, fats and blood having no phase separation at elevated temperatures, an increased metal and plastic material compatibility, that can be used for example in removing soil from a surface to be cleaned, preferably in a clean-out-of-place systems (COP) or in a clean-in-place system (CIP) or in manual or automatic instrument reprocessing, especially for cleaning endoscopes.
  • COP clean-out-of-place systems
  • CIP clean-in-place system
  • an aqueous detergent composition for removing of soil at elevated temperatures from a surface to be cleaned is provided.
  • an aqueous detergent composition comprising:
  • wt.-% of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
  • aqueous detergent composition can be used for removal of soil at elevated temperatures over an extended time period, while still providing excellent material compatibility properties.
  • the aqueous detergent composition is low- foaming.
  • the aqueous detergent composition doesn’t show a phase separation at elevated temperatures.
  • the cleaning cycle in for example an automated cleaning apparatus for devices such as endoscopes takes about 20 minutes to 1 hour and the cleaning temperatures are often between room temperature and 45° C
  • the canister of the enzyme containing cleaning composition of the present invention is often integrated in or arranged near by the cleaning apparatus thus subjected to heating temperatures of the water heating system of about > 50° C to about ⁇ 90° C for a continues time period until the canister is emptied, which can takes up to three weeks. Up to 90° C can be reached in the cleaning apparatus at the disinfection step.
  • Protease is stable in a water solution at temperatures up to about 43° C. Increasing the temperature of a protease-water solution to about 45° C shows a decrease of protease activity in a protease-water solution. It was surprisingly found that the decrease of protease activity at temperatures at about 45° C and above, such as > 50° C to about ⁇ 60 °C is significant less compared with a protease water-solution.
  • the present aqueous detergent composition allows an effective cleaning and removing soil from hard and/or soft surfaces at elevated temperature of about > 45° C to about ⁇ 60 °C without significant loss of the protease activity. The further advantage is that at temperatures of about > 45° C to about ⁇ 60 °C bacteria are destroyed.
  • milder cleaning and soil removal components can be selected due to a temperature induced higher activity and aggressive cleaning components can be avoided, while ensuring surprisingly the protease activity.
  • protease activity of the aqueous low-foaming detergent composition shows a significant increased life span compared with the same protease in water.
  • the present aqueous detergent composition is an improvement for cleaning and/or removing soil from for example endoscopes having metal and plastic sensitive parts compared with the alkaline cleaners typically used.
  • compositions of the present invention provide for reduced energy consumption, since it has an increased cleaning performance at low cleaning temperatures.
  • aqueous detergent composition that can be used in automated cleaning devices, like automated cleaning devices for medical instruments, in particular endoscopes.
  • the aqueous detergent composition is active at a low components concentration thus provides a reduced chemical consumption.
  • the aqueous detergent composition can be present in form of a concentrated solution.
  • the concentrated solution has advantages in transporting and storing.
  • the concentrated solution can be diluted, for example prior use, by admixing a solvent, preferably water.
  • the aqueous detergent composition can be free of at least one additive selected from the group of dye, color transfer inhibitor, anti-redeposition agents, optical brighteners, builder, oil and water repellant agents, color fastness agents, starch/sizing agents, fabric softening agents, anti-microbials, fungicides, UV absorbers, fragrances and/or mixtures thereof.
  • the present invention relates to aqueous detergent compositions and methods for removing soils from surfaces to be cleaned.
  • Surfaces to be cleaned are hard and/or soft surfaces.
  • the composition of the invention is applied in a clean in place process (CIP) and/or in a clean out of place process (COP).
  • CIP clean in place process
  • COP clean out of place process
  • compositions of the invention may be manually applied to the surface to be cleaned.
  • compositions of the invention can be used in hospital cleaning, cleaning of medical devices, for example chirurgical instruments, the food processing industry, such as meat processing industry, for cleaning purposes.
  • compositions of the invention may be used in manual or automatic instrument reprocessing, preferably medical instruments.
  • compositions of the invention may be used for manually or automatically cleaning of chirurgical instruments, in particular endoscopes.
  • the aqueous detergent composition can be a more component composition that can be mixed in situ at the place of use.
  • the aqueous detergent composition allows for the use of reduced levels of chemistry, because the aqueous detergent composition of the invention has a remarkable increased cleaning efficiency that allows the use of a lower concentrated detergent composition.
  • the methods of the present invention provide for reduced energy consumption, e.g., lower cleaning temperatures, and reduced chemical consumption.
  • by weight refers to the total weight of the composition. For example, if a composition has a total weight of 100 grams and comprises 40% (by weight) of an alcohol, the composition may comprise 40 grams of alcohol.
  • the total weight percent amount of all components, substances or agents of a composition are selected such that it does not exceed 100 wt.-%.
  • the weight. -% of the components are based on the total weight of the concentrated aqueous detergent composition, and the weight. -% of all components of the aqueous detergent composition are select so that it does not exceed 100 wt.-%.
  • the term refers to an inner and/or outer surface that can be contacted by the aqueous detergent composition at a cleaning and removal of soil process.
  • the term “bulsurface“ refers for example to a surface, such as outer and/or inner surface, of articles, such as a medical instrument, a healthcare setting, a tool, a machine, equipment, a structure, a building, or the like that is employed as part of a food processing, preparation, or storage activity.
  • healthcare settings include hospitals, doctor's offices and long term care facilities.
  • food processing surfaces include surfaces of food processing or preparation equipment, e.g., slicing, canning, or transport equipment, including flumes, of food processing wares, e.g., utensils, dishware, wash ware, and bar glasses), and of floors, walls, or fixtures of structures in which food processing occurs.
  • Food processing surfaces are found and employed in milking machines, food anti-spoilage air circulation systems, aseptic packaging sanitizing, food refrigeration and cooler cleaners and sanitizers, ware washing sanitizing, blancher cleaning and sanitizing, food packaging materials, cutting board additives, third-sink sanitizing, beverage chillers and warmers, meat chilling or scalding waters, auto dish sanitizers, sanitizing gels, cooling towers, food processing antimicrobial garment sprays, and non-to-low-aqueous food preparation lubricants, oils, and rinse additives.
  • the term refers to items such as eating and cooking utensils, dishes, and other hard surfaces such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, and floors.
  • the Ci- CValkyl of the ether can be butyl.
  • the term whabout“ refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients used to make the compositions or carry out the methods; and the like.
  • any numerical value recited herein includes all values from the lower value to the upper value, i.e., all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application.
  • concentration range is stated as 1% to 50%, it is intended that values such as 2% to 40%, 10% to 30%, or 1% to 3%, etc., are expressly enumerated in this specification. These are only examples of what is specifically intended.
  • compositions of the invention including the foam can have an alkaline pH, for example a pH of about 8.5 to about 12.
  • the aqueous detergent composition has a pH in the range of about > 8.5 and ⁇ 12, preferably of about > 9 and ⁇ 11.5, further preferred of about > 9.5 and ⁇ 11 and more preferred about 10 ⁇ 0.3.
  • Mw refers to an average molecular weight
  • compositions of the present invention can include, or consist essentially of, or consist of the steps, and ingredients of the present invention as well as other ingredients described herein.
  • the methods and compositions of the present invention may be applied to equipment generally cleaned using clean in place cleaning procedures.
  • equipment include evaporators, heat exchangers, including tube-in-tube exchangers, direct steam injection, and plate-in-frame exchangers, heating coils, including steam, flame or heat transfer fluid heated, re-crystallizers, pan crystallizers, spray dryers, drum dryers, and tanks.
  • the methods and compositions of the present invention may also be used to remove other soils that are not easily removed using conventional cleaning techniques.
  • Soil types suited to cleaning with the methods of the present invention include, but are not limited to, starch, cellulosic fiber, protein, simple carbohydrates and combinations of any of these soil types with mineral complexes.
  • Examples of specific food soils that are effectively removed using the methods of the present invention include, but are not limited to, meat residues, blood residues, protein residues, vegetable and fruit juices, brewing and fermentation residues, soils generated in sugar beet and cane processing, and soils generated in condiment and sauce manufacture, e.g., ketchup, tomato sauce, barbeque sauce.
  • compositions of the present invention may be preferably used in any application where body fluids, proteins, fats and/or carbohydrates, need to be removed.
  • Exemplary industries in which the methods and compositions of the present invention can be used include, but are not limited to: hospitals, such as for the cleaning of medical / chirurgical instruments, the food and beverage industry, e.g., the meat processing industry; dairy, cheese, sugar, and brewery industries; oil processing industry; industrial agriculture and ethanol processing; and the pharmaceutical manufacturing industry.
  • CIP as well as COP processing is generally well-known.
  • the process includes applying a composition of the invention onto the surface to be cleaned and/or soil removed.
  • the process to remove a soil according to the invention can include an alkaline wash.
  • a process to remove a soil can include a fresh water rinse and an alkaline wash or a fresh water rinse, an alkaline wash and a fresh water rinse.
  • Another embodiment of a process of the invention to remove soil can comprise the cleaning step: an alkaline wash, an acid solution wash, and then a fresh water rinse.
  • the alkaline wash softens the soils and removes the organic alkaline soluble soils.
  • the subsequent acid solution removes mineral soils left behind by the alkaline cleaning step.
  • the strength of the alkaline and acid solutions and the duration of the cleaning steps are typically dependent on the durability of the soil.
  • the water rinse removes any residual solution and soils, and cleans the surface prior to the equipment being returned on-line.
  • the process to remove a soil as described above includes at least one alkaline wash of the aqueous cleaning composition according to the invention.
  • the methods and compositions of the present invention can be used for enhanced soil removal at ambient temperatures, e.g., about > 20° C to ⁇ 65° C, preferably at about 40° C to about 60° C or at about 45° C to about 55° C or about 45° C to about 50° C.
  • the present invention also provides for a reduction in the amount of chemistry and water consumed during the cleaning process.
  • the present invention provides both energy and water savings, while achieving effective soil removal.
  • At least one surfactant or a surfactant mixture of an alkyl alkoxylate surfactant and/or an alkyl alkoxylate alkyl ether can be used in the aqueous detergent composition and methods of the present invention.
  • Ci-CValkyl of the ether can be butyl.
  • the Ci-CValkyl of the ether can be butyl.
  • the Ci-CValkyl of the ether can be butyl.
  • the Ci-CValkyl of the ether can be butyl.
  • the Ci-CValkyl of the ether can be butyl.
  • EO Cs-Cis-alkyl alkoxylate
  • Ci-CValkyl of the ether can be butyl.
  • EO Cs-Cis-alkyl alkoxylate
  • EO C i-Cs-alkyl ether
  • n 4 to 12.
  • the C i-Cs-alkyl of the ether can be butyl.
  • EO ix-alkyl alkoxylate
  • EO EO
  • EO Cio-Ci 4 -alkyl alkoxylate
  • EO Cio-Ci 4 -alkyl alkoxylate
  • EO C10-C14- alkyl alkoxylate
  • the C 2 -C 5 -alkyl of the ether can be butyl.
  • the CVCValkyl of the ether can be butyl.
  • the CVCValkyl of the ether can be butyl.
  • the surfactant can be selected from the group comprising:
  • the surfactant can be selected from the group comprising: a) lauryl ethoxylates:
  • Genapol® O 050 oleyl(ethoxylate with 5 EO Cl 6/ 18 alcohol, linear, unsaturated
  • Emulsogen® LCN 407 C 11 alkyl ethoxylate with 40 EO C 11 alcohol, branched
  • Genapol® X 020 isotridecyl ethoxylate with 2 EO C13 alcohol
  • Genapol® X 050 isotridecyl ethoxylate with 5 EO C13 alcohol
  • branched Genapol® X 060 isotridecyl ethoxylate with 6 EO C13 alcohol
  • Genapol® X 065 isotridecyl ethoxylate with 6.5 EO C13 alcohol, branched
  • Genapol® X 080 isotridecyl ethoxylate with 8 EO C13 alcohol, branched
  • Genapol® X 089 isotridecyl ethoxylate with 8 EO C13 alcohol, branched
  • Genapol® X 090 isotridecyl ethoxylate with 9 EO C13 alcohol, branched
  • Genapol® X 150 isotridecyl ethoxylate with 15 EO C13 alcohol, branched
  • Genapol® X 158 isotridecyl ethoxylate with 15 EO C13 alcohol, branched
  • Genapol® X 307 isotridecyl ethoxylate with 30 EO C13 alcohol, branched
  • Genapol® X 407 isotridecyl ethoxylate with 40 EO C13 alcohol, branched
  • Genapol® 1879 isotridecyl ethoxylate with 15 EO C13 alcohol, branched
  • Genapol® 3214 isotridecyl ethoxylate with 25 EO C13 alcohol, branched
  • Genapol® ID 030 isodecyl ethoxylate with 3 EO C10 alcohol, branched
  • Genapol® ID 060 isodecyl ethoxylate with 6 EO C10 alcohol, branched
  • Genapol® ID 070 isodecyl ethoxylate with 7 EO C10 alcohol, branched
  • Genapol® EP 1022 isodecyl ethoxylate with 2 EO, 2PO C10 alcohol, branched i) oxo-process alcohol ethoxylates:
  • alkyl alkoxylate alkyl ether of C12/C14-10EO, n-butyl end-capped which is known as Genapol® BE 2410, can be most preferred. It has been surprisingly found that composition comprising alkyl alkoxylate alkyl ether of C12/C14-10EO, n-butyl end-capped shows the lowest foam formation compared with the other composition of the present invention.
  • the aqueous detergent composition may comprises in addition at least one further anionic surfactant and/or further non-ionic surfactant.
  • the additional surfactant chosen may be compatible with the surface to be cleaned.
  • the additional surfactant can be preferably a non-ionic surfactant. It can be preferred that the additional surfactant may be selected from the group comprising of linear alkyl benzene sulfonates, alcohol sulfonates, amine oxides, alkyl phenol ethoxylates, polyethylene glycol esters and mixtures thereof.
  • the level and degree of low- foaming under the conditions of use and in subsequent recovery of the composition may be a factor for selecting particular surfactants and mixtures of surfactants.
  • the nonionics and anionics may be used in combination.
  • the aqueous detergent composition is may be free of an C 8 to C 14 alkyl sulfate and/or 2-ethylhexyl sulfate. However, it can be even more preferred that the aqueous detergent composition is may be free of an anionic surfactant.
  • the amount of total surfactant in the aqueous detergent composition can be about > 0.1 wt.-% to about ⁇ 15 wt.-%.
  • Acceptable levels of surfactants include about > 0.5 wt.-% to about ⁇ 12 wt.-%, about > 1 wt.-% to about ⁇ 10 wt.-%, about > 3 wt.-% to about ⁇ 9 wt.-%, or about > 6 wt.-% to about ⁇ 8 wt.-%.
  • the amount of total surfactant of an alkyl alkoxylate surfactant and/or an alkyl alkoxylate alkyl ether in the aqueous detergent composition can be about > 0. 1 wt.-% to about ⁇ 15 wt.-%, preferably about > 0. 5 wt.-% to about ⁇ 12 wt.-%, further preferred about > 1 wt.-% to about ⁇ 10 wt.-% and in addition preferred about > 3 wt.-% to about ⁇ 9 wt.-% or preferably about > 6 wt.-% to about ⁇ 8 wt.-%.
  • compositions of the present invention include a source of alkalinity.
  • exemplary alkaline sources suitable for use with the present invention include, but are not limited to are, basic salts, amines, alkanol amines, carbonates, silicates, and mixtures thereof, preferably the source of alkalinity is selected from the group comprising sodium hydroxide, potassium hydroxide or a mixture thereof, most preferred the source of alkalinity can be triethanol amine.
  • the source of alkalinity is selected from the group comprising alkanol amines, sodium hydroxide, potassium hydroxide or a mixture thereof, most preferred is triethanol amine.
  • the aqueous detergent composition may comprise a sources of alkalinity wherein the sources of alkalinity include alkanol amines, and most preferred the sources of alkalinity is triethanol amine.
  • the amount of alkaline source present is dependent on a variety of factors including, for example, the type of surface to be cleaned, and the amount and type of soil present on the surface.
  • the amount of alkaline source present in an aqueous detergent composition can be about > 1 wt.-% to about ⁇ 15 wt.- %, preferably about > 3 wt.-% to about ⁇ 10 wt.-%, and further preferred about > 6 wt.-% to about ⁇ 8 wt.-%; wherein the source of alkalinity can preferably triethanol amine.
  • the amount of alkaline source present in an additional diluted aqueous detergent composition can be about > 0.001 wt.-% to about ⁇ 1 wt.-%, preferably about > 0.01 wt.-% to about ⁇ 0.5 wt.-%, and further preferred about > 0.02 wt.-% to about ⁇ 0.05 wt.-%; wherein the source of alkalinity can be preferably triethanol amine.
  • the“surfactants” of the aqueous detergent composition are not regarded as an alkaline source.
  • aqueous detergent composition can be free of an alkali hydroxide
  • the aqueous detergent composition comprises at least one organic solvent.
  • the organic solvent can be a C 2 to Cx alcohol.
  • the organic solvent can be preferably a mixture of at least two alcohols selected from the group of C 2 to Cx alcohols.
  • the C 2 to Cx alcohol of the organic solvent can be a polyol.
  • a preferred polyol can be C 2 -CY, -alkyl diol or C 2 -CY, -alkyl triol. Further preferred the polyol containing only carbon, hydrogen and oxygen atoms.
  • the C 2 -CY, -alkyl diol can be preferably selected from dihydroxypropane, 1 ,2- propanediol, l,3-propandiol, butanediol, l,2-butanediol, l,3-butanediol, l,4-butanediol, hexylene glycol, glycerol, 2-methyl-2,4-pentanediol.
  • Suitable glycols include, but are not limited to, ethylene glycol (monoethylene glycol or MEG), diethylene glycol (propylene glycol or butoxy diglycol or DEG), triethylene glycol (TEG), tetraethylene glycol (TETRA EG), propylene glycol, dipropylene glycol, hexylene glycol, or combinations thereof.
  • the C 2 -CY, -alkyl triol can be l,2,3-trihydroxypropane, also named glycerin.
  • the mixture of at least two alcohols may comprises: a) at least one C 2 -C 6 -alkyl diol, preferably dihydroxypropane;
  • the mixture of at least two alcohols may comprises: a) at least one C 2 -CY, -alkyl diol, preferably dihydroxypropane;
  • the mixture may has a ratio of a) to b) of 6: 1 to 2: 1, or 5: 1 to 3: 1, or 4: 1 to 3.5 : 1.
  • the amount of the organic solvent may be present in the aqueous detergent composition from about > 1 wt.-% to about ⁇ 30 wt.-%, preferably about > 1.5 wt.-% to about ⁇ 4.5 wt.-%, further preferred about > 2 wt.-% to about ⁇ 4 wt.-%, and more preferred about > 2.5 wt.-% to about ⁇ 3.5 wt.-%.
  • the amount of the organic solvent may be present in the aqueous detergent composition from about > 1 wt.-% to about ⁇ 30 wt.-%, preferably about > 1.5 wt- % to about ⁇ 25 wt.-%, further preferred about > 2 wt.-% to about ⁇ 20 wt.-%, and more preferred about > 2.5 wt.-% to about ⁇ 15 wt.-%; or from about > 1 wt.-% to about ⁇ 10 wt- %, or from about > 1 wt.-% to about ⁇ 5 wt.-%, or from about > 2 wt.-% to about ⁇ 5 wt.-%.
  • the amount of the alcohol may be present in a diluted aqueous detergent composition, from about > 0.001 wt.-% to about ⁇ 0.5 wt.-%, preferably about > 0.006 wt.-% to about ⁇ 0.2 wt.-%, and more preferred about > 0.01 wt.-% to about ⁇ 0.1 wt.-%.
  • the amount of the C 2 -Ce- alkyl diol may be present in a concentrated aqueous detergent composition, from about > 1 wt.-% to about ⁇ 5 wt.-%, preferably about > 1.5 wt.-% to about ⁇ 4.5 wt.-%, further preferred about > 2 wt.-% to about ⁇ 4 wt.-%, and more preferred about > 2.5 wt.-% to about ⁇ 3.5 wt.- %.
  • the amount of the C 2 -Ce- alkyl triol may be present in a concentrated aqueous detergent composition, from about > 1 wt.-% to about ⁇ 5 wt.-%, preferably about > 1.5 wt.-% to about ⁇ 4.5 wt.-%, further preferred about > 2 wt.-% to about ⁇ 4 wt.-%, and more preferred about > 2.5 wt.-% to about ⁇ 3.5 wt.- %.
  • hydrotropes Solubilizing intermediaries called hydrotropes.
  • a hydrotrope is a compound that solubilizes hydrophobic compounds in aqueous solutions.
  • hydrotropes consist of a hydrophilic part and a hydrophobic part (like surfactants) but the hydrophobic part is generally too small to cause spontaneous self-aggregation. Hydrotropes may be present in the aqueous detergent composition.
  • Hydrotropes that can be suitable used are selected from the group comprising aromatic hydrocarbon sulfonate, preferably xylene sulfonate, toluene sulfonate, or cumene sulfonate; or n-octane sulfonate; or their sodium-, potassium- or ammonium salts or as salts of organic ammonium bases.
  • the hydrotrope may be selected from the group comprising of a xylene sulfonate, toluene sulfonate, or cumene sulfonate, n-octane sulfonate, and/or acids thereof and also more preferred cumene sulfonate.
  • Na-cumolsulfonate, linear alkylbenzene sulfonates (LAS) and/or xylene sulfonate, cumolsulfonate may be suitable to use as hydrotrope and having an improved wetting effect.
  • the aqueous detergent composition may comprise at least one hydrotrope that is a cumene sulfonate.
  • the aqueous detergent composition preferably the concentrated aqueous detergent composition, may comprise in addition a hydrotrope, preferably
  • cumolsulfonate or the acid thereof in the range of about > 0 wt.-% to about ⁇ 10 wt.-%, preferably about > 1 wt.-% to about ⁇ 5 wt.-% and more preferred about > 2 wt.-% to about ⁇ 4 wt.-%, by weight of the total aqueous detergent composition.
  • the aqueous detergent composition preferably a diluted aqueous detergent composition may comprise a hydrotrope, preferably cumolsulfonate or the acid thereof, in the range of about > 0 wt.-% to about ⁇ 0.1 wt.-%, preferably about > 0 wt.-% to about ⁇ 0.3 wt.-%, further preferred > 0.03 wt.-% to about ⁇ 0.15 wt.-%, and more preferred about > 0.06 wt.-% to about ⁇ 0.12 wt.-%, by weight of the total aqueous detergent composition.
  • a hydrotrope preferably cumolsulfonate or the acid thereof
  • hydrotrope can present in the form of an acid or salt thereof, depending on the pH of the aqueous detergent composition.
  • aqueous detergent composition can be free of a hydrotrope.
  • the aqueous detergent composition can be free of a hydrotrope. According to one aspect the aqueous detergent composition can be free of a hydrotrope, except cumene sulfonate.
  • the aqueous detergent composition may preferably exclude a polymeric
  • the aqueous detergent composition may include at least one polymeric polycarboxylate.
  • the polymeric polycarboxylates suitable for use include those having a pendant carboxylate (— C0 2 ) groups and include, for example, polyacrylic acid, maleic/olefin copolymer, acrylic/maleic copolymer, polymethacrylic acid, acrylic acid- methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile -methacrylonitrile copolymers, and the like.
  • copolymeric polycarboxylates are particularly those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which comprise about 50 wt.- % to about 90 wt.- % acrylic acid and about 50 wt.- % to about 10 wt.- % maleic acid, have proven to be particularly suitable.
  • More preferred suitable polycarboxylates are the polyacrylates, which preferably have a molecular weight of 1,000 to 50,000 g/mol and preferably about 2,000 to 10,000 g/mol.
  • the aqueous detergent composition may comprise a polymeric polycarboxylate, preferably a polyacrylate having a molecular weight of about 500 Mw to about 50000 Mw, preferably about 1000 Mw to about 20000 Mw, in addition preferred about 3000 Mw to about 10000 Mw and more preferred about 4000 Mw to about 6000 Mw, wherein the molecular weight of the polymeric polycarboxylate is based on a totally neutralized sodium polymeric polycarboxylate.
  • a polymeric polycarboxylate preferably a polyacrylate having a molecular weight of about 500 Mw to about 50000 Mw, preferably about 1000 Mw to about 20000 Mw, in addition preferred about 3000 Mw to about 10000 Mw and more preferred about 4000 Mw to about 6000 Mw, wherein the molecular weight of the polymeric polycarboxylate is based on a totally neutralized sodium polymeric polycarboxylate.
  • More preferred is a polymeric polycarboxylate that is a polyacrylate.
  • an aqueous detergent composition may comprise the polymeric polycarboxylate, preferably polyacrylate, in an amount of about > 0 wt.-% to about ⁇ 5 wt.-%, preferably about > 0.5 wt.- % to about ⁇ 2 wt.-% and more preferred about > 0.7 wt.-% to about ⁇ 1 wt.-% of a polycarboxylate, preferably polyacrylate of a polymeric polycarboxylate, based on the total weight amount of the aqueous detergent composition.
  • an aqueous detergent composition may comprise the polymeric polycarboxylate, preferably polyacrylate, in an amount of about > 0 wt.-% to about ⁇ 5 wt.-%, preferably about > 0.5 wt.- % to about ⁇ 2 wt.-% and more preferred about > 0.7 wt.-% to about ⁇ 1 wt.-% of a polycarboxylate, preferably polyacrylate having about 4000 Mw to about 6000 Mw, based on the total weight amount of the aqueous detergent composition.
  • an aqueous detergent composition may comprise the polymeric polycarboxylate, preferably polyacrylate, in an amount of about > 0 wt.-% to about ⁇ 0.15 wt.-%, preferably about > 0.015 wt.-% to about ⁇ 0.06 wt.-% and more preferred about > 0.021 wt.-% to about ⁇ 0.03 wt.-% of a polycarboxylate, preferably polyacrylate of a polymeric polycarboxylate, based on the total weight amount of the aqueous detergent composition.
  • an aqueous detergent composition may comprise the polymeric polycarboxylate, preferably polyacrylate, in an amount of about > 0 wt.-% to about ⁇ 0.15 wt.-%, preferably about > 0.015 wt.-% to about ⁇ 0.06 wt.-% and more preferred about > 0.021 wt.-% to about ⁇ 0.03 wt.-% of a polycarboxylate, preferably polyacrylate having about 4000 Mw to about 6000 Mw, based on the total weight amount of the aqueous detergent composition.
  • preferred representatives of this group of polymeric polycarboxylate are the short-chain polyacrylates, which have average molecular weight (Mw), based on free acids, of 2,000 g/mol to 10,000 g/mol and, more particularly, 4,000 g/mol to 6,000 g/mol.
  • Mw average molecular weight
  • aqueous detergent composition can be free of a polymeric polycarboxylate.
  • the aqueous detergent composition can be free of a polymeric polycarboxylate, except a polyacrylate.
  • Water is added add. 100 wt.-% to the aqueous detergent composition.
  • the water content, of the aqueous detergent composition is simply determined by subtracting the weight- % amounts of all the other components, based on the total weight of the aqueous detergent composition, except the solvent, from 100 wt. %.
  • an aqueous detergent composition comprises water in an amount of about > 30 wt.-%, preferably about > 50 wt.-%, further preferred about > 60 wt.-%, and in addition preferred about > 90 wt.-%, based on the total weight amount of the aqueous detergent composition.
  • an aqueous detergent composition comprises water in an amount of about > 30 wt.-% and ⁇ 95 wt.-%, preferably about > 50 wt.-% and ⁇ 95 wt.-%, and further preferred about > 60 wt.-% to about ⁇ 90 wt.-%, based on the total weight amount of the aqueous detergent composition.
  • an aqueous detergent composition may comprise water in an amount of about > 98 wt.-%, preferably about > 99 wt.-% and further preferred about > 99.9 wt.-%, based on the total weight amount of the aqueous detergent composition.
  • a diluted aqueous detergent composition is obtainable by diluting a concentrated liquid composition with a water, in a ratio of an aqueous detergent composition, preferably a concentrated liquid composition, to water, of about 1 : 10 to 1 : 1000, preferably of about 1 : 50 to 1 : 500, in particular of about 1 : 100 to 1 : 250, and also preferred of about 1 : 30 to 1 : 50.
  • the aqueous detergent composition may preferably exclude a chelating agent.
  • the aqueous detergent composition may comprises a chelating agent.
  • the chelating agent can be selected from the group of sodium gluconate, pentasodium salt of
  • diethylenetriamine pentaacetic acid, sodium glucoheptonate salts of ethylene diamine tetraacetic acid, salts of ethylene diamine tetraacetic acid, salts of hydroxyethyl ethylene diamine triacetic acid, salts of hydroxyethyl ethylene diamine triacetic acid, salts of nitrilotriacetic acid, salts of nitrilotriacetic acid, diethanolglycine sodium salt,
  • ethanoldiglycine disodium salt salts of hydroxymonocarboxylic acid compounds, salts of hydroxydicarboxylic acid compounds, salts of amine containing carboxylic acids, terasodium N,N-bis(carboxylatomethyl)-L-glutamate (GDLA) and mixtures thereof.
  • At least one chelating agent that exhibits soil removal properties when used at a pH of at least about 11 to about 14 and more preferred at a pH in the range of about 12 to about 13.5.
  • the chelating agent is provided for tying up metals in the soil to assist in cleaning and detergency.
  • the chelating agent can be provided as part of the solid alkaline composition.
  • Exemplary chelating agent that exhibit soil removal properties at a pH of greater than about 12.0 to about 13.5 that can be used according to the invention include sodium gluconate, pentasodium salt of diethylenetriamine pentaacetic acid (available under the name Versenex 80), sodium glucoheptonate, ethylene diamine tetraacetic acid (EDTA), salts of ethylene diamine tetraacetic acid, hydroxyethyl ethylene diamine triacetic acid (HEDTA), salts of hydroxyethyl ethylene diamine triacetic acid, nitrilotriacetic acid (NT A), salts of nitrilotriacetic acid, diethanolglycine sodium salt (DEG), ethanoldiglycine disodium salt (EDG), tetrasodium N,N-bis(carboxylatomethyl)-L-glutamate (GLDA), methyl glycine diacetic acid (MGDA) and mixtures thereof.
  • EDTA ethylene diamine
  • Exemplary salts of ethylene diamine tetraacetic acid include disodium salts, tetrasodium salts, diammonium salts, and trisodium salts.
  • An exemplary salt of hydroxyethyl ethylene diamine triacetic acid is the trisodium salt.
  • the chelating agent can include mixtures of different chelating agent agents.
  • an aqueous detergent composition may comprise a chelating agent, preferably a gluconate, in an amount of about > 0.1 wt.-% to about ⁇ 3 wt.-%, preferably about > 0.5 wt.-% to about ⁇ 2 wt.-%, further preferred about > 1.0 wt.-% to about ⁇ 1.7 wt.-% and more preferred about >
  • a chelating agent preferably a gluconate
  • an aqueous detergent composition may comprise a chelating agent, preferably a gluconate, in an amount of about > 0 wt.-% to about ⁇ 0.1 wt.-%, preferably about > 0.01 wt.-% to about ⁇ 0.05 wt.-%, further preferred about > 0.02 wt.-% to about ⁇ 0.04 wt.-% and more preferred about > 0.0375 wt.-% to about ⁇ 0.0395 wt.-%, based on the total weight amount of the aqueous detergent composition.
  • a chelating agent preferably a gluconate
  • an aqueous detergent composition may comprise a tetrasodium N,N-bis(carboxylatomethyl)-L- glutamate (GLDA), in an amount of about > 0 wt.-% to about ⁇ 5 wt.-%, preferably about > 0.5 wt.-% to about ⁇ 2 wt.-% and more preferred about > 0.7 wt.-% to about ⁇ 1 wt.-%, based on the total weight amount of the aqueous detergent composition.
  • GLDA tetrasodium N,N-bis(carboxylatomethyl)-L- glutamate
  • an aqueous detergent composition may comprise a tetrasodium N,N-bis(carboxylatomethyl)-L-glutamate (GLDA), in an amount of about > 0 wt.-% to about ⁇ 0.2 wt.-%, preferably about > 0.005 wt.- % to about ⁇ 0.05 wt.-%, further preferred about > 0.0228 wt.-% to about ⁇ 0.0232 wt.-%, based on the total weight amount of the aqueous detergent composition.
  • GLDA tetrasodium N,N-bis(carboxylatomethyl)-L-glutamate
  • an aqueous detergent composition may comprise a methyl glycine diacetic acid (MGDA), in an amount of about > 0 wt.-% to about ⁇ 5 wt.-%, preferably about > 0.5 wt.-% to about ⁇ 2 wt- % and more preferred about > 0.7 wt.-% to about ⁇ 1 wt.-%, based on the total weight amount of the aqueous detergent composition.
  • MGDA methyl glycine diacetic acid
  • an aqueous detergent composition may comprise a methyl glycine diacetic acid (MGDA), in an amount of about > 0 wt.-% to about ⁇ 0.2 wt.-%, preferably about > 0.005 wt.-% to about ⁇ 0.05 wt.- %, further preferred about > 0.018 wt.-% to about ⁇ 0.022 wt.-%, based on the total weight amount of the aqueous detergent composition.
  • MGDA methyl glycine diacetic acid
  • the aqueous detergent composition can be free of a chelating agent.
  • the aqueous detergent composition can be free of a chelating agent except gluconate.
  • the aqueous detergent composition can be free of a chelating agent except tetrasodium N,N-bis(carboxylatomethyl)-L-glutamate (GLDA).
  • GLDA tetrasodium N,N-bis(carboxylatomethyl)-L-glutamate
  • the aqueous detergent composition can be free of a chelating agent except methyl glycine diacetic acid (MGDA).
  • MGDA methyl glycine diacetic acid
  • the aqueous detergent composition may preferably exclude a sequestering agent.
  • the aqueous detergent composition may include at least one sequestering.
  • Exemplary commercially available sequestering agents for use with aqueous detergent composition of the present invention may include, but are not limited to: sodium
  • tripolyphosphate available from Innophos; Trilon A® available from BASF; Versene 100®, Low NTA Versene ®, Versene Powder®, and Versenol 120® all available from Dow;
  • dipicolinic acid and/or phosphonic acid and corresponding salts thereof are suitable for use as sequestering agents with the methods of the invention.
  • Phosphonates are suitable for use as sequestering agents with the methods of the invention and can be selected from the group comprising 2-aminoethylphosphonic acid (AEPn); dimethyl methylphosphonate (DMMP); 1 -hydroxy ethylidene-l,l-diphosphonic acid (HEDP); amino tris(methylene phosphonic acid) (ATMP); ethylenediamine tetra(methylene phosphonic acid) (EDTMP); tetramethylenediamine tetra(methylene phosphonic acid) TDTMP); hexamethylenediamine tetra(methylene phosphonic acid) (HDTMP);
  • AEPn 2-aminoethylphosphonic acid
  • DMMP dimethyl methylphosphonate
  • HEDP 1 -hydroxy ethylidene-l,l-diphosphonic acid
  • ATMP amino tris(methylene phosphonic acid)
  • ETMP ethylenediamine tetra(methylene
  • DTPMP diethylenetriamine penta(methylene phosphonic acid)
  • PBTC phosphonobutane- tricarboxylic acid
  • PMIDA N-(phosphonomethyl)iminodiacetic acid
  • CEP A 2- carboxyethyl phosphonic acid
  • HPAA 2-hydroxyphosphonocarboxylic acid
  • AMP amino- tris-(methylene-phosphonic acid)
  • Aminophosphonates are also suitable for use as sequestering agents with the methods of the invention and include ethylenediaminetetramethylene phosphonates,
  • nitrilotrismethylene phosphonates and diethylenetriamine-(pentamethylene phosphonate) for example. These aminophosphonates commonly contain alkyl or alkenyl groups with less than 8 carbon atoms.
  • the aqueous detergent composition preferably a concentrated aqueous detergent composition, comprises in an amount of about > 0 wt.-% to about ⁇ 5 wt- %, preferably about > 0.1 wt.-% to about ⁇ 2 wt.-%, further preferred > 0.3 wt.-% to about ⁇ 1 wt.-%, and also preferred > 0.5 wt.-% to about ⁇ 0.7 wt.-%, a sequestering agent, preferably phosphonobutane-tricarboxylic acid (PBTC), based on the total weight amount of the aqueous detergent composition.
  • PBTC phosphonobutane-tricarboxylic acid
  • the aqueous detergent composition preferably a diluted aqueous detergent composition, comprises in an amount of about > 0 wt.-% to about ⁇ 0.2 wt.-%, preferably about > 0.005 wt.-% to about ⁇ 0.05 wt.-%, further preferred > 0.01 wt.-% to about ⁇ 0.025 wt.-%, and also preferred > 0.018 wt.-% to about ⁇ 0.019 wt.-%, a sequestering agent, preferably phosphonobutane-tricarboxylic acid (PBTC), based on the total weight amount of the aqueous detergent composition.
  • PBTC phosphonobutane-tricarboxylic acid
  • the aqueous detergent composition can be free of a sequestering agent.
  • the aqueous detergent composition can be free of a sequestering agent except phosphonobutane-tricarboxylic acid (PBTC).
  • PBTC phosphonobutane-tricarboxylic acid
  • a penetrant may be used with the aqueous detergent composition of the present invention.
  • the penetrant is water miscible.
  • suitable penetrants include, but are not limited to short chain ethoxylated alcohols and phenol (having 1-6 ethoxylate groups).
  • Organic solvents are also suitable penetrants.
  • suitable organic solvents, for use as a penetrant include esters, ethers, ketones, amines, and nitrated and chlorinated hydrocarbons.
  • Ethoxylated alcohols are also suitable for use with the methods of the present invention.
  • ethoxylated alcohols include, but are not limited to, alky, aryl, and alkylaryl alkloxylates. These alkloxylates may be further modified by capping with chlorine-, bromine-, benzyl-, methyl-, ethyl-, propyl-, butyl- and alkyl-groups.
  • Ethoxylated alcohols may be present in the aqueous detergent composition from about > 0.1 wt% to about > 20 wt%.
  • Fatty acids are also suitable for use as penetrants in the methods of the present invention.
  • Some non-limiting examples of fatty acids are CY, to Ci 2 straight or branched fatty acids.
  • fatty acids used in the methods of the present invention are liquid at room temperature.
  • a penetrant for use in the methods of the present invention includes water soluble glycol ethers.
  • glycol ethers include dipropylene glycol methyl ether (available under the trade designation DOWANOL DPM from Dow Chemical Co.), diethylene glycol methyl ether (available under the trade designation DOWANOL DM from Dow Chemical Co.), propylene glycol methyl ether (available under the trade designation DOWANOL PM from Dow Chemical Co.), and ethylene glycol monobutyl ether (available under the trade designation DOWANOL EB from Dow Chemical Co.).
  • the aqueous detergent composition preferably a concentrated aqueous detergent composition, comprises in an amount of about > 0 wt.-% to about ⁇ 10 wt.- %, preferably about > 1 wt.-% to about ⁇ 8 wt.-%, further preferred > 3 wt.-% to about ⁇ 6 wt.-%, and also preferred > 4 wt.-% to about ⁇ 5 wt.-%, a penetrant, preferably diethylene glycol monobutyl ether, based on the total weight amount of the aqueous detergent composition.
  • a penetrant preferably diethylene glycol monobutyl ether
  • the aqueous detergent composition preferably a diluted aqueous detergent composition, comprises in an amount of about > 0 wt.-% to about ⁇ 0.4 wt.-%, preferably about > 0.01 wt.-% to about ⁇ 0.3 wt.-%, further preferred > 0.05 wt.-% to about ⁇ 0.2 wt.-%, and also preferred > 0.130 wt.-% to about ⁇ 0.135 wt.-%, a penetrant, preferably diethylene glycol monobutyl ether, based on the total weight amount of the aqueous detergent composition.
  • a penetrant preferably diethylene glycol monobutyl ether
  • the aqueous detergent composition can be free of a penetrant.
  • the aqueous detergent composition can be free of a penetrant except diethylene glycol monobutyl ether.
  • the aqueous detergent composition can be presented in a concentrated liquid form.
  • the concentrates include a liquid medium, preferably water, and relatively large
  • the concentrated aqueous detergent composition may have a pH in the range of about > 8.5 and ⁇ 12, preferably of about > 9 and ⁇ 11.5, further preferred of about > 9.5 and ⁇ 11 and more preferred about 10 ⁇ 0.3.
  • the diluted aqueous detergent composition may be adjusted to a pH of about 7.0 to pH of about 12.0, preferably to a pH of about 7.5 to about 10 and more preferred a pH in the range of about 8 to about 9.5 or 8.5 to about 9. pH
  • the aqueous detergent composition has a pH in the range of about > 8.5 and ⁇ 12, preferably of about > 9 and ⁇ 11.5, further preferred of about > 9.5 and ⁇ 11 and more preferred about 10 ⁇ 0.3.
  • the protease that can be suitable used for the aqueous detergent composition is a subtilisin protease.
  • the protease can be a serinprotease.
  • the protease can be a serinendoprotease.
  • the protease of the aqueous detergent composition comprises a peptide compound, wherein the peptide compound can be selected from di- substituted alanin amide or OH-substituted phenylalanine.
  • the protease may contain about 0.1 wt.-% to about 1% wt.-% peptide compound, wherein the peptide compound can be selected from di-substituted alanin amide or OH- substituted phenylalanine, preferably selected from OH-substituted phenylalanine, based on the raw protease material.
  • peptide compound wherein the peptide compound can be selected from di-substituted alanin amide or OH-substituted phenylalanine, preferably selected from OH-substituted phenylalanine, may increases the heat resistance of the protease, preferably of the serinprotease and more preferred of the serinendoprotease .
  • the peptide compound of OH-substituted phenylalanine that can be suitable used having the formula I:
  • R is hydrogen, CH3, CX3 , CHX 2 , or CH 2 X, preferably hydrogen;
  • X is a halogen atom, preferably Cl
  • Bi is a single amino acid residue
  • B 2 is one or more amino acid residues, B 2 optionally comprising an N-terminal protection group.
  • B 1 is a small amino acid residue. More preferably Bl is alanine or valine. In this context, the following are considered to be small amino acids: alanine, cysteine, glycine, proline, serine, threonine, valine, norvaline, norleucine.
  • the peptide compound may be an aldehyde wherein R is hydrogen, Bi is a single amino acid, preferably selected among small amino acids such as valirre and alanine, B 2 comprises at least two amino acid residues and wherein at least one of said two amino acid residues is selected among phenylalanine, glycine and leucine.
  • Aminoacid residues are abbreviated using standard one-letter or three-letter abbreviations, including the following abbreviations: alanine (A), phenylalanine (F), glycine (G), leueine (L), argirrirre (R), valirre (V), tryptophan (W), tyrosine (Y).
  • alanine (A) phenylalanine (F), glycine (G), leueine (L), argirrirre (R), valirre (V), tryptophan (W), tyrosine (Y).
  • the abbreviation "Y -H” demotes tyrosinal, meaning that the C-terminal end of the tyrosine residue is converted from a carboxylic group to an aldehyde group.
  • the second amino acid residue of B 2 can have a non-polar side chain selected among phenylalanine, glycine, leucine, tyrosine and tryptophan.
  • B 2 comprises an acetyl (Ac) N-terminal protection group, providing, inter alia, the peptide aldehyde compounds Ac- FGAY-H, Ac-LGAY-H, Ac-YGAY-H, Ac-FGVY-H and Ac-WLVY-H.
  • the compounds according to this aspect of the invention comprise less than 10 amino acid residues, such as 9, 8, 7, 6, 5 or most preferably 4 amino acid residues.
  • the peptide compound according to formula I may be a tri-peptide aldehyde wherein R is hydrogen, Bi is a single amino acid selected among small amino acids, e.g. valine and alanine, B 2 comprises an amino acid residue selected among arginine, glycine and leucine.
  • B 2 comprises an N-terminal protection group selected among benzyloxycarbonyl (Z) and acetyl (Ac), providing, inter alia, the peptide aldehyde compounds Z-RAY-H, Z-GAY-H, Z-GAL-H, Z-GAF-H, Z-GAV-H, Z-RVY-H, Z-LVY-H and Ac-GAY- H.
  • Z benzyloxycarbonyl
  • Z N-terminal protection group
  • B 2 comprises an N-terminal amino acid residue having a non polar side chain.
  • amino acids with non-polar side chain is meant an amino acid or amino acid residue selected from the group comprising: phenylalanine, tyrosine, tryptophan, isoleucine, leucine, methionine, valine, alanine, proline, glycine, norvaline, or norleucine.
  • Particularly preferred peptide aldehydes of the present invention include Z-RAY -H, Ac-GAY-H, Z-GAY-H, Z-GAL-H, Z-GAF-H, Z-GAV-H, Z-RVY-H, Z-LVY-H, AcLGAY- H, Ac-FGAY-H, Ac-YGAY-H, Ac-FGVY-H or AcWLVY-H, where Z is benzyloxycarbonyl and Ac is acetyl.
  • the N-terminal protecting group may be any aminoterminal protecting group which can be employed in peptide synthesis. Grassand Meinhoffer, eds., The Peptides, Vol. 3;
  • Suitable groups include formyl, acetyl, benzoyl, trifluoroacetyl, fluoromethoxy carbonyl, methoxysuccinyl, aromatic urethane protecting groups, such as, benzyloxylcarbonyl; and aliphatic urethane protecting groups, such as t-butyloxycarbonyl or adamantyloxycarbonyl, p-methoxybenzyl carbonyl (MOZ), benzyl (Bn), p-methoxybenzyl (PMB) or p-methoxyphenyl (PMP).
  • MOZ p-methoxybenzyl carbonyl
  • Bn benzyl
  • PMB p-methoxybenzyl
  • PMP p-methoxyphenyl
  • the N-terminal protection group of the present invention is selected among formyl, acetyl, benzoyl, aromatic or aliphatic urethanes, more preferably acetyl or
  • the N- terminal protection group is preferably an aromatic or aliphatic urethane or an aromatic N- terminal protection group, particularly benzyloxycarbonyl (Cbz), p-methoxybenzyl carbonyl (MOZ), benzyl (Bn), p-methoxybenzyl (PMB) or p-methoxyphenyl (PMP), more preferably benzyloxycarbonyl.
  • the N-terminal protection group is formyl, acetyl or benzoyl, more preferably acetyl.
  • R is hydrogen
  • Bi is a single amino acid, preferably selected among small amino acids such as valine and alanine
  • B 2 is -Z-GAY-H, wherein Z is an N-terminal protection group, preferably benzyloxycarbonyl
  • G is glycine
  • A is alanine and Y-H denotes tyrosinal.
  • the peptide compound may have the formula II:
  • R is hydrogen
  • B 3 is -Z-GAY-H, wherein Z is an N-terminal protection group, preferably benzyloxycarbonyl, G is glycine, A is alanine and Y-H denotes tyrosinal.
  • an aqueous detergent composition may comprise:
  • an aqueous detergent composition may comprise:
  • an aqueous detergent composition may comprise:
  • an aqueous detergent composition preferably a concentrated aqueous detergent composition, is provided comprising:
  • subtilisin protease - about > 1 wt.-% to about ⁇ 5 wt.-% of at least one subtilisin protease
  • an aqueous detergent composition preferably a concentrated aqueous detergent composition, is provided comprising:
  • subtilisin protease - about > 1 wt.-% to about ⁇ 5 wt.-% of at least one subtilisin protease
  • an aqueous detergent composition preferably a concentrated aqueous detergent composition, is provided comprising:
  • subtilisin protease - about > 1 wt.-% to about ⁇ 5 wt.-% of at least one subtilisin protease
  • an aqueous detergent composition preferably a concentrated aqueous detergent composition, is provided comprising:
  • subtilisin protease - about > 1 wt.-% to about ⁇ 5 wt.-% of at least one subtilisin protease
  • an aqueous detergent composition preferably a concentrated aqueous detergent composition, is provided comprising:
  • an aqueous detergent composition preferably a concentrated aqueous detergent composition, is provided comprising:
  • subtilisin protease - about > 1 wt.-% to about ⁇ 5 wt.-% of at least one subtilisin protease
  • an aqueous detergent composition preferably a concentrated aqueous detergent composition, is provided comprising:
  • an aqueous detergent composition preferably a concentrated aqueous detergent composition, is provided comprising:
  • an aqueous detergent composition preferably a concentrated aqueous detergent composition, is provided comprising:
  • an aqueous detergent composition preferably a concentrated aqueous detergent composition, is provided comprising:
  • sulfonate - optional about > 0.1 wt.-% to about ⁇ 0.3 wt.-% of at least one anionic surfactant, preferably an C 8 to Ci 4 alkyl sulfate and more preferred 2-ethylhexyl sulfate;
  • an aqueous detergent composition preferably a concentrated aqueous detergent composition, is provided comprising:
  • wt.-% of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
  • an aqueous detergent composition preferably a concentrated aqueous detergent composition, is provided comprising:
  • wt.-% of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
  • the surfactant selected from at least one alkyl alkoxylate surfactant and/or at least one alkyl alkoxylate alkyl being n-C2 to C5 alkyl end- capped and more preferred n-butyl end-capped.
  • the surfactant selected from at least one alkyl alkoxylate surfactant and/or at least one alkyl alkoxylate alkyl ether is an alkyl alkoxylate alkyl ether of about C10 to about C16 with about 8 EO to about 12 EO and being C2 to C5 alkyl end-capped, preferably n-C2 to n-C5 alkyl end-capped.
  • the surfactant selected from at least one alkyl alkoxylate surfactant and/or at least one alkyl alkoxylate alkyl ether is an alkyl alkoxylate alkyl ether C12/C14 of about 8 EO to about 12 EO, being n-C2 to n-C5 alkyl end-capped.
  • the surfactant selected from at least one alkyl alkoxylate surfactant and/or at least one alkyl alkoxylate alkyl ether is an alkyl alkoxylate alkyl ether of C12/C14-10EO and being n-butyl end-capped.
  • the aqueous detergent composition can be present in form of a diluted or so called “ready-to-use” composition.
  • the diluted compositions may be derived from a concentrated aqueous detergent composition, for example, by combining water, for example, deionized water, city or tap water, with said concentrate.
  • the so called ready-to-use compositions may be treated to reduce hardness.
  • the source of alkalinity and addition of the solvent, preferably water, are provided so that the diluted aqueous detergent composition may have a pH in the range of about 7 to about 12 and more preferred a pH in the range of about 8 to about 9.5.
  • the concentrated aqueous detergent composition can be diluted with a solvent, preferably water, to an about 1,0 wt.-% to about 10 wt.-%, preferably to an about 2,0 wt.-% to 5.5 wt.-%, diluted aqueous detergent composition, also named “ready-to-use solution”.
  • a solvent preferably water
  • a solvent preferably water is added to 100 wt.-% to the diluted aqueous detergent composition, wherein the weight.-% of the components are based on the total weight of the diluted aqueous detergent composition, and the weight. -% of all components of the aqueous detergent composition are select so that it does not exceed 100 wt.-%.
  • the present invention provides methods for removing soil from a surface.
  • the methods for removing soil from a surface include using a clean out of place (COP) or clean in place (CIP) cleaning process.
  • the methods include applying to the surface a composition of the invention.
  • the method for removing soil from a surface to be cleaned may comprises applying to the surface an aqueous detergent composition.
  • the method for removing soil from a surface to be cleaned may comprises applying to the surface a concentrated aqueous detergent composition.
  • the method for removing soil from a surface to be cleaned may comprises preferably applying to the surface a diluted aqueous detergent composition.
  • the method for removing soil from a surface to be cleaned may comprising:
  • a pre-treatment solution preferably water
  • aqueous detergent composition preferably the diluted aqueous detergent composition
  • the methods and compositions of the present invention are applied to surfaces which are normally cleaned using a clean out of place or in place cleaning technique.
  • surfaces include hard and soft surface, for example of upper outer and/or inner outer surfaces of materials such as ceramic, metal, plastic and/or glass, surface that came into contact with beverages and/or food, beverages such alcoholic or non alcoholic beverages such as beer or milk, food such as meat, vegetables and/or grain-products.
  • instruments and apparatus for example used in sanitary or medical services, evaporators, heat exchangers, including tube-in-tube exchangers, direct steam injection, and plate-in-frame exchangers, heating coils including steam, flame or heat transfer fluid heated re-crystallizers, pan crystallizers, spray dryers, drum dryers, and tanks.
  • evaporators heat exchangers, including tube-in-tube exchangers, direct steam injection, and plate-in-frame exchangers
  • heating coils including steam, flame or heat transfer fluid heated re-crystallizers, pan crystallizers, spray dryers, drum dryers, and tanks.
  • Additional surfaces capable of being cleaned using the methods and compositions of the present invention include, but are not limited to membranes, medical devices, laundry and/or textiles, and hard surfaces, e.g., walls, floors, dishes, flatware, pots and pans, heat exchange coils, ovens, fryers, smoke houses, sewer drain lines, and vehicles.
  • the surfaces may be cleaned using a clean in place method.
  • the methods of the present invention may also be used to remove dust from air handling equipment, for example, from air conditioners and refrigeration heat exchangers.
  • the methods of the present invention may be used for drain line microbial control, e.g., to reduce or remove biofilm formation.
  • Exemplary industries in which the methods and compositions of the present invention may be used include, but are not limited to: the food and beverage industry, e.g., the dairy, cheese, sugar, and brewery industries; oil processing industry; industrial agriculture and ethanol processing; and the pharmaceutical manufacturing industry.
  • the aqueous detergent composition can be used for:
  • COP clean-out-of-place system
  • CIP clean-in-place system
  • the manual or automatic medical instrument reprocessing comprises especially the manual or automatic chirurgical instrument reprocessing.
  • the methods and compositions of the present invention may be used, but are not limited to: manual or automatic medical instrument reprocessing, in particular cleaning an endoscope.
  • the manual or automatic medical instrument reprocessing comprises the cleaning and/or disinfection of medical instruments, in particular of endoscopes.
  • the methods and aqueous detergent composition for soil removal from surfaces can be applied at reduced temperatures, e.g., from about > 20° C to about ⁇ 60° C, preferably about > 35° C to about ⁇ 50° C and preferably at about 45° C ⁇ 3 0 C results in energy and cost savings compared to traditional cleaning techniques that require increased temperatures.
  • the present invention provides for effective soil removal on surfaces that cannot withstand high temperatures.
  • the methods of the present invention provide for soil removal at reduced temperatures, and using reduced amounts of chemistry, compared to conventional cleaning methods.
  • the methods of the present invention may use about 25% to about 50% less chemistry, e.g., source of alkalinity, than conventional cleaning methods.
  • the methods of the present invention may effectively remove soil at both low temperatures, and using a low concentration of chemicals, providing both an energy savings and a reduction in the amount of chemistry consumed per cleaning. Time
  • aqueous detergent composition for use with the methods of the present invention are applied to the surface for a sufficient amount of time such that the composition penetrates into the soil to be removed.
  • the aqueous detergent composition for use with the methods of the present invention is applied to the surface to be cleaned for about 1 minute to about 30 minutes. In some embodiments, the aqueous detergent composition for use with the methods of the present invention is applied to the surface to be cleaned for about 5 to about 15 minutes. In some embodiments, the aqueous detergent composition for use with the methods of the present invention is applied to the surface to be cleaned for about 10 minutes ⁇ 2 minutes. It is to be understood that any value between these ranges is to be encompassed by the methods of the present invention.
  • compositions of examples El to E4 of the invention were prepared by mixing the components at about 20° C as mentioned in table I in an amount obtaining a 50 ml aqueous solution.
  • Liquanase Evity 3.5 XL* 1 expressed as enzyme protein (aep) and obtainable from the company Novozymes A/S, located at Krogshoejvej 36, 2880 Bagsvaerd, Denmark.
  • Water* 2 is demineralized water.
  • Alkyl alkoxylate alkyl ether C12/C14-10EO, n-butyl end-capped* 3 can be preferably Genapol BE 2410.
  • Cl2/Cl5-oxo alcohol EO-PO-adduct* 4 can be preferably Genapol EP 2552.
  • C12/C14 fatty alcohol EO/PO-addition product* 5 can be preferably Genapol EP 2464.
  • Cl0/Cl2-fatty alcohol EO-PO-adduct* 6 can be preferably Genapol 0244.
  • the demineralized water (demin. water) is produced by a process of distillation and has an electrical conductivity of not more than 11 gS/cm and total dissolved solids of less than 10 mg/liter. Distillation involves boiling the water and then condensing the vapor into a clean container, leaving solid contaminants behind.
  • Table 1 shows that alkyl alkoxylate alkyl ether of example El has an improved phase stability and low foaming characteristic compared with examples E2 to E4.
  • compositions of examples E5 to E8 of the invention and comparative example C2 were prepared by additional diluting the compositions El to E4 and Cl at about 20° C to a 0.6% (w/w) solution with demineralized water.
  • the demineralized water (demin. water) is produced by a process of distillation and has an electrical conductivity of not more than 11 pS/cm and total dissolved solids of less than 10 mg/liter. Distillation involves boiling the water and then condensing the vapor into a clean container, leaving solid contaminants behind.
  • This test method provides a basis to assess the activity loss of protease for the compositions of examples E5 to E8 of the invention and comparative examples C2.
  • 50 ml solution of examples E5 to E8 and C2 respectively are each treated for 76 h at a constant temperature of 45° C.
  • the activity of the protease solutions of examples E5 to E8 and C2 slightly decrease. After 76 hours the temperature was raised for additional 4 hours to a constant temperature of 50° C.
  • the method of assaying the activity of the enzymes uses TNBS color reaction method and the San++ - analyzer available from Skalar Analytical BV. This assay measures the enzymatic hydrolysis of casein into polypeptides containing free amino groups. These amino groups react with 2,4,6-trinitrobenzene sulfonic acid (TNBS) to form a yellow colored complex. Thus, the more deeply colored the reaction, the more activity is measured.
  • TNBS 2,4,6-trinitrobenzene sulfonic acid
  • Continuous Flow System with computer and Flow Access V3 of San++, available from Skalar Analytical BV, also referred to as“Continuous Flow System”.
  • Brij 35 solution 10 % 50 g Brij 35 were dissolved in approximately 500 mL deionized water and filled up to 1 L with deionized water in a graduated flask.
  • the activity of the Liquanase Evity 3,5 LX was measured with the Continuous Flow System with computer and Flow Access V3 of San++. Three samples of 1 g of the protease Liquanase Evity 3,5 LX were weighted and diluted in 1 L protease solvent, solved for 20 minutes and further diluted 1/781 and 1/671 with Sodium Sulfite Solution before
  • the mean activity for the test substance Liquanase Evity 3,5 LX is: 176.200 CPE/g
  • a sample of a first placebo probe that is Example 1 but without protease and a sample of second probe, which is identical with the first placebo probe but with the exception that the substance Liquanase Evity 3,5 LX is added to the second test probe were prepared as described above under sample preparation.
  • the amount of Liquanase Evity 3,5 LX added to the second test probe was 2,0 wt.-%.
  • the first placebo probe was further diluted with 1/11 sodium sulfite solution. This is the lowest dilution that is used in complex matrices to avoid interferences from a product.
  • the spiked second probe was diluted 1/341 and 1/231 to be in the range of the calibration curve.
  • the placebo sample measured with the Continuous Flow System with computer and Flow Access V3 of San++ shows no activity peak.
  • the product does not contain any substance that might disturb the determination.
  • the sample of the spiked second probe measured with the Continuous Flow System with the added 2% of protease shows the expected protease activity peaks.
  • a calibration curve was made with 5 different concentrations of protease Liquanase Evity 3,5 LX placebo samples over a range of ⁇ 20% of the target concentration of 2 wt.-%. After 20 minutes of mixing several dilutions of this preparation with these placebo probes to which protease Liquanase Evity 3,5 LX were added were made.
  • the coefficient of determination R 2 is 0,9972
  • Examples E5 to E8 and C2 treated 76 hours at 45° C and for an additional time of 4 h at 50° C.
  • protease enzyme is still active after treated 76 h at 45° C and 4 h at 50° C. An expert would expect that the protease enzyme activity for examples E5 to E8 would be close to 0%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

An aqueous detergent composition is provided comprising: - about ≥ 1 wt.-% to about ≤ 15 wt.-% of at least one source of alkalinity; - about ≥ 1 wt.-% to about ≤ 15 wt.-% of at least one alkyl alkoxylate surfactant and/or an alkyl alkoxylate alkyl ether; - about ≥ 0.1 wt.-% to about ≤ 5 wt.-% of at least one protease; - about ≥ 1 wt.-% to about ≤ 30 wt.-% of at least one organic solvent; and - about ≥ 30 wt.% water; wherein the wt.-% of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.

Description

PHASE STABLE AND LOW FOAMING AQUEOUS DETERGENT COMPOSITIONS HAVING A LONG TIME ENZYME ACTIVITY
FIELD OF THE INVENTION
The present invention relates to aqueous cleaning compositions that are phase stable and having a long time enzyme activity, to a method of manufacture and the use thereof
BACKGROUND OF THE INVENTION
In many industrial cleaning and/or disinfection applications, such as cleaning and/or disinfection of hospitals, medical devices, for example chirurgical instruments, the
manufacture of foods and beverages, especially in the meat processing industry, hard as well as soft surfaces etc. commonly become contaminated with soils such as carbohydrate, proteins, blood and water hardness soils, food oil soils, fat soils and other soils. Such soils can arise from the manufacture of both liquid and solid residences/contaminants. Grease soils and residue soils such as proteins, fats, blood and oils, especially when dried, can be hard to remove soil. Similarly, carbohydrate soils, such as cellulosic, monosaccharides, disaccharides, oligosaccharides, starches, gums and other complex materials, when dried, can form tough, hard to remove soils, particularly when combined with other soil components such as proteins, blood, fats, oils, minerals, and others. The removal of such soils and residues, can be a significant problem.
Clean out of place systems (COP) cleaning techniques are a specific cleaning regimen adapted for removing soils from exterior surfaces of a wide variety of parts, such as ceramic surfaces, metallic surfaces, walls, wash tanks, soaking vessels, mop buckets, holding tanks, scrub sinks, vehicle parts washers, non-continuous batch washers and systems, ceilings, external parts of production machinery and the like.
Often clean out of place methods can involve a first rinse, the application of the cleaning solutions, and a second rinse with potable water followed by resumed operations.
The process can also include any other contacting step in which a rinse, acidic or basic functional fluid, solvent or other cleaning component such as hot water, cold water, etc. can be contacted with the equipment at any step during the process. Conventional clean in place as well as clean out of place methods require high temperatures, up to about 80° C. In production rooms, the elevated water temperature currently used for that kind of cleaning processes is in the range of about 40° C to about 60° C. Conventional clean out of place techniques (COP) thus require the consumption of large amounts of energy.
In particular, manual or automatic instrument reprocessing requires a specific cleaning regimen and cleaning compositions adapted for removing soils from surfaces.
Detergent compositions generally used in cleaning instruments, such as medical instruments, especially endoscopes, require detergent compositions having a high activity of soil removal. These cleaning compositions suffers in their material compatibility.
It is therefore always a need to provide cleaning compositions having a high cleaning activity for removing soils such as proteins, fats and blood and having a good material compatibility, for example of metallic surfaces and/or plastic parts like plastic seals, and can be used for example in manual or automatic instrument reprocessing.
Cleaning processes at elevated temperatures in the range of about 40° C to about 60° C requires cleaning composition that are not corrosive to the metallic surface to be cleaned as well as doesn’t affect or being aggressive to plastic parts, like plastic seals.
What is needed therefore is a non-aqueous detergent composition for removing soils such as proteins, fats and blood having no phase separation at elevated temperatures, an increased metal and plastic material compatibility and can be used in manual or automatic instrument reprocessing, especially for cleaning endoscopes.
SUMMARY OF THE INVENTION
The object addressed by the present invention is to provide an aqueous detergent composition for removing soils such as proteins, fats and blood having no phase separation at elevated temperatures, an increased metal and plastic material compatibility, that can be used for example in removing soil from a surface to be cleaned, preferably in a clean-out-of-place systems (COP) or in a clean-in-place system (CIP) or in manual or automatic instrument reprocessing, especially for cleaning endoscopes.
According to one aspect an aqueous detergent composition for removing of soil at elevated temperatures from a surface to be cleaned is provided.
According to one aspect an aqueous detergent composition is provided comprising:
- about > 1 wt.-% to about < 15 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one alkyl alkoxylate surfactant and/or an alkyl alkoxylate alkyl ether;
- about > 0.1 wt.-% to about < 5 wt.-% of at least one protease; - about > 1 wt.-% to about < 30 wt.-% of at least one organic solvent; and
- about > 30 wt.% water;
wherein the wt.-% of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
It has been surprisingly found that the aqueous detergent composition can be used for removal of soil at elevated temperatures over an extended time period, while still providing excellent material compatibility properties.
It has been further surprisingly found that the aqueous detergent composition is low- foaming.
It has been further surprisingly found that the aqueous detergent composition doesn’t show a phase separation at elevated temperatures.
In addition it has been surprisingly found that the reduction of protease activity at elevated temperatures of about > 45° C to about < 60 °C is less due to an unexpected stabilization effect of the detergent composition compared to a protease water solution over an extended time period.
Although the cleaning cycle in for example an automated cleaning apparatus for devices such as endoscopes takes about 20 minutes to 1 hour and the cleaning temperatures are often between room temperature and 45° C it has to assume that the canister of the enzyme containing cleaning composition of the present invention is often integrated in or arranged near by the cleaning apparatus thus subjected to heating temperatures of the water heating system of about > 50° C to about < 90° C for a continues time period until the canister is emptied, which can takes up to three weeks. Up to 90° C can be reached in the cleaning apparatus at the disinfection step. That means it’s not the temperature at the cleaning step of 20 to 60 minutes at temperatures up to < 60 °C the enzyme of the cleaning composition needs to withstand it’s merely the temperature the container containing the enzyme comprising composition needs to withstand at various temperatures from about > 50° C to about < 90° C for example up to 24 hours a day until the container is emptied, which can take two days and up to 3 weeks depending on the intensive of total cleaning apparatus running time.
Protease is stable in a water solution at temperatures up to about 43° C. Increasing the temperature of a protease-water solution to about 45° C shows a decrease of protease activity in a protease-water solution. It was surprisingly found that the decrease of protease activity at temperatures at about 45° C and above, such as > 50° C to about < 60 °C is significant less compared with a protease water-solution. The present aqueous detergent composition allows an effective cleaning and removing soil from hard and/or soft surfaces at elevated temperature of about > 45° C to about < 60 °C without significant loss of the protease activity. The further advantage is that at temperatures of about > 45° C to about < 60 °C bacteria are destroyed.
In addition, due to the evaluated temperatures milder cleaning and soil removal components can be selected due to a temperature induced higher activity and aggressive cleaning components can be avoided, while ensuring surprisingly the protease activity.
Further, the protease activity of the aqueous low-foaming detergent composition shows a significant increased life span compared with the same protease in water.
Thus the present aqueous detergent composition is an improvement for cleaning and/or removing soil from for example endoscopes having metal and plastic sensitive parts compared with the alkaline cleaners typically used.
Further, the compositions of the present invention provide for reduced energy consumption, since it has an increased cleaning performance at low cleaning temperatures.
It has been further surprisingly found that the aqueous detergent composition that can be used in automated cleaning devices, like automated cleaning devices for medical instruments, in particular endoscopes.
Furthermore, the aqueous detergent composition is active at a low components concentration thus provides a reduced chemical consumption.
The aqueous detergent composition can be present in form of a concentrated solution. The concentrated solution has advantages in transporting and storing. The concentrated solution can be diluted, for example prior use, by admixing a solvent, preferably water.
It should be understood that the aqueous detergent composition can be free of at least one additive selected from the group of dye, color transfer inhibitor, anti-redeposition agents, optical brighteners, builder, oil and water repellant agents, color fastness agents, starch/sizing agents, fabric softening agents, anti-microbials, fungicides, UV absorbers, fragrances and/or mixtures thereof.
DETAILED DESCRIPTION
In some aspects, the present invention relates to aqueous detergent compositions and methods for removing soils from surfaces to be cleaned. Surfaces to be cleaned are hard and/or soft surfaces. In some embodiments, the composition of the invention is applied in a clean in place process (CIP) and/or in a clean out of place process (COP). According to the present invention it may be preferred that the clean in place process (CIP) is a fully automated cleaning process that may requires no reconstruction of the production plant before execution of the cleaning.
In other embodiments, the compositions of the invention may be manually applied to the surface to be cleaned. In particular the compositions of the invention can be used in hospital cleaning, cleaning of medical devices, for example chirurgical instruments, the food processing industry, such as meat processing industry, for cleaning purposes.
The compositions of the invention may be used in manual or automatic instrument reprocessing, preferably medical instruments.
In another embodiments, the compositions of the invention may be used for manually or automatically cleaning of chirurgical instruments, in particular endoscopes.
The aqueous detergent composition can be a more component composition that can be mixed in situ at the place of use.
The aqueous detergent composition allows for the use of reduced levels of chemistry, because the aqueous detergent composition of the invention has a remarkable increased cleaning efficiency that allows the use of a lower concentrated detergent composition. Thus, the methods of the present invention provide for reduced energy consumption, e.g., lower cleaning temperatures, and reduced chemical consumption.
So that the invention may be more readily understood, certain terms are defined.
As used herein, "by weight" refers to the total weight of the composition. For example, if a composition has a total weight of 100 grams and comprises 40% (by weight) of an alcohol, the composition may comprise 40 grams of alcohol.
It is understood that the total weight percent amount of all components, substances or agents of a composition are selected such that it does not exceed 100 wt.-%.
It is understood that the weight. -% of the components are based on the total weight of the concentrated aqueous detergent composition, and the weight. -% of all components of the aqueous detergent composition are select so that it does not exceed 100 wt.-%.
It is understood that, as used here,„percent”,„%”, and the like are intended to be synonymous with„weight percent”,„wt-%“, etc..
As used herein, the term„surface“ refers to an inner and/or outer surface that can be contacted by the aqueous detergent composition at a cleaning and removal of soil process.
The term„surface“ refers for example to a surface, such as outer and/or inner surface, of articles, such as a medical instrument, a healthcare setting, a tool, a machine, equipment, a structure, a building, or the like that is employed as part of a food processing, preparation, or storage activity. Examples of healthcare settings include hospitals, doctor's offices and long term care facilities. Examples of food processing surfaces include surfaces of food processing or preparation equipment, e.g., slicing, canning, or transport equipment, including flumes, of food processing wares, e.g., utensils, dishware, wash ware, and bar glasses), and of floors, walls, or fixtures of structures in which food processing occurs. Food processing surfaces are found and employed in milking machines, food anti-spoilage air circulation systems, aseptic packaging sanitizing, food refrigeration and cooler cleaners and sanitizers, ware washing sanitizing, blancher cleaning and sanitizing, food packaging materials, cutting board additives, third-sink sanitizing, beverage chillers and warmers, meat chilling or scalding waters, auto dish sanitizers, sanitizing gels, cooling towers, food processing antimicrobial garment sprays, and non-to-low-aqueous food preparation lubricants, oils, and rinse additives.
As used herein, the term„ware“ refers to items such as eating and cooking utensils, dishes, and other hard surfaces such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, and floors.
As used herein, the term„active components" refers to the components comprising source of alkalinity; alkyl alkoxylate surfactant selected from the group comprising a CVCix- alkyl alkoxylate (EO)n/(PO)m and/or a CVCix-alkyl alkoxylate (EO)n/(PO)m Ci-CValkyl ether, wherein n = 1 to 16 and m = 0 to 16; protease; and organic solvent. Preferably the Ci- CValkyl of the ether can be butyl.
According to an another embodiment the CVCix-alkyl alkoxylate (EO)n/(PO)m ether, wherein n = 1 to 16 and m = 0 to 16 can be preferably Ci-CValkyl caped.
The C8-Ci8-alkyl alkoxylate (EO)n/(PO)m Ci-CValkyl ether, wherein n = 1 to 16 and m = 0 to 16 can be preferably butyl-end caped.
As used herein, the term„about“ refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients used to make the compositions or carry out the methods; and the like.
The term„about“ also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term„about“, the claims include equivalents to the quantities.
If not other where stated the temperatures is about 23° C.
If not other where stated the humidity is about 40% ±5% at about 23° C. It should be noted that, as used in this specification and the appended claims, the singular forms„a”,„an”, and„the“ include plural referents unless the content clearly dictates otherwise. Thus, for example, reference to a composition containing„a compound" includes a composition having two or more compounds.
It should also be noted that the term„or“ is generally employed in its sense including „and/or“ unless the content clearly dictates otherwise.
It is specifically understood that any numerical value recited herein (e.g., ranges) includes all values from the lower value to the upper value, i.e., all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application. For example, if a concentration range is stated as 1% to 50%, it is intended that values such as 2% to 40%, 10% to 30%, or 1% to 3%, etc., are expressly enumerated in this specification. These are only examples of what is specifically intended.
It is to be understood that all values and ranges between values and ranges are encompassed by the methods of the present invention.
In some embodiments, the compositions of the invention including the foam can have an alkaline pH, for example a pH of about 8.5 to about 12.
According to one aspect the aqueous detergent composition has a pH in the range of about > 8.5 and < 12, preferably of about > 9 and < 11.5, further preferred of about > 9.5 and < 11 and more preferred about 10 ± 0.3.
The term“Mw” refers to an average molecular weight.
The methods, and compositions of the present invention can include, or consist essentially of, or consist of the steps, and ingredients of the present invention as well as other ingredients described herein.
As used herein,“consisting essentially of’ means that the methods, and compositions may include additional steps, or ingredients, but only if the additional steps, or ingredients do not materially alter the basic and novel characteristics of the claimed methods, and compositions.
In some aspects, the methods and compositions of the present invention may be applied to equipment generally cleaned using clean in place cleaning procedures. Examples of such equipment include evaporators, heat exchangers, including tube-in-tube exchangers, direct steam injection, and plate-in-frame exchangers, heating coils, including steam, flame or heat transfer fluid heated, re-crystallizers, pan crystallizers, spray dryers, drum dryers, and tanks. The methods and compositions of the present invention may also be used to remove other soils that are not easily removed using conventional cleaning techniques. Soil types suited to cleaning with the methods of the present invention include, but are not limited to, starch, cellulosic fiber, protein, simple carbohydrates and combinations of any of these soil types with mineral complexes. Examples of specific food soils that are effectively removed using the methods of the present invention include, but are not limited to, meat residues, blood residues, protein residues, vegetable and fruit juices, brewing and fermentation residues, soils generated in sugar beet and cane processing, and soils generated in condiment and sauce manufacture, e.g., ketchup, tomato sauce, barbeque sauce.
The methods and compositions of the present invention may be preferably used in any application where body fluids, proteins, fats and/or carbohydrates, need to be removed.
Exemplary industries in which the methods and compositions of the present invention can be used include, but are not limited to: hospitals, such as for the cleaning of medical / chirurgical instruments, the food and beverage industry, e.g., the meat processing industry; dairy, cheese, sugar, and brewery industries; oil processing industry; industrial agriculture and ethanol processing; and the pharmaceutical manufacturing industry.
Conventional CIP as well as COP processing is generally well-known. The process includes applying a composition of the invention onto the surface to be cleaned and/or soil removed.
The process to remove a soil according to the invention can include an alkaline wash. According to one embodiment of the invention a process to remove a soil can include a fresh water rinse and an alkaline wash or a fresh water rinse, an alkaline wash and a fresh water rinse. Another embodiment of a process of the invention to remove soil can comprise the cleaning step: an alkaline wash, an acid solution wash, and then a fresh water rinse. The alkaline wash softens the soils and removes the organic alkaline soluble soils. The subsequent acid solution removes mineral soils left behind by the alkaline cleaning step. The strength of the alkaline and acid solutions and the duration of the cleaning steps are typically dependent on the durability of the soil. The water rinse removes any residual solution and soils, and cleans the surface prior to the equipment being returned on-line.
The process to remove a soil as described above includes at least one alkaline wash of the aqueous cleaning composition according to the invention.
The methods and compositions of the present invention can be used for enhanced soil removal at ambient temperatures, e.g., about > 20° C to < 65° C, preferably at about 40° C to about 60° C or at about 45° C to about 55° C or about 45° C to about 50° C. The present invention also provides for a reduction in the amount of chemistry and water consumed during the cleaning process. Thus, the present invention provides both energy and water savings, while achieving effective soil removal.
Surfactants
At least one surfactant or a surfactant mixture of an alkyl alkoxylate surfactant and/or an alkyl alkoxylate alkyl ether can be used in the aqueous detergent composition and methods of the present invention.
According to one aspect of the aqueous detergent composition the surfactant can be selected from the group comprising a CVCix-alkyl alkoxylate (EO)n/(PO)m and/or a Cx-Cix- alkyl alkoxylate (EO)n/(PO)m Ci-CValkyl ether, wherein n = 1 to 16 and m = 0 to 16.
Preferably the Ci-CValkyl of the ether can be butyl.
According to another aspect of the aqueous detergent composition the surfactant can be selected from the group comprising a CVCix-alkyl alkoxylate (EO)n/(PO)m and/or a CV Ci8-alkyl alkoxylate (EO)n/(PO)m Ci-CValkyl ether, wherein n = 2 to 14 and m = > 0 to 14. Preferably the Ci-CValkyl of the ether can be butyl.
According to another aspect of the aqueous detergent composition the surfactant can be selected from the group comprising a CVCix-alkyl alkoxylate (EO)n/(PO)m and/or a CV Ci8-alkyl alkoxylate (EO)n/(PO)m Ci-CValkyl ether, wherein n = 4 to 12 and m = > 0 to 10. Preferably the Ci-CValkyl of the ether can be butyl.
According to another aspect of the aqueous detergent composition the surfactant can be selected from the group comprising a Cs-Cis-alkyl alkoxylate (EO)n/(PO)m and/or a Cs- Cis-alkyl alkoxylate (EO)n/(PO)m Ci-CValkyl ether, wherein n = 5 to 10 and m = > 0 to 5. Preferably the Ci-CValkyl of the ether can be butyl.
According to another aspect of the aqueous detergent composition the surfactant can be selected from the group comprising a Cs-Cis-alkyl alkoxylate (EO)n and/or a Cs-Cis-alkyl alkoxylate (EO)n Ci-CValkyl ether, wherein n = 1 to 16. Preferably the Ci-CValkyl of the ether can be butyl.
According to another aspect of the aqueous detergent composition the surfactant can be selected from the group comprising a Cs-Cis-alkyl alkoxylate (EO)n and/or a Cs-Cis-alkyl alkoxylate (EO)n Ci-CValkyl ether, wherein n = 2 to 14. Preferably the Ci-CValkyl of the ether can be butyl.
According to another aspect of the aqueous detergent composition the surfactant can be selected from the group comprising a Cs-Cis-alkyl alkoxylate (EO)n and/or a Cs-Cis-alkyl alkoxylate (EO)n C i-Cs-alkyl ether, wherein n = 4 to 12. Preferably the C i-Cs-alkyl of the ether can be butyl.
According to another aspect of the aqueous detergent composition the surfactant can be selected from the group comprising a CVC ix-alkyl alkoxylate (EO)n and/or a CVCix-alkyl alkoxylate (EO)n C CValkyl ether, wherein n = 5 to 10, preferably 10. Preferably the C1-C5- alkyl of the ether can be butyl.
According to another aspect of the aqueous detergent composition the surfactant can be selected from the group comprising a Cio-Ci4-alkyl alkoxylate (EO)n and/or a C10-C14- alkyl alkoxylate (EO)n C2-C5-alkyl ether, preferably C4-alkyl ether, wherein n = 2 to 14, preferably 10. Preferably the C2-C5-alkyl of the ether can be butyl.
According to another aspect of the aqueous detergent composition the surfactant can be selected from the group comprising a Ci2-Ci4-alkyl alkoxylate (EO)n and/or a Ci2-Ci4- alkyl alkoxylate (EO)n CVCValkyl ether, preferably C4-alkyl ether, wherein n = 5 to 10, preferably 10. Preferably the CVCValkyl of the ether can be butyl.
According to another aspect of the aqueous detergent composition the surfactant can be Ci2-Ci4-alkyl alkoxylate (EO)n CVCValkyl ether, preferably C4-alkyl ether, wherein n = 5 to 10, preferably 10. Preferably the CVCValkyl of the ether can be butyl.
According to another aspect of the aqueous detergent composition the surfactant can be selected from the group comprising:
- Ci2-Ci4-alkyl alkoxylate (EO)n butyl ether, wherein n = 10; and/or
- Ci2-Ci5-alkyl alkoxylate (EO)n/(PO)m, wherein n = 5 and m = 2; and/or
- Ci2-Ci4-alkyl alkoxylate (EO)n/(PO)m, wherein n = 6 and m = 4; and/or
- Cio-Ci2-alkyl alkoxylate (EO)n/(PO)m, wherein n = 4 and m = 4.
According to another aspect of the aqueous detergent composition the surfactant can be selected from the group comprising a Ci2-Ci4-alkyl alkoxylate (EO)n butyl ether, wherein n = 10.
According to another aspect of the aqueous detergent composition the surfactant can be selected from the group comprising a Ci2-Cis-alkyl alkoxylate (EO)n/(PO)m, wherein n =
5 and m = 2.
According to another aspect of the aqueous detergent composition the surfactant can be selected from the group comprising a Ci2-Ci4-alkyl alkoxylate (EO)n/(PO)m, wherein n =
6 and m = 4. According to another aspect of the aqueous detergent composition the surfactant can be selected from the group comprising a Cio-Ci2-alkyl alkoxylate (EO)n/(PO)m, wherein n = 4 and m = 4.
According to another aspect the surfactant can be selected from the group comprising: a) lauryl ethoxylates:
Genapol® LA 020 lauryl ethoxylate with 2 EO Cl 2/ 14 alcohol, linear
Genapol® LA 030 lauryl ethoxylate with 3 EO Cl 2/ 14 alcohol, linear
Genapol® LA 040 lauryl ethoxylate with 4 EO Cl 2/ 14 alcohol, linear
Genapol® LA 050 lauryl ethoxylate with 5 EO Cl 2/ 14 alcohol, linear
Genapol® LA 070 lauryl ethoxylate with 7 EO Cl 2/ 14 alcohol, linear
Genapol® LA 080 lauryl ethoxylate with 8 EO Cl 2/14 alcohol, linear
Genapol® LA 090 lauryl ethoxylate with 9 EO Cl 2/ 14 alcohol, linear
Genapol® LA 110 lauryl ethoxylate with 11 EO Cl 2/ 14 alcohol, linear
Genapol® LA 200 lauryl ethoxylate with 20 EO Cl 2/ 14 alcohol, linear
Genapol® LA 2310 lauryl ethoxylate with 23 EO Cl 2/ 14 alcohol, linear
Genapol® LA 250 lauryl ethoxylate with 25 EO Cl 2/ 14 alcohol, linear
b) cocoalkyl ethoxylates:
Genapol® C 050 C12/14/16 alkyl ethoxylate with 5 EO C12/14/16 alcohol, linear
Genapol® C 100 Cl 2/ 14/ 16 alkyl ethoxylate with 10 EO Cl 2/ 14/ 16 alcohol, linear
Genapol® C 200 Cl 2/ 14/ 16 alkyl ethoxylate with 20 EO Cl 2/ 14/ 16 alcohol, linear
Genapol® C 250 Cl 2/14/16 alkyl ethoxylate with 25 EO Cl 2/ 14/ 16 alcohol, linear
Genapol® U 100 Cl 4/ 16/ 18 alkyl ethoxylate with 10 EO Cl 4/ 16/ 18 alcohol, unsaturated Genapol® U 200 Cl 4/ 16/ 18 alkyl ethoxylate with 20 EO Cl 4/ 16/ 18 alcohol, unsaturated Genapol® GS 080 Cl 2-20 alkyl ethoxylate with 8 EO Cl 2-20 alcohol, linear
c) oleyl ethoxylates:
Genapol® O 020 oleyl ethoxylate with 2 EO Cl 6/ 18 alcohol, linear, unsaturated
Genapol® O 050 oleyl(ethoxylate with 5 EO Cl 6/ 18 alcohol, linear, unsaturated
Genapol® O 080 oleyl ethoxylate with 8 EO Cl 6/ 18 alcohol, linear, unsaturated
Genapol® O 100 oleyl ethoxylate with 10 EO Cl 6/ 18 alcohol, linear, unsaturated
Genapol® O 120 oleyl ethoxylate with 12 EO Cl 6/ 18 alcohol, linear, unsaturated
Genapol® O 150 oleyl ethoxylate with 15 EO Cl 6/ 18 alcohol, linear, unsaturated
Genapol® O 200 oleyl ethoxylate with 20 EO Cl 6/ 18 alcohol, linear, unsaturated
Genapol® O 230 oleyl ethoxylate with 23 EO Cl 6/ 18 alcohol, linear, unsaturated
Genapol® O 250 oleyl ethoxylate with 25 EO Cl 6/ 18 alcohol, linear, unsaturated Genapol® O 300 oleyl ethoxylate with 30 EO Cl 6/ 18 alcohol, linear, unsaturated d) tallow alkyl ethoxylates:
Genapol® T 080 tallowalkyl ethoxylate with 8 EO Cl 6/18 alcohol, linear, unsaturated Genapol® T 110 tallowalkyl ethoxylate with 11 EO Cl 6/ 18 alcohol, linear, unsaturated Genapol® T 150 tallowalkyl ethoxylate with 15 EO Cl 6/ 18 alcohol, linear, unsaturated Genapol® T 200 tallowalkyl ethoxylate with 20 EO Cl 6/ 18 alcohol, linear, unsaturated Genapol® T 250 tallowalkyl ethoxylate with 25 EO Cl 6/ 18 alcohol; linear; unsaturated Genapol® T 500 tallowalkyl ethoxylate with 50 EO Cl 6/ 18 alcohol, linear, unsaturated Genapol® T 800 tallowalkyl ethoxylate with 80 EO Cl 6/18 alcohol, linear, unsaturated e) stearyl alcohol ethoxylates:
Genapol® HS 020 stearyl alcohol with 2 EO Cl 6/ 18 alcohol, linear, saturated
Genapol® HS 200 stearyl alcohol with 20 EO Cl 6/ 18 alcohol, linear, saturated
f) Cl 1 alkyl ethoxylates:
Emulsogen® EPN 118 Cl 1 alkyl ethoxylate with 11 EO Cl 1 alcohol, linear, little branching Emulsogen® EPN 287 Cl 1 alkyl ethoxylate with 28 EO Cl 1 alcohol, linear, little branching Emulsogen® EPN 407 Cl 1 alkyl ethoxylate with 40 EO Cl 1 alcohol, linear, little branching Emulsogen® LCN 050 Cl 1 alkyl ethoxylate with 5 EO Cl 1 alcohol, branched
Emulsogen® LCN 070 Cl 1 alkyl ethoxylate with 7 EO Cl 1 alcohol, branched
Emulsogen® LCN 088 Cl 1 alkyl ethoxylate with 8 EO Cl 1 alcohol, branched
Emulsogen® LCN 118 C 11 alkyl ethoxylate with 11 EO C 11 alcohol, branched
Emulsogen® LCN 158 Cl 1 alkyl ethoxylate with 15 EO Cl 1 alcohol, branched
Emulsogen® LCN 217 Cl 1 alkyl ethoxylate with 21 EO alcohol, branched
Emulsogen® LCN 287 Cl 1 alkyl ethoxylate with 28 EO Cl 1 alcohol, branched
Emulsogen® LCN 407 C 11 alkyl ethoxylate with 40 EO C 11 alcohol, branched
Emulsogen® LCN 506 Cl 1 alkyl ethoxylate with 50 EO Cl 1 alcohol, branched
Genapol® UD 030 Cl 1 alkyl ethoxylate with 3 EO Cl 1 alcohol, linear, little branching
Genapol® UD 050 Cl 1 alkyl ethoxylate with 5 EO Cl 1 alcohol, linear, little branching
Genapol® UD 079 Cl 1 alkyl ethoxylate with 7 EO Cl 1 alcohol, linear, little branching
Genapol® UD 080 Cl 1 alkyl ethoxylate with 8 EO Cl 1 alcohol, linear, little branching
Genapol® UD 088 Cl 1 alkyl ethoxylate with 8 EO Cl 1 alcohol, linear, little branching
Genapol® UD 110 Cl 1 alkyl ethoxylate with 11 EO Cl 1 alcohol, linear, little branching g) isotridecyl ethoxylates:
Genapol® X 020 isotridecyl ethoxylate with 2 EO C13 alcohol, branched Genapol® X 050 isotridecyl ethoxylate with 5 EO C13 alcohol, branched Genapol® X 060 isotridecyl ethoxylate with 6 EO C13 alcohol, branched
Genapol® X 065 isotridecyl ethoxylate with 6.5 EO C13 alcohol, branched
Genapol® X 080 isotridecyl ethoxylate with 8 EO C13 alcohol, branched
Genapol® X 089 isotridecyl ethoxylate with 8 EO C13 alcohol, branched
Genapol® X 090 isotridecyl ethoxylate with 9 EO C13 alcohol, branched
Genapol® X 100 isotridecyl ethoxylate with 10 EO C13 alcohol, branched
Genapol® X 150 isotridecyl ethoxylate with 15 EO C13 alcohol, branched
Genapol® X 158 isotridecyl ethoxylate with 15 EO C13 alcohol, branched
Genapol® X 307 isotridecyl ethoxylate with 30 EO C13 alcohol, branched
Genapol® X 407 isotridecyl ethoxylate with 40 EO C13 alcohol, branched
Genapol® X 1003 isotridecyl ethoxylate with 100 EO C13 alcohol, branched
Genapol® X 1005 isotridecyl ethoxylate with 100 EO C13 alcohol, branched
Genapol® 1879 isotridecyl ethoxylate with 15 EO C13 alcohol, branched
Genapol® 3214 isotridecyl ethoxylate with 25 EO C13 alcohol, branched
h) isodecyl ethoxylates:
Genapol® ID 030 isodecyl ethoxylate with 3 EO C10 alcohol, branched
Genapol® ID 060 isodecyl ethoxylate with 6 EO C10 alcohol, branched
Genapol® ID 070 isodecyl ethoxylate with 7 EO C10 alcohol, branched
Genapol® EP 1022 isodecyl ethoxylate with 2 EO, 2PO C10 alcohol, branched i) oxo-process alcohol ethoxylates:
Genapol® OX 030 Cl 2/15 alkyl ethoxylate with 3 EO Cl 2/ 15 alcohol, little branching Genapol® OX 050 Cl 2/15 alkyl ethoxylate with 5 EO Cl 2/ 15 alcohol, little branching Genapol® OX 070 Cl 2/ 15 alkyl ethoxylate with 7 EO Cl 2/ 15 alcohol, little branching Genapol® OX 080 Cl 2/15 alkyl ethoxylate with 8 EO Cl 2/15 alcohol, little branching Genapol® OX 100 Cl 2/ 15 alkyl ethoxylate with 10 EO Cl 2/ 15 alcohol, little branching Genapol® OX 109 Cl 2/ 15 alkyl ethoxylate with 10 EO Cl 2/ 15 alcohol, little branching Genapol® OA 030 04/15 oxo-process alcohol with 3 EO 04/15 oxo-process alcohol Genapol® OA 3070 04/15 oxo alcohol, 3EO, 7PO 04/15 oxo-process alcohol Genapol® OA 040 04/15 oxo-process alcohol with 4 EO 04/15 oxo-process alcohol Genapol® OA 050 04/15 oxo-process alcohol with 5 EO 04/15 oxo-process alcohol Genapol® OA 070 04/15 oxo-process alcohol with 7 EO 04/15 oxo-process alcohol Genapol® OA 080 04/15 oxo-process alcohol with 8 EO 04/15 oxo-process alcohol Hostacerin® T3 cetyl alcohol with 3 EO 06 alcohol, linear, saturated Hostacerin® CS 200 cetyl alcohol with 20 EO C16 alcohol, linear, saturated
Emulsogen® HCO 040 PEG-40 castor oil, hydrogenated Cl 6/ 18 hydroxyalcohol, linear, saturated
Emulsogen® HCO 060 PEG-60 castor oil, hydrogenated Cl 6/ 18 hydroxyalcohol, linear, saturated
j) alcohol alkoxylates, EO/PO:
Genapol® EO 0244 Cl 0/12 alcohol with 4 EO and 4 PO Cl 0/12 alcohol
Genapol® EP 1182 Cl 1 oxo-process alcohol with 8 EO and 2 PO Cl 1 oxo-process alcohol,
Genapol® EP 2464 Cl 2/ 14 alcohol having 6 EO and 4 PO Cl 2/ 14 alcohol
Genapol® EP 2544 Cl 2/15 oxo-process alcohol with 4 EO and 4 PO Cl 2/15 oxo-process alcohol
Genapol® EP 2564 C12/15 oxo-process alcohol with 6 EO and 4 PO C12/15 oxo-process alcohol
Genapol® EP 2584 Cl 2/15 oxo-process alcohol with 8 EO and 4 PO Cl 2/15 oxo-process alcohol
Genapol® EP2525 Cl 2/15 oxo-process alcohol with 2 EO and 5 PO Cl 2/15 oxo-process alcohol
Genapol® EP 2552 C12/15 oxo-process alcohol with 5 EO and 2 PO C12/15 oxo-process alcohol.
However, alkyl alkoxylate alkyl ether of C12/C14-10EO, n-butyl end-capped, which is known as Genapol® BE 2410, can be most preferred. It has been surprisingly found that composition comprising alkyl alkoxylate alkyl ether of C12/C14-10EO, n-butyl end-capped shows the lowest foam formation compared with the other composition of the present invention.
According to one embodiment the aqueous detergent composition may comprises in addition at least one further anionic surfactant and/or further non-ionic surfactant. The additional surfactant chosen may be compatible with the surface to be cleaned. The additional surfactant can be preferably a non-ionic surfactant. It can be preferred that the additional surfactant may be selected from the group comprising of linear alkyl benzene sulfonates, alcohol sulfonates, amine oxides, alkyl phenol ethoxylates, polyethylene glycol esters and mixtures thereof.
In addition, the level and degree of low- foaming under the conditions of use and in subsequent recovery of the composition may be a factor for selecting particular surfactants and mixtures of surfactants. In particular, the nonionics and anionics may be used in combination.
It can be more preferred that the aqueous detergent composition is may be free of an C8 to C14 alkyl sulfate and/or 2-ethylhexyl sulfate. However, it can be even more preferred that the aqueous detergent composition is may be free of an anionic surfactant.
The examples mentioned in the specification are merely specific illustrations of the numerous surfactants which may find application within the scope of this invention. It should be understood that the selection of particular surfactants or combinations of surfactants may be based on a number of factors including compatibility with the surface to be cleaned at the intended use concentration and the intended environmental conditions including temperature and pH.
In some embodiments, the amount of total surfactant in the aqueous detergent composition, preferably in a concentrated aqueous detergent composition, can be about > 0.1 wt.-% to about < 15 wt.-%. Acceptable levels of surfactants include about > 0.5 wt.-% to about < 12 wt.-%, about > 1 wt.-% to about < 10 wt.-%, about > 3 wt.-% to about < 9 wt.-%, or about > 6 wt.-% to about < 8 wt.-%.
In some embodiments, the amount of total surfactant of an alkyl alkoxylate surfactant and/or an alkyl alkoxylate alkyl ether in the aqueous detergent composition, preferably in a concentrated aqueous detergent composition, can be about > 0. 1 wt.-% to about < 15 wt.-%, preferably about > 0. 5 wt.-% to about < 12 wt.-%, further preferred about > 1 wt.-% to about < 10 wt.-% and in addition preferred about > 3 wt.-% to about < 9 wt.-% or preferably about > 6 wt.-% to about < 8 wt.-%.
In some embodiments, the amount of total surfactant of alkyl (EO)n/(PO)m-alkoxylate surfactant, wherein n = 1 to 12, or 2 to 10, and m = 0 to 12, or 1 to 10, or 5 to 8, in the aqueous detergent composition, preferably in a concentrated aqueous detergent composition, can be about > 0. 1 wt.-% to about < 15 wt.-%, preferably about > 0. 5 wt.-% to about < 12 wt.-%, further preferred about > 1 wt.-% to about < 10 wt.-% and in addition preferred about > 3 wt.-% to about < 9 wt.-% or preferably about > 6 wt.-% to about < 8 wt.-%.
In some embodiments, the amount of total surfactant of alkyl (EO)n-alkoxylate surfactant, wherein n = 1 to 12, or 5 to 10 in the aqueous detergent composition, preferably in a concentrated aqueous detergent composition, can be about > 0. 1 wt.-% to about < 15 wt.-%, preferably about > 0. 5 wt.-% to about < 12 wt.-%, further preferred about > 1 wt.-% to about < 10 wt.-% and in addition preferred about > 3 wt.-% to about < 9 wt.-% or preferably about > 6 wt.-% to about < 8 wt.-%. In some embodiments, the amount of total surfactant of alkyl (EO)n-alkoxylate alkyl ether surfactant, wherein n = 1 to 12, or 5 to 10 in the aqueous detergent composition, preferably in a concentrated aqueous detergent composition, can be about > 0. 1 wt.-% to about < 15 wt.-%, preferably about > 0. 5 wt.-% to about < 12 wt.-%, further preferred about
> 1 wt.-% to about < 10 wt.-% and in addition preferred about > 3 wt.-% to about < 9 wt.-% or preferably about > 6 wt.-% to about < 8 wt.-%.
In some embodiments, the amount of total surfactant of alkyl (PO)n-alkoxylate surfactant, wherein n = 1 to 12, or 5 to 10 in the aqueous detergent composition, preferably in a concentrated aqueous detergent composition, can be about > 0. 1 wt.-% to about < 15 wt.-%, preferably about > 0. 5 wt.-% to about < 12 wt.-%, further preferred about > 1 wt.-% to about < 10 wt.-% and in addition preferred about > 3 wt.-% to about < 9 wt.-% or preferably about > 6 wt.-% to about < 8 wt.-%.
In some embodiments, the amount of total surfactant of alkyl (PO)n-alkoxylate alkyl ether surfactant, wherein n = 1 to 12, or 5 to 10 in the aqueous detergent composition, preferably in a concentrated aqueous detergent composition, can be about > 0. 1 wt.-% to about < 15 wt.-%, preferably about > 0. 5 wt.-% to about < 12 wt.-%, further preferred about
> 1 wt.-% to about < 10 wt.-% and in addition preferred about > 3 wt.-% to about < 9 wt.-% or preferably about > 6 wt.-% to about < 8 wt.-%.
Alkalinity Source
In some aspects, the compositions of the present invention include a source of alkalinity. Exemplary alkaline sources suitable for use with the present invention include, but are not limited to are, basic salts, amines, alkanol amines, carbonates, silicates, and mixtures thereof, preferably the source of alkalinity is selected from the group comprising sodium hydroxide, potassium hydroxide or a mixture thereof, most preferred the source of alkalinity can be triethanol amine.
Preferably, the source of alkalinity is selected from the group comprising alkanol amines, sodium hydroxide, potassium hydroxide or a mixture thereof, most preferred is triethanol amine.
According to a more preferred aspect the aqueous detergent composition may comprise a sources of alkalinity wherein the sources of alkalinity include alkanol amines, and most preferred the sources of alkalinity is triethanol amine. The amount of alkaline source present is dependent on a variety of factors including, for example, the type of surface to be cleaned, and the amount and type of soil present on the surface.
In some embodiments of the aqueous detergent composition, the amount of alkaline source present in an aqueous detergent composition can be about > 1 wt.-% to about < 15 wt.- %, preferably about > 3 wt.-% to about < 10 wt.-%, and further preferred about > 6 wt.-% to about < 8 wt.-%; wherein the source of alkalinity can preferably triethanol amine.
In some embodiments of the aqueous detergent composition, the amount of alkaline source present in an additional diluted aqueous detergent composition can be about > 0.001 wt.-% to about < 1 wt.-%, preferably about > 0.01 wt.-% to about < 0.5 wt.-%, and further preferred about > 0.02 wt.-% to about < 0.05 wt.-%; wherein the source of alkalinity can be preferably triethanol amine.
It is understood that the“surfactants” of the aqueous detergent composition are not regarded as an alkaline source.
According to one aspect the aqueous detergent composition can be free of an alkali hydroxide
Organic solvent
According to one aspect the aqueous detergent composition comprises at least one organic solvent.
The organic solvent can be a C2 to Cx alcohol. The organic solvent can be preferably a mixture of at least two alcohols selected from the group of C2 to Cx alcohols.
The C2 to Cx alcohol of the organic solvent can be a polyol.
A preferred polyol can be C2-CY, -alkyl diol or C2-CY, -alkyl triol. Further preferred the polyol containing only carbon, hydrogen and oxygen atoms.
The C2-CY, -alkyl diol can be preferably selected from dihydroxypropane, 1 ,2- propanediol, l,3-propandiol, butanediol, l,2-butanediol, l,3-butanediol, l,4-butanediol, hexylene glycol, glycerol, 2-methyl-2,4-pentanediol.
Suitable glycols include, but are not limited to, ethylene glycol (monoethylene glycol or MEG), diethylene glycol (propylene glycol or butoxy diglycol or DEG), triethylene glycol (TEG), tetraethylene glycol (TETRA EG), propylene glycol, dipropylene glycol, hexylene glycol, or combinations thereof.
The C2-CY, -alkyl triol can be l,2,3-trihydroxypropane, also named glycerin.
According to an embodiment the mixture of at least two alcohols may comprises: a) at least one C2-C6-alkyl diol, preferably dihydroxypropane;
b) at least one C2-C6-alkyl triol, preferably glycerin.
According to an embodiment the mixture of at least two alcohols may comprises: a) at least one C2-CY, -alkyl diol, preferably dihydroxypropane;
b) at least one C2-CY, -alkyl triol, preferably glycerin;
wherein the mixture may has a ratio of a) to b) of 6: 1 to 2: 1, or 5: 1 to 3: 1, or 4: 1 to 3.5 : 1.
In some embodiments of the aqueous detergent composition, the amount of the organic solvent, preferably a C2-CY, -alkyl diol and/or C2-CY, -alkyl triol, may be present in the aqueous detergent composition from about > 1 wt.-% to about < 30 wt.-%, preferably about > 1.5 wt.-% to about < 4.5 wt.-%, further preferred about > 2 wt.-% to about < 4 wt.-%, and more preferred about > 2.5 wt.-% to about < 3.5 wt.-%.
In some embodiments of the aqueous detergent composition, the amount of the organic solvent, preferably a C2-CY, -alkyl diol and/or C2-Ce-alkyl triol, may be present in the aqueous detergent composition from about > 1 wt.-% to about < 30 wt.-%, preferably about > 1.5 wt- % to about < 25 wt.-%, further preferred about > 2 wt.-% to about < 20 wt.-%, and more preferred about > 2.5 wt.-% to about < 15 wt.-%; or from about > 1 wt.-% to about < 10 wt- %, or from about > 1 wt.-% to about < 5 wt.-%, or from about > 2 wt.-% to about < 5 wt.-%.
In some embodiments of the aqueous detergent composition, the amount of the alcohol, preferably a C2-CY, -alkyl diol and/or C2-CY, -alkyl triol, may be present in a diluted aqueous detergent composition, from about > 0.001 wt.-% to about < 0.5 wt.-%, preferably about > 0.006 wt.-% to about < 0.2 wt.-%, and more preferred about > 0.01 wt.-% to about < 0.1 wt.-%.
In some embodiments of the aqueous detergent composition, the amount of the C2-Ce- alkyl diol may be present in a concentrated aqueous detergent composition, from about > 1 wt.-% to about < 5 wt.-%, preferably about > 1.5 wt.-% to about < 4.5 wt.-%, further preferred about > 2 wt.-% to about < 4 wt.-%, and more preferred about > 2.5 wt.-% to about < 3.5 wt.- %.
In some embodiments of the aqueous detergent composition, the amount of the C2-Ce- alkyl triol may be present in a concentrated aqueous detergent composition, from about > 1 wt.-% to about < 5 wt.-%, preferably about > 1.5 wt.-% to about < 4.5 wt.-%, further preferred about > 2 wt.-% to about < 4 wt.-%, and more preferred about > 2.5 wt.-% to about < 3.5 wt.- %.
Hydrotropes Solubilizing intermediaries called hydrotropes. A hydrotrope is a compound that solubilizes hydrophobic compounds in aqueous solutions. Typically, hydrotropes consist of a hydrophilic part and a hydrophobic part (like surfactants) but the hydrophobic part is generally too small to cause spontaneous self-aggregation. Hydrotropes may be present in the aqueous detergent composition.
Hydrotropes that can be suitable used are selected from the group comprising aromatic hydrocarbon sulfonate, preferably xylene sulfonate, toluene sulfonate, or cumene sulfonate; or n-octane sulfonate; or their sodium-, potassium- or ammonium salts or as salts of organic ammonium bases.
In some preferred embodiments the hydrotrope may be selected from the group comprising of a xylene sulfonate, toluene sulfonate, or cumene sulfonate, n-octane sulfonate, and/or acids thereof and also more preferred cumene sulfonate.
In some embodiments, Na-cumolsulfonate, linear alkylbenzene sulfonates (LAS) and/or xylene sulfonate, cumolsulfonate may be suitable to use as hydrotrope and having an improved wetting effect.
According to a more preferred aspect the aqueous detergent composition may comprise at least one hydrotrope that is a cumene sulfonate.
In some embodiments, the aqueous detergent composition, preferably the concentrated aqueous detergent composition, may comprise in addition a hydrotrope, preferably
cumolsulfonate or the acid thereof, in the range of about > 0 wt.-% to about < 10 wt.-%, preferably about > 1 wt.-% to about < 5 wt.-% and more preferred about > 2 wt.-% to about < 4 wt.-%, by weight of the total aqueous detergent composition.
In some embodiments, the aqueous detergent composition, preferably a diluted aqueous detergent composition may comprise a hydrotrope, preferably cumolsulfonate or the acid thereof, in the range of about > 0 wt.-% to about < 0.1 wt.-%, preferably about > 0 wt.-% to about < 0.3 wt.-%, further preferred > 0.03 wt.-% to about < 0.15 wt.-%, and more preferred about > 0.06 wt.-% to about < 0.12 wt.-%, by weight of the total aqueous detergent composition.
It should be understood that the hydrotrope can present in the form of an acid or salt thereof, depending on the pH of the aqueous detergent composition.
It should be understood that the aqueous detergent composition can be free of a hydrotrope.
According to one aspect the aqueous detergent composition can be free of a hydrotrope. According to one aspect the aqueous detergent composition can be free of a hydrotrope, except cumene sulfonate.
Polymeric polycarboxylate
The aqueous detergent composition may preferably exclude a polymeric
polycarboxylate. However, the aqueous detergent composition may include at least one polymeric polycarboxylate. The polymeric polycarboxylates suitable for use include those having a pendant carboxylate (— C02) groups and include, for example, polyacrylic acid, maleic/olefin copolymer, acrylic/maleic copolymer, polymethacrylic acid, acrylic acid- methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile -methacrylonitrile copolymers, and the like.
Further suitable copolymeric polycarboxylates are particularly those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
Copolymers of acrylic acid with maleic acid, which comprise about 50 wt.- % to about 90 wt.- % acrylic acid and about 50 wt.- % to about 10 wt.- % maleic acid, have proven to be particularly suitable.
More preferred suitable polycarboxylates are the polyacrylates, which preferably have a molecular weight of 1,000 to 50,000 g/mol and preferably about 2,000 to 10,000 g/mol.
In some embodiments the aqueous detergent composition may comprise a polymeric polycarboxylate, preferably a polyacrylate having a molecular weight of about 500 Mw to about 50000 Mw, preferably about 1000 Mw to about 20000 Mw, in addition preferred about 3000 Mw to about 10000 Mw and more preferred about 4000 Mw to about 6000 Mw, wherein the molecular weight of the polymeric polycarboxylate is based on a totally neutralized sodium polymeric polycarboxylate.
More preferred is a polymeric polycarboxylate that is a polyacrylate.
In some embodiments an aqueous detergent composition, preferably a concentrated aqueous detergent composition, may comprise the polymeric polycarboxylate, preferably polyacrylate, in an amount of about > 0 wt.-% to about < 5 wt.-%, preferably about > 0.5 wt.- % to about < 2 wt.-% and more preferred about > 0.7 wt.-% to about < 1 wt.-% of a polycarboxylate, preferably polyacrylate of a polymeric polycarboxylate, based on the total weight amount of the aqueous detergent composition.
In some embodiments an aqueous detergent composition, preferably a concentrated aqueous detergent composition, may comprise the polymeric polycarboxylate, preferably polyacrylate, in an amount of about > 0 wt.-% to about < 5 wt.-%, preferably about > 0.5 wt.- % to about < 2 wt.-% and more preferred about > 0.7 wt.-% to about < 1 wt.-% of a polycarboxylate, preferably polyacrylate having about 4000 Mw to about 6000 Mw, based on the total weight amount of the aqueous detergent composition.
In some embodiments an aqueous detergent composition, preferably a diluted aqueous detergent composition, may comprise the polymeric polycarboxylate, preferably polyacrylate, in an amount of about > 0 wt.-% to about < 0.15 wt.-%, preferably about > 0.015 wt.-% to about < 0.06 wt.-% and more preferred about > 0.021 wt.-% to about < 0.03 wt.-% of a polycarboxylate, preferably polyacrylate of a polymeric polycarboxylate, based on the total weight amount of the aqueous detergent composition.
In some embodiments an aqueous detergent composition, preferably a diluted aqueous detergent composition, may comprise the polymeric polycarboxylate, preferably polyacrylate, in an amount of about > 0 wt.-% to about < 0.15 wt.-%, preferably about > 0.015 wt.-% to about < 0.06 wt.-% and more preferred about > 0.021 wt.-% to about < 0.03 wt.-% of a polycarboxylate, preferably polyacrylate having about 4000 Mw to about 6000 Mw, based on the total weight amount of the aqueous detergent composition.
By virtue of their superior solubility, preferred representatives of this group of polymeric polycarboxylate are the short-chain polyacrylates, which have average molecular weight (Mw), based on free acids, of 2,000 g/mol to 10,000 g/mol and, more particularly, 4,000 g/mol to 6,000 g/mol.
It should be understood that the aqueous detergent composition can be free of a polymeric polycarboxylate.
According to one aspect the aqueous detergent composition can be free of a polymeric polycarboxylate, except a polyacrylate.
Water
Water is added add. 100 wt.-% to the aqueous detergent composition. The water content, of the aqueous detergent composition is simply determined by subtracting the weight- % amounts of all the other components, based on the total weight of the aqueous detergent composition, except the solvent, from 100 wt. %.
In some embodiments an aqueous detergent composition comprises water in an amount of about > 30 wt.-%, preferably about > 50 wt.-%, further preferred about > 60 wt.-%, and in addition preferred about > 90 wt.-%, based on the total weight amount of the aqueous detergent composition. In some embodiments an aqueous detergent composition comprises water in an amount of about > 30 wt.-% and < 95 wt.-%, preferably about > 50 wt.-% and < 95 wt.-%, and further preferred about > 60 wt.-% to about < 90 wt.-%, based on the total weight amount of the aqueous detergent composition.
In some embodiments an aqueous detergent composition may comprise water in an amount of about > 98 wt.-%, preferably about > 99 wt.-% and further preferred about > 99.9 wt.-%, based on the total weight amount of the aqueous detergent composition.
A diluted aqueous detergent composition is obtainable by diluting a concentrated liquid composition with a water, in a ratio of an aqueous detergent composition, preferably a concentrated liquid composition, to water, of about 1 : 10 to 1 : 1000, preferably of about 1 : 50 to 1 : 500, in particular of about 1 : 100 to 1 : 250, and also preferred of about 1 : 30 to 1 : 50.
Chelating agent
The aqueous detergent composition may preferably exclude a chelating agent.
However, the aqueous detergent composition may comprises a chelating agent. The chelating agent can be selected from the group of sodium gluconate, pentasodium salt of
diethylenetriamine pentaacetic acid, sodium glucoheptonate, salts of ethylene diamine tetraacetic acid, salts of ethylene diamine tetraacetic acid, salts of hydroxyethyl ethylene diamine triacetic acid, salts of hydroxyethyl ethylene diamine triacetic acid, salts of nitrilotriacetic acid, salts of nitrilotriacetic acid, diethanolglycine sodium salt,
ethanoldiglycine disodium salt, salts of hydroxymonocarboxylic acid compounds, salts of hydroxydicarboxylic acid compounds, salts of amine containing carboxylic acids, terasodium N,N-bis(carboxylatomethyl)-L-glutamate (GDLA) and mixtures thereof.
In particular preferred is at least one chelating agent that exhibits soil removal properties when used at a pH of at least about 11 to about 14 and more preferred at a pH in the range of about 12 to about 13.5. The chelating agent is provided for tying up metals in the soil to assist in cleaning and detergency. The chelating agent can be provided as part of the solid alkaline composition. Exemplary chelating agent that exhibit soil removal properties at a pH of greater than about 12.0 to about 13.5 that can be used according to the invention include sodium gluconate, pentasodium salt of diethylenetriamine pentaacetic acid (available under the name Versenex 80), sodium glucoheptonate, ethylene diamine tetraacetic acid (EDTA), salts of ethylene diamine tetraacetic acid, hydroxyethyl ethylene diamine triacetic acid (HEDTA), salts of hydroxyethyl ethylene diamine triacetic acid, nitrilotriacetic acid (NT A), salts of nitrilotriacetic acid, diethanolglycine sodium salt (DEG), ethanoldiglycine disodium salt (EDG), tetrasodium N,N-bis(carboxylatomethyl)-L-glutamate (GLDA), methyl glycine diacetic acid (MGDA) and mixtures thereof. Exemplary salts of ethylene diamine tetraacetic acid include disodium salts, tetrasodium salts, diammonium salts, and trisodium salts. An exemplary salt of hydroxyethyl ethylene diamine triacetic acid is the trisodium salt.
It should be understood that the chelating agent can include mixtures of different chelating agent agents.
In some embodiments an aqueous detergent composition, preferably a concentrated aqueous detergent composition, may comprise a chelating agent, preferably a gluconate, in an amount of about > 0.1 wt.-% to about < 3 wt.-%, preferably about > 0.5 wt.-% to about < 2 wt.-%, further preferred about > 1.0 wt.-% to about < 1.7 wt.-% and more preferred about >
1.2 wt.-% to about < 1.4 wt.-%, based on the total weight amount of the aqueous detergent composition.
In some embodiments an aqueous detergent composition, preferably a diluted aqueous detergent composition, may comprise a chelating agent, preferably a gluconate, in an amount of about > 0 wt.-% to about < 0.1 wt.-%, preferably about > 0.01 wt.-% to about < 0.05 wt.-%, further preferred about > 0.02 wt.-% to about < 0.04 wt.-% and more preferred about > 0.0375 wt.-% to about < 0.0395 wt.-%, based on the total weight amount of the aqueous detergent composition.
In some embodiments an aqueous detergent composition, preferably a concentrated aqueous detergent composition, may comprise a tetrasodium N,N-bis(carboxylatomethyl)-L- glutamate (GLDA), in an amount of about > 0 wt.-% to about < 5 wt.-%, preferably about > 0.5 wt.-% to about < 2 wt.-% and more preferred about > 0.7 wt.-% to about < 1 wt.-%, based on the total weight amount of the aqueous detergent composition.
In some embodiments an aqueous detergent composition, preferably a diluted aqueous detergent composition, may comprise a tetrasodium N,N-bis(carboxylatomethyl)-L-glutamate (GLDA), in an amount of about > 0 wt.-% to about < 0.2 wt.-%, preferably about > 0.005 wt.- % to about < 0.05 wt.-%, further preferred about > 0.0228 wt.-% to about < 0.0232 wt.-%, based on the total weight amount of the aqueous detergent composition.
In some embodiments an aqueous detergent composition, preferably a concentrated aqueous detergent composition, may comprise a methyl glycine diacetic acid (MGDA), in an amount of about > 0 wt.-% to about < 5 wt.-%, preferably about > 0.5 wt.-% to about < 2 wt- % and more preferred about > 0.7 wt.-% to about < 1 wt.-%, based on the total weight amount of the aqueous detergent composition. In some embodiments an aqueous detergent composition, preferably a diluted aqueous detergent composition, may comprise a methyl glycine diacetic acid (MGDA), in an amount of about > 0 wt.-% to about < 0.2 wt.-%, preferably about > 0.005 wt.-% to about < 0.05 wt.- %, further preferred about > 0.018 wt.-% to about < 0.022 wt.-%, based on the total weight amount of the aqueous detergent composition.
According to one aspect the aqueous detergent composition can be free of a chelating agent.
According to one aspect the aqueous detergent composition can be free of a chelating agent except gluconate.
According to one aspect the aqueous detergent composition can be free of a chelating agent except tetrasodium N,N-bis(carboxylatomethyl)-L-glutamate (GLDA).
According to one aspect the aqueous detergent composition can be free of a chelating agent except methyl glycine diacetic acid (MGDA).
Sequestering agent
The aqueous detergent composition may preferably exclude a sequestering agent.
In some embodiments, the aqueous detergent composition may include at least one sequestering.
Exemplary commercially available sequestering agents for use with aqueous detergent composition of the present invention may include, but are not limited to: sodium
tripolyphosphate available from Innophos; Trilon A® available from BASF; Versene 100®, Low NTA Versene ®, Versene Powder®, and Versenol 120® all available from Dow;
Dissolvine D-40 available from Akzo; and sodium citrate.
In some embodiments, dipicolinic acid and/or phosphonic acid and corresponding salts thereof are suitable for use as sequestering agents with the methods of the invention.
Phosphonates are suitable for use as sequestering agents with the methods of the invention and can be selected from the group comprising 2-aminoethylphosphonic acid (AEPn); dimethyl methylphosphonate (DMMP); 1 -hydroxy ethylidene-l,l-diphosphonic acid (HEDP); amino tris(methylene phosphonic acid) (ATMP); ethylenediamine tetra(methylene phosphonic acid) (EDTMP); tetramethylenediamine tetra(methylene phosphonic acid) TDTMP); hexamethylenediamine tetra(methylene phosphonic acid) (HDTMP);
diethylenetriamine penta(methylene phosphonic acid) (DTPMP); phosphonobutane- tricarboxylic acid (PBTC); N-(phosphonomethyl)iminodiacetic acid (PMIDA); 2- carboxyethyl phosphonic acid (CEP A); 2-hydroxyphosphonocarboxylic acid (HPAA); amino- tris-(methylene-phosphonic acid) (AMP); and/or salts thereof.
Aminophosphonates are also suitable for use as sequestering agents with the methods of the invention and include ethylenediaminetetramethylene phosphonates,
nitrilotrismethylene phosphonates, and diethylenetriamine-(pentamethylene phosphonate) for example. These aminophosphonates commonly contain alkyl or alkenyl groups with less than 8 carbon atoms.
In some embodiments, the aqueous detergent composition, preferably a concentrated aqueous detergent composition, comprises in an amount of about > 0 wt.-% to about < 5 wt- %, preferably about > 0.1 wt.-% to about < 2 wt.-%, further preferred > 0.3 wt.-% to about < 1 wt.-%, and also preferred > 0.5 wt.-% to about < 0.7 wt.-%, a sequestering agent, preferably phosphonobutane-tricarboxylic acid (PBTC), based on the total weight amount of the aqueous detergent composition.
In some embodiments, the aqueous detergent composition, preferably a diluted aqueous detergent composition, comprises in an amount of about > 0 wt.-% to about < 0.2 wt.-%, preferably about > 0.005 wt.-% to about < 0.05 wt.-%, further preferred > 0.01 wt.-% to about < 0.025 wt.-%, and also preferred > 0.018 wt.-% to about < 0.019 wt.-%, a sequestering agent, preferably phosphonobutane-tricarboxylic acid (PBTC), based on the total weight amount of the aqueous detergent composition.
According to one aspect the aqueous detergent composition can be free of a sequestering agent.
According to one aspect the aqueous detergent composition can be free of a sequestering agent except phosphonobutane-tricarboxylic acid (PBTC).
Penetrants
In some embodiments, a penetrant may be used with the aqueous detergent composition of the present invention.
In some embodiments, the penetrant is water miscible.
Examples of suitable penetrants include, but are not limited to short chain ethoxylated alcohols and phenol (having 1-6 ethoxylate groups). Organic solvents are also suitable penetrants. Examples of suitable organic solvents, for use as a penetrant, include esters, ethers, ketones, amines, and nitrated and chlorinated hydrocarbons.
Ethoxylated alcohols are also suitable for use with the methods of the present invention. Examples of ethoxylated alcohols include, but are not limited to, alky, aryl, and alkylaryl alkloxylates. These alkloxylates may be further modified by capping with chlorine-, bromine-, benzyl-, methyl-, ethyl-, propyl-, butyl- and alkyl-groups. Ethoxylated alcohols may be present in the aqueous detergent composition from about > 0.1 wt% to about > 20 wt%.
Fatty acids are also suitable for use as penetrants in the methods of the present invention. Some non-limiting examples of fatty acids are CY, to Ci2 straight or branched fatty acids. In some embodiments, fatty acids used in the methods of the present invention are liquid at room temperature.
In some embodiments, a penetrant for use in the methods of the present invention includes water soluble glycol ethers. Examples of glycol ethers include dipropylene glycol methyl ether (available under the trade designation DOWANOL DPM from Dow Chemical Co.), diethylene glycol methyl ether (available under the trade designation DOWANOL DM from Dow Chemical Co.), propylene glycol methyl ether (available under the trade designation DOWANOL PM from Dow Chemical Co.), and ethylene glycol monobutyl ether (available under the trade designation DOWANOL EB from Dow Chemical Co.).
In some embodiments, the aqueous detergent composition, preferably a concentrated aqueous detergent composition, comprises in an amount of about > 0 wt.-% to about < 10 wt.- %, preferably about > 1 wt.-% to about < 8 wt.-%, further preferred > 3 wt.-% to about < 6 wt.-%, and also preferred > 4 wt.-% to about < 5 wt.-%, a penetrant, preferably diethylene glycol monobutyl ether, based on the total weight amount of the aqueous detergent composition.
In some embodiments, the aqueous detergent composition, preferably a diluted aqueous detergent composition, comprises in an amount of about > 0 wt.-% to about < 0.4 wt.-%, preferably about > 0.01 wt.-% to about < 0.3 wt.-%, further preferred > 0.05 wt.-% to about < 0.2 wt.-%, and also preferred > 0.130 wt.-% to about < 0.135 wt.-%, a penetrant, preferably diethylene glycol monobutyl ether, based on the total weight amount of the aqueous detergent composition.
According to one aspect the aqueous detergent composition can be free of a penetrant.
According to one aspect the aqueous detergent composition can be free of a penetrant except diethylene glycol monobutyl ether.
Concentrate The aqueous detergent composition can be presented in a concentrated liquid form. The concentrates include a liquid medium, preferably water, and relatively large
concentrations of the active cleaning component or cleaning components.
The concentrated aqueous detergent composition may have a pH in the range of about > 8.5 and < 12, preferably of about > 9 and < 11.5, further preferred of about > 9.5 and < 11 and more preferred about 10 ± 0.3.
The diluted aqueous detergent composition the pH may be adjusted to a pH of about 7.0 to pH of about 12.0, preferably to a pH of about 7.5 to about 10 and more preferred a pH in the range of about 8 to about 9.5 or 8.5 to about 9. pH
The aqueous detergent composition has a pH in the range of about > 8.5 and < 12, preferably of about > 9 and < 11.5, further preferred of about > 9.5 and < 11 and more preferred about 10 ± 0.3.
Protease
The protease that can be suitable used for the aqueous detergent composition is a subtilisin protease.
According to one preferred embodiment the protease can be a serinprotease.
According to a more preferred embodiment the protease can be a serinendoprotease.
According to one embodiment the protease of the aqueous detergent composition comprises a peptide compound, wherein the peptide compound can be selected from di- substituted alanin amide or OH-substituted phenylalanine.
The protease may contain about 0.1 wt.-% to about 1% wt.-% peptide compound, wherein the peptide compound can be selected from di-substituted alanin amide or OH- substituted phenylalanine, preferably selected from OH-substituted phenylalanine, based on the raw protease material.
It has been surprisingly found that the addition of peptide compound, wherein the peptide compound can be selected from di-substituted alanin amide or OH-substituted phenylalanine, preferably selected from OH-substituted phenylalanine, may increases the heat resistance of the protease, preferably of the serinprotease and more preferred of the serinendoprotease .
The peptide compound of OH-substituted phenylalanine that can be suitable used having the formula I:
Figure imgf000030_0001
R is hydrogen, CH3, CX3 , CHX2, or CH2X, preferably hydrogen;
X is a halogen atom, preferably Cl;
Bi is a single amino acid residue; and
B2 is one or more amino acid residues, B2 optionally comprising an N-terminal protection group.
It is preferred that B 1 is a small amino acid residue. More preferably Bl is alanine or valine. In this context, the following are considered to be small amino acids: alanine, cysteine, glycine, proline, serine, threonine, valine, norvaline, norleucine.
The peptide compound may be an aldehyde wherein R is hydrogen, Bi is a single amino acid, preferably selected among small amino acids such as valirre and alanine, B2 comprises at least two amino acid residues and wherein at least one of said two amino acid residues is selected among phenylalanine, glycine and leucine.
Aminoacid residues are abbreviated using standard one-letter or three-letter abbreviations, including the following abbreviations: alanine (A), phenylalanine (F), glycine (G), leueine (L), argirrirre (R), valirre (V), tryptophan (W), tyrosine (Y). The abbreviation "Y -H” demotes tyrosinal, meaning that the C-terminal end of the tyrosine residue is converted from a carboxylic group to an aldehyde group.
The second amino acid residue of B2 can have a non-polar side chain selected among phenylalanine, glycine, leucine, tyrosine and tryptophan. Preferably, B2 comprises an acetyl (Ac) N-terminal protection group, providing, inter alia, the peptide aldehyde compounds Ac- FGAY-H, Ac-LGAY-H, Ac-YGAY-H, Ac-FGVY-H and Ac-WLVY-H. Preferably, the compounds according to this aspect of the invention comprise less than 10 amino acid residues, such as 9, 8, 7, 6, 5 or most preferably 4 amino acid residues.
In another aspect, the peptide compound according to formula I may be a tri-peptide aldehyde wherein R is hydrogen, Bi is a single amino acid selected among small amino acids, e.g. valine and alanine, B2 comprises an amino acid residue selected among arginine, glycine and leucine. Preferably, B2 comprises an N-terminal protection group selected among benzyloxycarbonyl (Z) and acetyl (Ac), providing, inter alia, the peptide aldehyde compounds Z-RAY-H, Z-GAY-H, Z-GAL-H, Z-GAF-H, Z-GAV-H, Z-RVY-H, Z-LVY-H and Ac-GAY- H. Most preferred, according to this aspect, is the benzyloxycarbonyl (Z) N-terminal protection group.
In a preferred aspect, where the peptide compound according to formula I comprises at least four amino acid residues, B2 comprises an N-terminal amino acid residue having a non polar side chain. In the context of the present invention, by "amino acids with non-polar side chain" is meant an amino acid or amino acid residue selected from the group comprising: phenylalanine, tyrosine, tryptophan, isoleucine, leucine, methionine, valine, alanine, proline, glycine, norvaline, or norleucine.
Particularly preferred peptide aldehydes of the present invention include Z-RAY -H, Ac-GAY-H, Z-GAY-H, Z-GAL-H, Z-GAF-H, Z-GAV-H, Z-RVY-H, Z-LVY-H, AcLGAY- H, Ac-FGAY-H, Ac-YGAY-H, Ac-FGVY-H or AcWLVY-H, where Z is benzyloxycarbonyl and Ac is acetyl.
The N-terminal protecting group may be any aminoterminal protecting group which can be employed in peptide synthesis. Grassand Meinhoffer, eds., The Peptides, Vol. 3;
3-88 (1981), Academic Press, New York 1981, discloses numerous suitable amine protecting groups and is incorporated herein by reference forthat purpose. Examples of suitable groups include formyl, acetyl, benzoyl, trifluoroacetyl, fluoromethoxy carbonyl, methoxysuccinyl, aromatic urethane protecting groups, such as, benzyloxylcarbonyl; and aliphatic urethane protecting groups, such as t-butyloxycarbonyl or adamantyloxycarbonyl, p-methoxybenzyl carbonyl (MOZ), benzyl (Bn), p-methoxybenzyl (PMB) or p-methoxyphenyl (PMP).
Preferably, the N-terminal protection group of the present invention is selected among formyl, acetyl, benzoyl, aromatic or aliphatic urethanes, more preferably acetyl or
benzyloxycarbonyl. Where the peptide compound comprises three amino acids, the N- terminal protection group is preferably an aromatic or aliphatic urethane or an aromatic N- terminal protection group, particularly benzyloxycarbonyl (Cbz), p-methoxybenzyl carbonyl (MOZ), benzyl (Bn), p-methoxybenzyl (PMB) or p-methoxyphenyl (PMP), more preferably benzyloxycarbonyl. Where the peptide compound comprises four or more amino acids, it is preferred that the N-terminal protection group is formyl, acetyl or benzoyl, more preferably acetyl.
In a more preferred aspect of the peptide compound of formula I, R is hydrogen, Bi is a single amino acid, preferably selected among small amino acids such as valine and alanine, B2 is -Z-GAY-H, wherein Z is an N-terminal protection group, preferably benzyloxycarbonyl, G is glycine, A is alanine and Y-H denotes tyrosinal.
In a more preferred aspect the peptide compound may have the formula II:
Figure imgf000032_0001
wherein
R is hydrogen, B3 is -Z-GAY-H, wherein Z is an N-terminal protection group, preferably benzyloxycarbonyl, G is glycine, A is alanine and Y-H denotes tyrosinal.
Aqueous detergent composition
According to one aspect, an aqueous detergent composition may comprise:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one alkyl alkoxylate surfactant;
- about > 1 wt.-% to about < 5 wt.-% of at least one protease;
- about > 1 wt.-% to about < 30 wt.-% of at least one organic solvent; and
about > 50 wt.-% water; wherein the wt.-% of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
According to one aspect, an aqueous detergent composition may comprise:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one alkyl alkoxylate surfactant selected from the group comprising at least one CYCix-alkyl alkoxylate (EO)n/(PO)m and/or at least one CYCix-alkyl alkoxylate (EO)n/(PO)m Ci-Cs-alkyl ether, preferably the C1-C5- alkyl of the ether can be butyl, wherein n = 1 to 16 and m = 0 to 16;
- about > 1 wt.-% to about < 5 wt.-% of at least one protease;
- about > 1 wt.-% to about < 30 wt.-% of at least one an C2-C8-alcohol as organic solvent; and
- about > 50 wt.-% water; wherein the wt.-% of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%. According to one aspect, an aqueous detergent composition may comprise:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one CVCV-alkyl alkoxylate (EO)n/(PO)m and/or at least one CVCV-alkyl alkoxylate (EO)n/(PO)m CVCValkyl ether, preferably the Ci-C5-alkyl of the ether can be butyl, wherein n = 1 to 16 and m = 0 to 16;
- about > 1 wt.-% to about < 5 wt.-% of at least one protease;
- about > 1 wt.-% to about < 30 wt.-% of at least one C2-C6-alkyl diol or C2-C6-alkyl triol as organic solvent; and
about > 50 wt.-% water; wherein the wt.-% of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%
According to one aspect an aqueous detergent composition, preferably a concentrated aqueous detergent composition, is provided comprising:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one alkyl alkoxylate surfactant selected from the group comprising at least one CVCix-alkyl alkoxylate (EO)n/(PO)m and/or at least one CVCix-alkyl alkoxylate (EO)n/(PO)m CVCValkyl ether, preferably the C1-C5- alkyl of the ether can be butyl, wherein n = 2 to 14 and m = 0 to 10;
- about > 1 wt.-% to about < 5 wt.-% of at least one subtilisin protease;
- about > 1 wt.-% to about < 30 wt.-% of at least one organic solvent, preferably a CVCV alkyl diol or CVCValkyl triol, and more preferred a dihydroxypropane; and
- about > 50 wt.-% water; wherein the weight % of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
According to one aspect an aqueous detergent composition, preferably a concentrated aqueous detergent composition, is provided comprising:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one CVCV-alkyl alkoxylate (EO)n/(PO)m and/or at least one CVCV-alkyl alkoxylate (EO)n/(PO)m CVCValkyl ether, preferably the CVCValkyl of the ether can be butyl, wherein n = 2 to 14 and m = 0 to 10;
- about > 1 wt.-% to about < 5 wt.-% of at least one subtilisin protease;
- about > 1 wt.-% to about < 5 wt.-% of a CVCValkyl diol or CVCValkyl triol, and more preferred a dihydroxypropane; and about > 50 wt.-% water; wherein the weight % of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
According to one aspect an aqueous detergent composition, preferably a concentrated aqueous detergent composition, is provided comprising:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one CVCix-alkyl alkoxylate (EO)n/(PO)m and at least one Cx-Cix-alkyl alkoxylate (EO)n/(PO)m Ci-CValkyl ether, preferably the Ci- CValkyl of the ether can be butyl, wherein n = 2 to 14 and m = 0 to 10;
- about > 1 wt.-% to about < 5 wt.-% of at least one subtilisin protease;
- about > 1 wt.-% to about < 5 wt.-% of a C2-C6-alkyl diol or C2-C6-alkyl triol, and more preferred a dihydroxypropane; and
- about > 50 wt.-% water; wherein the weight % of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
According to one aspect an aqueous detergent composition, preferably a concentrated aqueous detergent composition, is provided comprising:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one Cx-Cix-alkyl alkoxylate (EO)n/(PO)m, wherein n = 2 to 14 and m = 0 to 10;
- about > 1 wt.-% to about < 5 wt.-% of at least one subtilisin protease;
- about > 1 wt.-% to about < 5 wt.-% of a CVCValkyl diol or CVCValkyl triol, and more preferred a dihydroxypropane; and
- about > 50 wt.-% water; wherein the weight % of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
According to one aspect an aqueous detergent composition, preferably a concentrated aqueous detergent composition, is provided comprising:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one CVCix-alkyl alkoxylate (EO)n/(PO)m
Ci-C5-alkyl ether, preferably the CVCValkyl of the ether can be butyl, wherein n = 2 to 14 and m = 0 to 10;
- about > 1 wt.-% to about < 5 wt.-% of at least one subtilisin protease; - about > 1 wt.-% to about < 5 wt.-% of a C2-C6-alkyl diol or C2-C6-alkyl triol, and more preferred a dihydroxypropane; and
- about > 50 wt.-% water; wherein the weight % of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
According to one aspect an aqueous detergent composition, preferably a concentrated aqueous detergent composition, is provided comprising:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one Cx-Cix-alkyl alkoxylate (EO)n/(PO)m and/or at least one Cx-Cix-alkyl alkoxylate (EO)n/(PO)m Ci-CValkyl ether, preferably the Ci-C5-alkyl of the ether can be butyl, wherein n = 2 to 14 and m = 0 to 10;
- about > 1 wt.-% to about < 5 wt.-% of at least one subtilisin protease;
- about > 1 wt.-% to about < 5 wt.-% of dihydroxypropane; and
- about > 50 wt.-% water; wherein the weight % of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
According to one aspect an aqueous detergent composition, preferably a concentrated aqueous detergent composition, is provided comprising:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one alkyl alkoxylate surfactant selected from the group comprising at least one Cx-Cix-alkyl alkoxylate (EO)n/(PO)m and/or at least one Cx-Cix-alkyl alkoxylate (EO)n/(PO)m Ci-CValkyl ether, preferably the C1-C5- alkyl of the ether can be butyl, wherein n = 2 to 10 and m = 0 to 5;
- about > 0.1 wt.-% to about < 5 wt.-% of at least one serinprotease;
- about > 1 wt.-% to about < 30 wt.-% of at least one organic solvent, preferably a CVCV alkyl diol or C2-CY, -alkyl triol, and more preferred a dihydroxypropane; and
- about > 60 wt.-% of water; wherein the weight % of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
According to one aspect an aqueous detergent composition, preferably a concentrated aqueous detergent composition, is provided comprising:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one alkyl alkoxylate surfactant selected from the group comprising at least one CVCix-alkyl ethoxylate (EO)n and/or at least one C8-Ci8-alkyl ethoxylate (EO)n Ci-Cs-alkyl ether, preferably the Ci-Cs-alkyl of the ether can be butyl, wherein n = 2 to 10;
- about > 0.01 wt.-% to about < 1 wt.-% of at least one serinprotease;
- about > 1 wt.-% to about < 30 wt.-% of at least one organic solvent, preferably a
dihydroxypropane;
- about > 1 wt.-% to about < 10 wt.-% of at least one hydrotrope; and
- about > 70 wt.-% of water; wherein the weight % of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
According to one aspect an aqueous detergent composition, preferably a concentrated aqueous detergent composition, is provided comprising:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one alkyl alkoxylate surfactant selected from the group comprising at least one Cs-Cis-alkyl ethoxylate (EO)n and/or at least one Cs-Cis-alkyl ethoxylate (EO)n Ci-Cs-alkyl ether, preferably the Ci-Cs-alkyl of the ether can be butyl, wherein n = 2 to 10, preferably n = 5 to 10;
- about > 0.01 wt.-% to about < 1 wt.-% of at least one serinendoprotease;
- about > 1 wt.-% to about < 30 wt.-% of at least one organic solvent, preferably a
dihydroxypropane;
- about > 1 wt.-% to about < 10 wt.-% of at least one hydrotrope;
- about > 0.05 wt.-% to about < 0.5 wt.-% of at least one antifoaming agent;
- about > 50 wt.-% of water; wherein the weight % of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
According to one aspect an aqueous detergent composition, preferably a concentrated aqueous detergent composition, is provided comprising:
- about > 6 wt.-% to about < 8 wt.-% of triethanol amine;
- about > 8.5 wt.-% to about < 10.5 wt.-% of at least one Cs-Cis-alkyl alcohol ethoxylate (EO)n Ci-Cs-alkyl ether, preferably the Ci-Cs-alkyl of the ether can be butyl, wherein n = 5 to 10, preferably Ci2-Ci4-alkyl alcohol ethoxylate (EO)n C4- alkyl ether, wherein n = 10;
- about > 0.05 wt.-% to about < 0.2 wt.-% of at least one serinendoprotease;
- about > 2 wt.-% to about < 4 wt.-% of dihydroxy propane;
- about > 7 wt.-% to about < 9 wt.-% of at least one hydrotrope, preferably cumene
sulfonate; - optional about > 0.1 wt.-% to about < 0.3 wt.-% of at least one anionic surfactant, preferably an C8 to Ci4 alkyl sulfate and more preferred 2-ethylhexyl sulfate;
- about > 65 wt.-%, preferably > 70 wt.-% of water; wherein the weight % of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
According to one aspect an aqueous detergent composition, preferably a concentrated aqueous detergent composition, is provided comprising:
- about > 1 wt.-% to about < 15 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one alkyl alkoxylate end-capped alkyl ether;
- about > 0.1 wt.-% to about < 5 wt.-% of at least one protease;
- about > 1 wt.-% to about < 30 wt.-% of at least one organic solvent; and
- about > 30 wt.% water;
wherein the wt.-% of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
According to one aspect an aqueous detergent composition, preferably a concentrated aqueous detergent composition, is provided comprising:
- about > 1 wt.-% to about < 15 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one alkyl alkoxylate alkyl ether C12/C14-
10EO, being n-butyl end-capped;
- about > 0.1 wt.-% to about < 5 wt.-% of at least one protease;
- about > 1 wt.-% to about < 30 wt.-% of at least one organic solvent; and
- about > 30 wt.% water;
wherein the wt.-% of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
According to one aspect of the aqueous detergent composition, preferably a concentrated aqueous detergent composition, the surfactant selected from at least one alkyl alkoxylate surfactant and/or at least one alkyl alkoxylate alkyl being n-C2 to C5 alkyl end- capped and more preferred n-butyl end-capped.
According to one aspect of the aqueous detergent composition, preferably a concentrated aqueous detergent composition, the surfactant selected from at least one alkyl alkoxylate surfactant and/or at least one alkyl alkoxylate alkyl ether is an alkyl alkoxylate alkyl ether of about C10 to about C16 with about 8 EO to about 12 EO and being C2 to C5 alkyl end-capped, preferably n-C2 to n-C5 alkyl end-capped.
According to one aspect of the aqueous detergent composition, preferably a concentrated aqueous detergent composition, the surfactant selected from at least one alkyl alkoxylate surfactant and/or at least one alkyl alkoxylate alkyl ether is an alkyl alkoxylate alkyl ether C12/C14 of about 8 EO to about 12 EO, being n-C2 to n-C5 alkyl end-capped.
According to one aspect of the aqueous detergent composition, preferably a concentrated aqueous detergent composition, the surfactant selected from at least one alkyl alkoxylate surfactant and/or at least one alkyl alkoxylate alkyl ether is an alkyl alkoxylate alkyl ether of C12/C14-10EO and being n-butyl end-capped.
Readv-to-use composition
The aqueous detergent composition can be present in form of a diluted or so called “ready-to-use” composition. The diluted compositions may be derived from a concentrated aqueous detergent composition, for example, by combining water, for example, deionized water, city or tap water, with said concentrate. The so called ready-to-use compositions may be treated to reduce hardness.
The source of alkalinity and addition of the solvent, preferably water, are provided so that the diluted aqueous detergent composition may have a pH in the range of about 7 to about 12 and more preferred a pH in the range of about 8 to about 9.5.
According to one aspect, the concentrated aqueous detergent composition can be diluted with a solvent, preferably water, to an about 1,0 wt.-% to about 10 wt.-%, preferably to an about 2,0 wt.-% to 5.5 wt.-%, diluted aqueous detergent composition, also named “ready-to-use solution”.
As a solvent, preferably water is added to 100 wt.-% to the diluted aqueous detergent composition, wherein the weight.-% of the components are based on the total weight of the diluted aqueous detergent composition, and the weight. -% of all components of the aqueous detergent composition are select so that it does not exceed 100 wt.-%.
Methods of Cleaning
In some aspects, the present invention provides methods for removing soil from a surface. In some embodiments, the methods for removing soil from a surface include using a clean out of place (COP) or clean in place (CIP) cleaning process. The methods include applying to the surface a composition of the invention. The method for removing soil from a surface to be cleaned may comprises applying to the surface an aqueous detergent composition. According to another aspect the method for removing soil from a surface to be cleaned may comprises applying to the surface a concentrated aqueous detergent composition. According to another aspect the method for removing soil from a surface to be cleaned may comprises preferably applying to the surface a diluted aqueous detergent composition.
The method for removing soil from a surface to be cleaned may comprising:
a) optional applying a pre-treatment solution, preferably water, to the surface to be cleaned for an amount of time sufficient to substantially penetrate a soil on the surface to be cleaned and/or pre-clean a soil on the surface to be cleaned;
b) applying the aqueous detergent composition, preferably the diluted aqueous detergent composition, to the surface to be cleaned for an amount of time for cleaning the surface to be cleaned;
c) optional a rinsing step before and/or after the application (a) and/or (b).
In some embodiments, the methods and compositions of the present invention are applied to surfaces which are normally cleaned using a clean out of place or in place cleaning technique. Examples of such surfaces include hard and soft surface, for example of upper outer and/or inner outer surfaces of materials such as ceramic, metal, plastic and/or glass, surface that came into contact with beverages and/or food, beverages such alcoholic or non alcoholic beverages such as beer or milk, food such as meat, vegetables and/or grain-products. Other surfaces that can be cleaned are instruments and apparatus, for example used in sanitary or medical services, evaporators, heat exchangers, including tube-in-tube exchangers, direct steam injection, and plate-in-frame exchangers, heating coils including steam, flame or heat transfer fluid heated re-crystallizers, pan crystallizers, spray dryers, drum dryers, and tanks.
Additional surfaces capable of being cleaned using the methods and compositions of the present invention include, but are not limited to membranes, medical devices, laundry and/or textiles, and hard surfaces, e.g., walls, floors, dishes, flatware, pots and pans, heat exchange coils, ovens, fryers, smoke houses, sewer drain lines, and vehicles. In some embodiments, the surfaces may be cleaned using a clean in place method. The methods of the present invention may also be used to remove dust from air handling equipment, for example, from air conditioners and refrigeration heat exchangers. In other embodiments, the methods of the present invention may be used for drain line microbial control, e.g., to reduce or remove biofilm formation. Exemplary industries in which the methods and compositions of the present invention may be used include, but are not limited to: the food and beverage industry, e.g., the dairy, cheese, sugar, and brewery industries; oil processing industry; industrial agriculture and ethanol processing; and the pharmaceutical manufacturing industry.
The aqueous detergent composition can be used for:
- removing soil, preferably for removing soil from a surface in a clean-out-of-place system (COP), from a surface in a clean-in-place system (CIP);
- manual or automatic medical instrument reprocessing;
- cleaning an endoscope.
The manual or automatic medical instrument reprocessing, comprises especially the manual or automatic chirurgical instrument reprocessing.
More preferred, the methods and compositions of the present invention may be used, but are not limited to: manual or automatic medical instrument reprocessing, in particular cleaning an endoscope.
The manual or automatic medical instrument reprocessing comprises the cleaning and/or disinfection of medical instruments, in particular of endoscopes.
Temperature
The methods and aqueous detergent composition for soil removal from surfaces can be applied at reduced temperatures, e.g., from about > 20° C to about < 60° C, preferably about > 35° C to about < 50° C and preferably at about 45° C ± 3 0 C results in energy and cost savings compared to traditional cleaning techniques that require increased temperatures.
Further, the present invention provides for effective soil removal on surfaces that cannot withstand high temperatures.
It has also been found that the methods of the present invention provide for soil removal at reduced temperatures, and using reduced amounts of chemistry, compared to conventional cleaning methods. In some embodiments, the methods of the present invention may use about 25% to about 50% less chemistry, e.g., source of alkalinity, than conventional cleaning methods. Thus, the methods of the present invention may effectively remove soil at both low temperatures, and using a low concentration of chemicals, providing both an energy savings and a reduction in the amount of chemistry consumed per cleaning. Time
In some aspects of the aqueous detergent composition for use with the methods of the present invention are applied to the surface for a sufficient amount of time such that the composition penetrates into the soil to be removed.
In some embodiments, the aqueous detergent composition for use with the methods of the present invention is applied to the surface to be cleaned for about 1 minute to about 30 minutes. In some embodiments, the aqueous detergent composition for use with the methods of the present invention is applied to the surface to be cleaned for about 5 to about 15 minutes. In some embodiments, the aqueous detergent composition for use with the methods of the present invention is applied to the surface to be cleaned for about 10 minutes ± 2 minutes. It is to be understood that any value between these ranges is to be encompassed by the methods of the present invention.
The following non-limiting examples illustrate certain advantages of the present invention.
EXAMPLES
Examples El to E8 and Comparative examples Cl
The compositions of examples El to E4 of the invention were prepared by mixing the components at about 20° C as mentioned in table I in an amount obtaining a 50 ml aqueous solution.
Table 1
Phase stability and foaming characteristic
Figure imgf000041_0001
Figure imgf000042_0001
Liquanase Evity 3.5 XL*1: expressed as enzyme protein (aep) and obtainable from the company Novozymes A/S, located at Krogshoejvej 36, 2880 Bagsvaerd, Denmark.
Water*2: is demineralized water.
Alkyl alkoxylate alkyl ether C12/C14-10EO, n-butyl end-capped*3: can be preferably Genapol BE 2410.
Cl2/Cl5-oxo alcohol EO-PO-adduct*4: can be preferably Genapol EP 2552.
C12/C14 fatty alcohol EO/PO-addition product*5: can be preferably Genapol EP 2464. Cl0/Cl2-fatty alcohol EO-PO-adduct*6: can be preferably Genapol 0244.
The demineralized water (demin. water) is produced by a process of distillation and has an electrical conductivity of not more than 11 gS/cm and total dissolved solids of less than 10 mg/liter. Distillation involves boiling the water and then condensing the vapor into a clean container, leaving solid contaminants behind.
Table 1 shows that alkyl alkoxylate alkyl ether of example El has an improved phase stability and low foaming characteristic compared with examples E2 to E4.
Preparation of examples E5 to E8 and comparative example C2
The compositions of examples E5 to E8 of the invention and comparative example C2 were prepared by additional diluting the compositions El to E4 and Cl at about 20° C to a 0.6% (w/w) solution with demineralized water.
The demineralized water (demin. water) is produced by a process of distillation and has an electrical conductivity of not more than 11 pS/cm and total dissolved solids of less than 10 mg/liter. Distillation involves boiling the water and then condensing the vapor into a clean container, leaving solid contaminants behind.
This test method provides a basis to assess the activity loss of protease for the compositions of examples E5 to E8 of the invention and comparative examples C2. 50 ml solution of examples E5 to E8 and C2 respectively are each treated for 76 h at a constant temperature of 45° C. The activity of the protease solutions of examples E5 to E8 and C2 slightly decrease. After 76 hours the temperature was raised for additional 4 hours to a constant temperature of 50° C.
Set Up for Validation
Table 2
Test System / Technical Equipment / Instruments
Figure imgf000043_0001
Table 3
Reference Materials, Chemicals and Consumables
Figure imgf000043_0002
Protease Enzyme Activity Test
The method of assaying the activity of the enzymes, such as Liquanase, uses TNBS color reaction method and the San++ - analyzer available from Skalar Analytical BV. This assay measures the enzymatic hydrolysis of casein into polypeptides containing free amino groups. These amino groups react with 2,4,6-trinitrobenzene sulfonic acid (TNBS) to form a yellow colored complex. Thus, the more deeply colored the reaction, the more activity is measured.
Equipment
Continuous Flow System with computer and Flow Access V3 of San++, available from Skalar Analytical BV, also referred to as“Continuous Flow System”.
The activity of the Fiquanase Evity 3.5 EX, available from Novozymes, was measured with the Continuous Flow System with computer and Flow Access V3 of San++, available from Skalar Analytical BV. The Casein-solution and color reagent was dosed by the Continuous Flow System.
Casein-solution
3 g of Casein, N,N-dimethylated (DMC) were dissolved in ± 500 mF deionized water and stirred for approximately 15 min. After that the solution was heated up over 95°C under stirring and nitrogen gas was led into the solution. After holding the temperature over 95°C for approximately 1 hour 32,40 g Sodium Tetraborate x 10 H20 were added. After dissolving 16,63 g Sodium dihydrogen phosphate were added and the solution was stirred for further 15 min at over 95°C. After the 15 min 400 g ice made from deionized water were added to cool down to room temperature. After reaching room temperature the pH was set to 8 and the solution was filled up to 1 F with deionized water.
Color reagent
2 mF 2,4,6-Trinitrobenzene Sulfonic Acid were mixed with 200 mF deionized water. This reagent was prepared freshly before use and stored cold during analysis.
Brij 35 solution. 10 % 50 g Brij 35 were dissolved in approximately 500 mL deionized water and filled up to 1 L with deionized water in a graduated flask.
Sodium Sulfite stock solution
200 g Sodium Sulfite were dissolved in 1 L deionized water.
Sodium Sulfite working solution
50 mL Sodium Sulfite stock solution were given in a 1 L graduated flask and filled up to the mark with deionized water.
Flowing liquid and Protease solvent
50 mL Sodium Sulfite working solution and 1 mL Brij 35 solution were given in a 1 L graduated flask and filled up to the mark with deionized water.
Conduct and Results of Validation
The activity of the Liquanase Evity 3,5 LX was measured with the Continuous Flow System with computer and Flow Access V3 of San++. Three samples of 1 g of the protease Liquanase Evity 3,5 LX were weighted and diluted in 1 L protease solvent, solved for 20 minutes and further diluted 1/781 and 1/671 with Sodium Sulfite Solution before
measurement to fit into the range of the calibration curve.
Table 4
activity of the Liquanase Evity 3,5 LX
Figure imgf000045_0002
Figure imgf000045_0001
because of injection error
The mean activity for the test substance Liquanase Evity 3,5 LX is: 176.200 CPE/g
Selectivity/Specificity
A sample of a first placebo probe that is Example 1 but without protease and a sample of second probe, which is identical with the first placebo probe but with the exception that the substance Liquanase Evity 3,5 LX is added to the second test probe were prepared as described above under sample preparation. The amount of Liquanase Evity 3,5 LX added to the second test probe was 2,0 wt.-%.
After stirring the first placebo probe was further diluted with 1/11 sodium sulfite solution. This is the lowest dilution that is used in complex matrices to avoid interferences from a product.
The spiked second probe was diluted 1/341 and 1/231 to be in the range of the calibration curve.
Result
The placebo sample measured with the Continuous Flow System with computer and Flow Access V3 of San++ shows no activity peak. The product does not contain any substance that might disturb the determination. The sample of the spiked second probe measured with the Continuous Flow System with the added 2% of protease shows the expected protease activity peaks.
Linearity
A calibration curve was made with 5 different concentrations of protease Liquanase Evity 3,5 LX placebo samples over a range of ± 20% of the target concentration of 2 wt.-%. After 20 minutes of mixing several dilutions of this preparation with these placebo probes to which protease Liquanase Evity 3,5 LX were added were made.
Table 5
Concentration of protease after dilution %
Figure imgf000046_0001
Approximately 2 g of this dilutions were weighted into a 100 mL volumetric flask, filled up to the mark with sodium sulfite solution, stirred for 20 minutes, further diluted 1/341 and 1/231 with sodium sulfite solution to be in the range of the calibration curve and measured.
Table 6
Protease activity CPE/g
Figure imgf000047_0001
The calibration curve for the Liquanase Evity 3,5 LX at diffemet concentration of Table 6 is shown in Fig.1.
Acceptance criterion linearity test: The correlation coefficient R should be better than 0.99 Result linearity test: The coefficient of correlation R is 0,9986
The coefficient of determination R2 is 0,9972
Loss of protease activity
Examples E5 to E8 and C2 treated 76 hours at 45° C and for an additional time of 4 h at 50° C. The protease activity was measured at the start at 50° C (t = 0 at 50° C) and set to be 100% activity and then the protease activity was measured for the solutions of examples E5 to E8 and C2 after 4 hours at 50° C (t = 4 at 50° C) again and compared with the protease activity set to be 100% measured after 76 hours at 45° C.
For measuring the loss of protease activity six independent samples about 2 g of the liquid samples E5 to E8 and C2 were filled up to the mark in a 100 mL volumetric flask with sodium sulfite solution and stirred for 20 minutes at room temperature and measured with the San++, available from Skalar Analytical BV against the calibration curve.
Table 7 shows the mean protease activity in % of the six independent samples of examples E5 to E8 and C2 treated 76 hours at 45° C and thereafter 4 h at 50° C, whereby the enzyme activity was measured at the start at 50° C (t = 0 at 50° C) and set to be 100% activity and the protease activity was measured again for a probe of the solutions of examples E5 to E8 and C2 after 4 hours at 50° C (t = 4 at 50° C).
It can be seen from table 7, that the loss of protease activity in a protease water solution of composition C2 is higher compared with examples E5 to E8. Table 7
Residual activity [%]
Figure imgf000048_0001
It is surprising that the protease enzyme is still active after treated 76 h at 45° C and 4 h at 50° C. An expert would expect that the protease enzyme activity for examples E5 to E8 would be close to 0%.
It is further surprising that the protease enzyme activity for examples E5 to E8 at 50°
C is more stable compared with the aqueous solution C2.
It is to be understood that wherever values and ranges are provided herein, all values and ranges encompassed by these values and ranges, are meant to be encompassed within the scope of the present invention. Moreover, all values that fall within these ranges, as well as the upper or lower limits of a range of values, are also contemplated by the present application.
Embodiments of the present invention have been disclosed above for illustrative purposes. Those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. In the embodiments of the present invention, the foaming compositions has been taken as an example for description. However, this is only an example, and the foaming composition in accordance with embodiments of the present invention may be applied to other products. The scope of the invention should be limited only by the accompanying claims.

Claims

1. An aqueous detergent composition comprising:
- about > 1 wt.-% to about < 15 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one alkyl alkoxylate surfactant and/or an alkyl alkoxylate alkyl ether;
- about > 0.1 wt.-% to about < 5 wt.-% of at least one protease;
- about > 1 wt.-% to about < 30 wt.-% of at least one organic solvent; and
- about > 30 wt.% water;
wherein the wt.-% of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
2. The aqueous detergent composition of claim 1 comprising:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one alkyl alkoxylate surfactant selected from the group comprising at least one Cs-Ci 8-alkyl alkoxylate
(EO)n/(PO)m and/or at least one CVCix-alkyl alkoxylate (EO)n/(PO)m Ci-Cs-alkyl ether, preferably the Ci-Cs-alkyl of the ether is butyl, wherein n = 1 to 16 and m = 0 to 16;
- about > 1 wt.-% to about < 5 wt.-% of at least one protease;
- about > 1 wt.-% to about < 30 wt.-% of at least one organic solvent, preferably an C2-C8-alcohol, further preferred a C2-C6-alkyl diol or C2-CY, -alkyl triol; and
- about > 50 wt.-% water; wherein the wt.-% of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
3. The aqueous detergent composition of claim 1 or 2 comprising:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one alkyl alkoxylate surfactant selected from the group comprising at least one Cs-Ci 8-alkyl alkoxylate
(EO)n/(PO)m and/or at least one Cs-Cis-alkyl alkoxylate (EO)n/(PO)m Ci-Cs-alkyl ether preferably the Ci-Cs-alkyl of the ether is butyl, wherein n = 2 to 14 and m = 0 to 10;
- about > 1 wt.-% to about < 5 wt.-% of at least one subtilisin protease;
- about > 1 wt.-% to about < 30 wt.-% of at least one organic solvent, preferably a C2-
CY, -alkyl diol or C2-C6-alkyl triol, and more preferred a dihydroxypropane; and
- about > 50 wt.-% water; wherein the weight % of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
4. The aqueous detergent composition according to any of the preceding claims 1 to 3 comprising:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one alkyl alkoxylate surfactant selected from the group comprising at least one Cs-Ci 8-alkyl alkoxylate
(EO)n/(PO)m and/or at least one CVCix-alkyl alkoxylate (EO)n/(PO)m Ci-CY-alkyl ether preferably the Ci-Cs-alkyl of the ether is butyl, wherein n = 2 to 10 and m = 0 to 5;
- about > 0.1 wt.-% to about < 5 wt.-% of at least one serinprotease;
- about > 1 wt.-% to about < 30 wt.-% of at least one organic solvent, preferably a C2- CY-alkyl diol or C CY-alkyl triol, and more preferred a dihydroxypropane; and
- about > 60 wt.-% of water; wherein the weight % of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
5. The aqueous detergent composition according to any of the preceding claims 1 to 4 comprising:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one alkyl alkoxylate surfactant selected from the group comprising at least one Cs-Ci 8-alkyl ethoxylate (EO)n and/or at least one Cx-Cix-alkyl ethoxylate (EO)n Ci-CY-alkyl ether, preferably the C1-C5- alkyl of the ether is butyl, wherein n = 2 to 10;
- about > 0.01 wt.-% to about < 1 wt.-% of at least one serinprotease;
- about > 1 wt.-% to about < 30 wt.-% of at least one organic solvent, preferably a dihydroxypropane; - about > 1 wt.-% to about < 10 wt.-% of at least one hydrotrope; and
- about > 70 wt.-% of water; wherein the weight % of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
6. The aqueous detergent composition according to any of the preceding claims 1 to 5 comprising:
- about > 1 wt.-% to about < 10 wt.-% of at least one source of alkalinity;
- about > 1 wt.-% to about < 15 wt.-% of at least one alkyl alkoxylate surfactant selected from the group comprising at least one Cs-Ci 8-alkyl ethoxylate (EO)n and/or at least one C Cix-alkyl ethoxylate (EO)n Ci-Cs-alkyl ether, preferably the C1-C5- alkyl of the ether is butyl, wherein n = 2 to 10, preferably n = 5 to 10;
- about > 0.01 wt.-% to about < 1 wt.-% of at least one serinendoprotease;
- about > 1 wt.-% to about < 30 wt.-% of at least one organic solvent, preferably a dihydroxypropane;
- about > 1 wt.-% to about < 10 wt.-% of at least one hydrotrope;
- about > 0.05 wt.-% to about < 0.5 wt.-% of at least one antifoaming agent;
- about > 50 wt.-% of water; wherein the weight % of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
7. The aqueous detergent composition according to any of the preceding claims 1 to 6 comprising:
- about > 6 wt.-% to about < 8 wt.-% of triethanol amine;
- about > 8.5 wt.-% to about < 10.5 wt.-% of at least one Cs-Cis-alkyl alcohol
ethoxylate (EO)n Ci-Cs-alkyl ether, wherein n = 5 to 10, preferably Ci2-Ci4-alkyl alcohol ethoxylate (EO)n C4-alkyl ether, preferably the Ci-Cs-alkyl of the ether is butyl, wherein n = 10;
- about > 0.05 wt.-% to about < 0.2 wt.-% of at least one serinendoprotease;
- about > 2 wt.-% to about < 4 wt.-% of dihydroxy propane;
- about > 7 wt.-% to about < 9 wt.-% of at least one hydrotrope, preferably cumene sulfonate; - about > 65 wt.-%, preferably > 70 wt.-% of water; wherein the weight % of the components are based on the total weight of the detergent composition and the total wt.-% of all components of the detergent composition does not exceed 100 wt.-%.
8. The aqueous detergent composition according to any of the preceding claims 1 to 7, wherein the protease is a subtilisin protease, preferably a serinprotease and more preferred a serinendoprotease.
9. The aqueous detergent composition according to any of the preceding claims 1 to 8, wherein the composition comprises an a peptide compound, preferably the peptide compound is selected from di-substituted alanin amide or OH-substituted phenylalanine and further preferred peptide compound is an OH-substituted phenylalanine according to formula I or II.
10. The aqueous detergent composition according to any of the preceding claims 1 to 9, wherein the source of alkalinity is selected from the group comprising basic salts, amines, alkyl amines, alkanol amines, carbonates, silicates, and mixtures thereof, preferably the source of alkalinity is selected from the group comprising C1-C4 trialkanol amine, and most preferred the source of alkalinity is triethanol amine.
11. The aqueous detergent composition according to any of the preceding claims 1 to 10, wherein the alkyl alcohol ethoxylate alkyl ether is a Cio-Ci4-alkyl alcohol ethoxylate (EO)n C2-C5-alkyl ether, wherein n = 4 to 14, preferably a Ci2-Ci4-alkyl alcohol ethoxylate (EO)n C2-Cs-alkyl ether, wherein n = 5 to 12, further preferred a Ci2-Ci4- alkyl alcohol ethoxylate (EO)n CVCs-alkyl ether, wherein n = 5 to 10, and more preferred a Ci2-Ci4-alkyl alcohol ethoxylate (EO)n C4-alkyl ether, wherein n = 10, and most preferred a Ci2-Ci4-alkyl alcohol ethoxylate (EO)n butyl ether, wherein n = 10.
12. The aqueous detergent composition according to any of the preceding claims 1 to 11, wherein the organic solvent is dihydroxy propane, preferably 1,2 dihydroxy propane.
13. The aqueous detergent composition according to any of the preceding claims 1 to 12, wherein the hydrotrope is selected from the group comprising of a toluene sulfonate, xylene sulfonate, cumene sulfonate and preferably a cumene sulfonate.
14. The aqueous detergent composition according to any of the preceding claims 1 to 13, comprising in addition at least one component selected from the group comprising:
- at least one preservative, preferably l,2-benzisothiazol-3(2H)-one and/or 3-iodo-2- propynyl butyl carbamate; and/or
- at least one salt of an carbonic acid, preferably citrate; and/or
- at least one corrosion inhibitor, preferably hydroxyethyl amino bis(methylene phosphonate).
15. The aqueous detergent composition according to any of the preceding claims 1 to 14, wherein The aqueous detergent composition has a pH in the range of about > 8.5 and < 12, preferably of about > 9 and < 11.5, further preferred of about > 9.5 and < 11 and more preferred about 10 ± 0.3.
16. The aqueous detergent composition according to any of the preceding claims 1 to 15 is additional diluted with water 1 : 10 to 1 : 1000, preferably the composition is diluted with water 1 : 50 to 1 : 500, further preferred the composition is diluted with water 1 : 100 to 1 : 250 and more preferred the composition is diluted with water 1 : 150 to 1 : 180.
17. A method for removing soil from a surface comprising applying to the surface an
aqueous detergent composition according to any of the preceding claims 1 to 16.
18. The method of claim 17 comprising:
a) optional applying a pre -treatment solution to the surface to be disinfected and/or cleaned for an amount of time sufficient to substantially penetrate a soil on the surface to be cleaned and/or pre-clean a soil on the surface to be cleaned;
b) applying the aqueous detergent composition according to any of the preceding claims 1 to 16 to the surface to be disinfected and/or cleaned;
c) optional a rinsing step before and/or after the application (a) and/or (b).
20. Use of the aqueous detergent composition according to any of the preceding claims 1 to 16 for cleaning and removing soil from surfaces, preferably for cleaning and removing soil from surfaces from articles in a clean-out-of-place system (COP), further preferred for cleaning and removing soil from surfaces from articles in a clean-in-place system (CIP), in addition preferred for cleaning and removing soil from surfaces of articles that are medical instruments in manual or automatic medical instrument reprocessing, more preferred for cleaning and removing soil from surfaces of endoscope.
PCT/EP2018/074488 2018-09-11 2018-09-11 Phase stable and low foaming aqueous detergent compositions having a long time enzyme activity WO2020052743A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP18778381.6A EP3850068A1 (en) 2018-09-11 2018-09-11 Phase stable and low foaming aqueous detergent compositions having a long time enzyme activity
PCT/EP2018/074488 WO2020052743A1 (en) 2018-09-11 2018-09-11 Phase stable and low foaming aqueous detergent compositions having a long time enzyme activity

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2018/074488 WO2020052743A1 (en) 2018-09-11 2018-09-11 Phase stable and low foaming aqueous detergent compositions having a long time enzyme activity

Publications (1)

Publication Number Publication Date
WO2020052743A1 true WO2020052743A1 (en) 2020-03-19

Family

ID=63683839

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2018/074488 WO2020052743A1 (en) 2018-09-11 2018-09-11 Phase stable and low foaming aqueous detergent compositions having a long time enzyme activity

Country Status (2)

Country Link
EP (1) EP3850068A1 (en)
WO (1) WO2020052743A1 (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0342499A2 (en) * 1988-05-17 1989-11-23 Henkel Kommanditgesellschaft auf Aktien Method for cleaning and disinfecting heat and corrosion sensitive medical devices, especially endoscopes, and product for carrying out the method
WO2009118375A2 (en) * 2008-03-26 2009-10-01 Novozymes A/S Stabilized liquid enzyme compositions
US20100249005A1 (en) * 2007-03-30 2010-09-30 Melton Sherwood Thoele Enzymatic detergent
GB2482164A (en) * 2010-07-22 2012-01-25 Fujifilm Europ Nv Cleaning composition
US20150147802A1 (en) * 2012-05-28 2015-05-28 Kao Corporation Cleaning agent composition for medical-instrument cleaner
WO2015167828A1 (en) * 2014-05-02 2015-11-05 Case Medical, Inc. Compositions and methods for handling potential prion contamination
US20170198237A1 (en) * 2016-01-13 2017-07-13 The Procter & Gamble Company Laundry detergent compositions comprising renewable components
WO2017151840A1 (en) * 2016-03-02 2017-09-08 The Procter & Gamble Company Compositions containing alkyl sulfates and/or alkoxylated alkyl sulfates and a solvent comprising a diol
WO2018113979A1 (en) * 2016-12-22 2018-06-28 Ecolab Usa Inc. Aqueous foaming detergent composition with increased foam dwell time and moistening content

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0342499A2 (en) * 1988-05-17 1989-11-23 Henkel Kommanditgesellschaft auf Aktien Method for cleaning and disinfecting heat and corrosion sensitive medical devices, especially endoscopes, and product for carrying out the method
US20100249005A1 (en) * 2007-03-30 2010-09-30 Melton Sherwood Thoele Enzymatic detergent
WO2009118375A2 (en) * 2008-03-26 2009-10-01 Novozymes A/S Stabilized liquid enzyme compositions
GB2482164A (en) * 2010-07-22 2012-01-25 Fujifilm Europ Nv Cleaning composition
US20150147802A1 (en) * 2012-05-28 2015-05-28 Kao Corporation Cleaning agent composition for medical-instrument cleaner
WO2015167828A1 (en) * 2014-05-02 2015-11-05 Case Medical, Inc. Compositions and methods for handling potential prion contamination
US20170198237A1 (en) * 2016-01-13 2017-07-13 The Procter & Gamble Company Laundry detergent compositions comprising renewable components
WO2017151840A1 (en) * 2016-03-02 2017-09-08 The Procter & Gamble Company Compositions containing alkyl sulfates and/or alkoxylated alkyl sulfates and a solvent comprising a diol
WO2018113979A1 (en) * 2016-12-22 2018-06-28 Ecolab Usa Inc. Aqueous foaming detergent composition with increased foam dwell time and moistening content

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"The Peptides", vol. 3, 1981, ACADEMIC PRESS, pages: 3 - 88
AKZONOBEL: "Berol LFG 61 - High performance surfactant blend for I&I cleaning", 1 January 2013 (2013-01-01), pages 1 - 2, XP055583444, Retrieved from the Internet <URL:https://www.julius-hoesch.de/wp-content/uploads/2018/09/Berol_LFG_61.pdf> [retrieved on 20190425] *

Also Published As

Publication number Publication date
EP3850068A1 (en) 2021-07-21

Similar Documents

Publication Publication Date Title
JP7358158B2 (en) Cleaning composition containing phosphinosuccinic acid adduct and method for using the same
CN112292442B (en) Enzyme detergent for pan
US11208613B2 (en) Long lasting cleaning foam
JP6581785B2 (en) Liquid detergent composition for hard surface, dishwashing method using the same, and medical instrument washing method
JP2022089915A (en) Use of eo/po block copolymer surfactant for controlling viscoelasticity in highly concentrated liquid compound
JP2006265469A (en) Alkaline cleaning agent composition for cip
EP3559190A1 (en) Aqueous foaming detergent composition with increased foam dwell time and moistening content
CN104350139A (en) Detergent composition for automatic dishwashing machines
JP7315948B2 (en) Disinfectant detergent composition
JP2022508191A (en) Acidic cleaning composition for enhanced stain removal
JP6864339B2 (en) Cleaning agent composition for automatic washing machine
WO2020052743A1 (en) Phase stable and low foaming aqueous detergent compositions having a long time enzyme activity
JP7230254B1 (en) liquid detergent composition
JP6035447B1 (en) Cleaning composition for automatic cleaning machine
JP6734022B2 (en) Liquid cleaning composition for automatic cleaning machine for medical equipment and cleaning method
JP5396707B2 (en) Cleaning composition
JP2004263057A (en) Detergent composition for automatic dish washer, and preparation process therefor
WO2020247199A1 (en) Automatic dishwashing compositions and method of cleaning articles
JP7421351B2 (en) Cleaning composition for dishwashers
JP4455289B2 (en) Detergent composition for food manufacturing and processing equipment
WO2023210554A1 (en) Surfactant composition
JP4455290B2 (en) Detergent composition for food manufacturing and processing equipment
US20240174946A1 (en) Detergent composition for use in automatic dishwasher
JP2022083462A (en) Liquid detergent composition and cleaning method
JP2023042613A (en) Liquid detergent composition for tableware

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18778381

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2018778381

Country of ref document: EP

Effective date: 20210412