EP3850068A1 - Phasenstabile und schwach schäumende wässrige waschmittelzusammensetzungen mit langer enzymaktivität - Google Patents

Phasenstabile und schwach schäumende wässrige waschmittelzusammensetzungen mit langer enzymaktivität

Info

Publication number
EP3850068A1
EP3850068A1 EP18778381.6A EP18778381A EP3850068A1 EP 3850068 A1 EP3850068 A1 EP 3850068A1 EP 18778381 A EP18778381 A EP 18778381A EP 3850068 A1 EP3850068 A1 EP 3850068A1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
alkyl
aqueous detergent
ether
preferred
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18778381.6A
Other languages
English (en)
French (fr)
Inventor
Nadine Göhring
Peter Forth
Isabelle FRIEDRICH
Silke Denzin
Sabine Swoboda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ecolab USA Inc
Original Assignee
Ecolab USA Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ecolab USA Inc filed Critical Ecolab USA Inc
Publication of EP3850068A1 publication Critical patent/EP3850068A1/de
Pending legal-status Critical Current

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%.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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EP18778381.6A 2018-09-11 2018-09-11 Phasenstabile und schwach schäumende wässrige waschmittelzusammensetzungen mit langer enzymaktivität Pending EP3850068A1 (de)

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DE3816734A1 (de) * 1988-05-17 1989-11-30 Henkel Kgaa Verfahren zur reinigung und desinfektion von hitze- und korrosionsempfindlichen medizinischen geraeten, insbesondere von endoskopen und mittel zur durchfuehrung des verfahrens
US8420584B2 (en) * 2007-03-30 2013-04-16 Melton Sherwood Thoele Enzymatic detergent
US9181296B2 (en) * 2008-03-26 2015-11-10 Novozymes A/S Stabilized liquid enzyme compositions
GB2482164A (en) * 2010-07-22 2012-01-25 Fujifilm Europ Nv Cleaning composition
CN104334704B (zh) * 2012-05-28 2017-03-08 花王株式会社 医疗器具清洗机用洗涤剂组合物
EP3137588A4 (de) * 2014-05-02 2018-03-14 Case Medical Inc. Zusammensetzungen und verfahren zur handhabung von möglicher prionenkontamination
US9796948B2 (en) * 2016-01-13 2017-10-24 The Procter & Gamble Company Laundry detergent compositions comprising renewable components
US9840684B2 (en) * 2016-03-02 2017-12-12 The Procter & Gamble Company Compositions containing alkyl sulfates and/or alkoxylated alkyl sulfates and a solvent comprising a diol
EP3559190A1 (de) * 2016-12-22 2019-10-30 Ecolab USA Inc. Schäumende wässerige reinigungszusammensetzung mit erhöhter schaumverweilzeit und befeuchtungsgehalt

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