EP4012010A1 - Compositions and their use in chlorinated water - Google Patents
Compositions and their use in chlorinated water Download PDFInfo
- Publication number
- EP4012010A1 EP4012010A1 EP20212931.8A EP20212931A EP4012010A1 EP 4012010 A1 EP4012010 A1 EP 4012010A1 EP 20212931 A EP20212931 A EP 20212931A EP 4012010 A1 EP4012010 A1 EP 4012010A1
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- EP
- European Patent Office
- Prior art keywords
- chelating agent
- compositions
- inventive
- composition according
- acid
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- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
Definitions
- the present invention is directed to compositions containing
- Modern cleaning compositions need to meet many requirements. They need to work under various conditions, for example various temperatures. They need to yield excellent results, in the case of hard surface cleaners and in particular automatic dishwashing formulations they need to provide excellent results with respect to spotting and filming and detergency. In case of laundry care compositions, they need to give excellent cleaning effects at comparably low temperatures. Cleaning compositions need to be environmentally friendly, and they have to work even under conditions where only so-called "hard water” is available, for example water with a comparatively high content of Mg 2+ and Ca 2+ salts.
- Chlorine is a strong disinfectant and kills germs. In alkaline environment, chlorine undergoes disproportionation to chloride and hypochlorite. However, chlorine also has disadvantages. It has a pungent odor, and it may affect various ingredients in cleaning compositions, for example automatic dishwashing compositions and laundry cleaning compositions and especially in liquid laundry compositions. Chlorine bleach even in ppm levels in wash water can impact the stability and efficiency of components of cleaning agents such as enzymes during the cleaning process and hence negatively impact the cleaning performance of detergent. It can also lead to faster fading for fabrics washed.
- compositions defined at the outset have been found, hereinafter also referred to as inventive compositions or compositions according to the present invention.
- compositions contain
- Chelating agent (A) and monoethanolamine (B) will be described in more detail below.
- Alkali metal salts may be selected from lithium potassium salts and sodium salts and combinations therefrom.
- Preferred examples of alkali metal cations are sodium and potassium and combinations of sodium and potassium, and even more preferred in compound according to general formula (I a) and (I b) all M are the same and they are all Na.
- Preferred chelating agents (A) are selected from trisodium salt of MGDA and disodium salt of MGDA and combinations thereof.
- the overall formula (I) [CH 3 -CH(COO)-N(CH 2 -COO) 2 ]M 3-x H x (I) wherein M is selected from ammonium and alkali metal cations, same or different, for example cations of sodium, potassium, and combinations of the foregoing. Even more preferred in compound according to general formula (I) all M are the same and they are all Na, and x in formula (I) is in the range of from zero to 1.0, preferably 0.015 to 0.5.
- MGDA and its respective alkali metal salts are selected from the racemic mixtures, the D-isomers and the L-isomers, and from mixtures of the D- and L-isomers other than the racemic mixtures.
- MGDA and its respective alkali metal salts are selected from the racemic mixture and from mixtures containing in the range of from 55 to 85 mole-% of the L-isomer, the balance being D-isomer.
- Particularly preferred are mixtures containing in the range of from 60 to 80 mole-% of the L-isomer, the balance being D-isomer.
- Other particularly preferred embodiments are racemic mixtures.
- chelating agent (A) may bear a cation other than alkali metal. It is thus possible that minor amounts, such as 0.01 to 5 mol-% of total MGDA, respectively, bear alkali earth metal cations such as Mg 2+ or Ca 2+ , or an Fe 2+ or Fe 3+ cation.
- chelating agent (A) may contain one or more impurities that may result from the synthesis of the respective chelating agent (A).
- impurities may be selected from propionic acid, lactic acid, alanine, nitrilotriacetic acid (NTA) or the like and their respective alkali metal salts.
- Such impurities are usually present in minor amounts.
- Minor amounts in this context refer to a total of 0.1 to 5% by weight, referring to chelating agent (A), preferably up to 2.5% by weight. In the context of the present invention, such minor amounts are neglected when determining the composition of the inventive composition.
- compositions furthermore contain (B) monethanolamine, H 2 N-CH 2 CH 2 -OH.
- compositions are present in a weight ratio of from 3:1 to 8:1, wherein chelating agent (A) is calculated as the free acid.
- a weight ratio of (A) and (B) from 4:1 to 7:1.
- inventive compositions are aqueous compositions.
- aqueous compositions include gels and solutions in which water is comprised as solvent for various ingredients.
- Aqueous compositions may contain solvents other than water, e.g., propylene glycol, diethylene glycol and the like.
- Such organic solvents may serve as hydrotropes.
- Hydrotropes in the context with the present invention are compounds that facilitate the dissolution of compounds that exhibit limited solubility in water. Examples of hydrotropes are organic solvents such as ethanol, isopropanol, ethylene glycol, 1,2-propylene glycol, and further organic solvents that are water-miscible under normal conditions without limitation.
- hydrotropes are the sodium salts of toluene sulfonic acid, of xylene sulfonic acid, and of cumene sulfonic acid.
- the main solvent by volume in inventive aqueous compositions is water, for example 50 to 90 % by volume or oven up to 100% by volume, referring to the total solvent content.
- anionic surfactants (C) are alkali metal and ammonium salts of C 8 -C 18 -alkyl sulfates, of C 8 -C 18 -fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated C 4 -C 12 -alkylphenols (ethoxylation: 1 to 50 mol of ethylene oxide/mol), C 12 -C 18 sulfo fatty acid alkyl esters, for example of C 12 -C 18 sulfo fatty acid methyl esters, furthermore of C 12 -C 18 -alkylsulfonic acids and of C 10 -C 18 -alkylarylsulfonic acids.
- anionic surfactants (C) are soaps, for example the sodium or potassium salts of stearic acid, oleic acid, palmitic acid, ether carboxylates, and alkylether phosphates.
- anionic surfactant (C) is selected from compounds according to general formula (II) R 1 -O(CH 2 CH 2 O) x -SO 3 M (II) wherein
- anionic surfactant (C) may be an average number and therefore n is not necessarily a whole number, while in individual molecules according to formula (I), x denotes a whole number.
- inventive compositions may contain 0.1 to 60 % by weight of anionic surfactant (C), preferably 5 to 50 % by weight.
- compositions may comprise ingredients other than the aforementioned.
- examples are non-ionic surfactants, fragrances, dyestuffs, biocides, preservatives, enzymes, hydrotropes, builders, viscosity modifiers, polymers, buffers, defoamers, and anti-corrosion additives.
- Preferred inventive compositions may contain one or more non-ionic surfactants.
- Preferred non-ionic surfactants are alkoxylated alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl polyglycosides (APG), hydroxyalkyl mixed ethers and amine oxides.
- APG alkyl polyglycosides
- alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (III a) in which the variables are defined as follows:
- e and f are in the range from zero to 300, where the sum of e and f is at least one, preferably in the range of from 3 to 50.
- e is in the range from 1 to 100 and f is in the range from 0 to 30.
- compounds of the general formula (III) may be block copolymers or random copolymers, preference being given to block copolymers.
- alkoxylated alcohols are, for example, compounds of the general formula (III b) in which the variables are defined as follows:
- the sum a + b + d is preferably in the range of from 5 to 100, even more preferably in the range of from 9 to 50.
- Compounds of the general formula (III) may be block copolymers or random copolymers, preference being given to block copolymers.
- nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Further suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl polyglycosides, especially linear C 4 -C 16 -alkyl polyglucosides and branched C 8 -C 14 -alkyl polyglycosides such as compounds of general average formula (IV) are likewise suitable. wherein:
- non-ionic surfactants are compounds of general formula (V) and (VI)
- Mixtures of two or more different nonionic surfactants selected from the foregoing may also be present.
- surfactants that may be present are selected from amphoteric (zwitterionic) surfactants and anionic surfactants and mixtures thereof.
- amphoteric surfactants are those that bear a positive and a negative charge in the same molecule under use conditions.
- Preferred examples of amphoteric surfactants are so-called betaine-surfactants.
- Many examples of betaine-surfactants bear one quaternized nitrogen atom and one carboxylic acid group per molecule.
- a particularly preferred example of amphoteric surfactants is cocamidopropyl betaine (lauramidopropyl betaine).
- amine oxide surfactants are compounds of the general formula (VII) R 9 R 10 R 11 N ⁇ O (VII) wherein R 9 , R 10 , and R 11 are selected independently from each other from aliphatic, cycloaliphatic or C2-C4-alkylene C 10 -C 20 -alkylamido moieties.
- R 9 is selected from C 8 -C 20 -alkyl or C 2 -C 4 -alkylene C 10 -C 20 -alkylamido and R 10 and R 11 are both methyl.
- a particularly preferred example is lauryl dimethyl aminoxide, sometimes also called lauramine oxide.
- a further particularly preferred example is cocamidylpropyl dimethylaminoxide, sometimes also called cocamidopropylamine oxide.
- inventive compositions may contain 0.1 to 60 % by weight of at least one surfactant, selected from non-ionic surfactants, amphoteric surfactants and amine oxide surfactants.
- inventive solid compositions for cleaners and especially those for automatic dishwashing do not contain any anionic surfactant.
- compositions may contain at least one bleaching agent, also referred to as bleach.
- Bleaching agents may be selected from chlorine bleach and peroxide bleach, and peroxide bleach may be selected from inorganic peroxide bleach and organic peroxide bleach.
- Preferred are inorganic peroxide bleaches, selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate.
- organic peroxide bleaches are organic percarboxylic acids, especially organic percarboxylic acids.
- alkali metal percarbonates especially sodium percarbonates
- Such coatings may be of organic or inorganic nature. Examples are glycerol, sodium sulfate, silicate, sodium carbonate, and combinations of at least two of the foregoing, for example combinations of sodium carbonate and sodium sulfate.
- Suitable chlorine-containing bleaches are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.
- compositions may comprise, for example, in the range from 3 to 10% by weight of chlorine-containing bleach.
- Inventive compositions may comprise one or more bleach catalysts.
- Bleach catalysts can be selected from bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes.
- Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also cobalt-, iron-, copper- and ruthenium-amine complexes can also be used as bleach catalysts.
- compositions may comprise one or more bleach activators, for example N-methylmorpholinium-acetonitrile salts ("MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
- MMA salts N-methylmorpholinium-acetonitrile salts
- DADHT 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine
- nitrile quats trimethylammonium acetonitrile salts
- TAED tetraacetylethylenediamine
- TAED tetraacetylhexylenediamine
- fragrances are benzyl salicylate, 2-(4-tert.-butylphenyl) 2-methylpropional, commercially available as Lilial ® , and hexyl cinnamaldehyde.
- dyestuffs are Acid Blue 9, Acid Yellow 3, Acid Yellow 23, Acid Yellow 73, Pigment Yellow 101, Acid Green 1, Solvent Green 7, and Acid Green 25.
- compositions may comprise one more enzymes.
- enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.
- inventive compositions may comprise, for example, up to 5% by weight of enzyme, preference being given to 0.1 to 3% by weight.
- Said enzyme may be stabilized, for example with the sodium salt of at least one C 1 -C 3 -carboxylic acid or C 4 -C 10 -dicarboxylic acid.
- Preferred are formates, acetates, adipates, and succinates.
- Inventive compositions may contain one or more preservatives or biocides.
- Biocides and preservatives prevent alterations of inventive liquid detergent compositions due to attacks from microorganisms.
- examples of biocides and preservatives are BTA (1,2,3-benzotriazole), benzalkonium chlorides, 1,2-benzisothiazolin-3-one ("BIT”), 2-methyl-2H-isothiazol-3-one (“MIT”) and 5-chloro-2-methyl-2H-isothiazol-3-one (“CIT”), benzoic acid, sorbic acid, iodopropynyl butylcarbamate (“IPBC”), dichlorodimethylhydantoine (“DCDMH”), bromochlorodimethylhydantoine (“BCDMH”), and dibromodimethylhydantoine (“DBDMH”).
- BTA 1,2-benzisothiazolin-3-one
- MIT 2-methyl-2H-isothiazol-3-
- viscosity modifiers examples include agar-agar, carragene, tragacanth, gum arabic, alginates, pectins, hydroxyethyl cellulose, hydroxypropyl cellulose, starch, gelatin, locust bean gum, cross-linked poly(meth)acrlyates, for example polyacrlyic acid cross-linked with bis-(meth)acrylamide, furthermore silicic acid, clay such as - but not limited to - montmorrilionite, zeolite, dextrin, and casein.
- cross-linked poly(meth)acrlyates for example polyacrlyic acid cross-linked with bis-(meth)acrylamide, furthermore silicic acid, clay such as - but not limited to - montmorrilionite, zeolite, dextrin, and casein.
- polymers other than polymer (A) are especially polyacrylic acid and its respective alkali metal salts, especially its sodium salt.
- a suitable polymer is in particular polyacrylic acid, preferably with an average molecular weight M w in the range from 2,000 to 40,000 g/mol. preferably 2,000 to 10,000 g/mol, in particular 3,000 to 8,000 g/mol, each partially or fully neutralized with alkali, especially with sodium.
- Suitable as well are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid.
- Polyacrylic acid and its respective alkali metal salts may serve as soil anti-redeposition agents.
- polymers are polyvinylpyrrolidones (PVP).
- PVP polyvinylpyrrolidones
- Polyvinylpyrrolidones may serve as dye transfer inhibitors.
- polymers are polyethylene terephthalates, polyoxyethylene terephthalates, and polyethylene terephthalates that are end-capped with one or two hydrophilic groups per molecule, hydrophilic groups being selected from CH 2 CH 2 CH 2 -SO 3 Na, CH 2 CH(CH 2 -SO 3 Na) 2 , and CH 2 CH(CH 2 SO 2 Na)CH 2 -SO 3 Na.
- buffers is N,N,N-triethanolamine.
- inventive compositions contain at least one enzyme, for example a protease,
- defoamers are silicones.
- Inventive compositions are not only good in cleaning soiled laundry with respect to organic fatty soil such as oil.
- Inventive liquid detergent compositions are very useful for removing non-bleachable stains such as, but not limited to stains from red wine, tea, coffee, vegetables, and various fruit juices like berry juices from laundry. They still do not leave residues on the clothes.
- inventive compositions may be in bulk form or as unit doses, for example in the form of sachets or pouches.
- Suitable materials for pouches are water-soluble polymers such as polyvinyl alcohol.
- inventive compositions are liquid or gel-type.
- inventive compositions are liquid or gel-type and have a pH value in the range of from 7 to 9, preferably 7.5 to 8.5.
- inventive compositions are liquid or gel-type at ambient temperature.
- inventive compositions are liquid or gel-type at ambient temperature and have a total solids content in the range of from 8 to 80%, preferably 10 to 50%, determined by drying under vacuum at 80°C.
- Inventive compositions may be used as or for the manufacture of cleaning compositions, for example automatic dishwashing compositions, hand dishwash compositions, and compositions for hard surfaces other than automatic dishwashing compositions.
- Preferred are laundry cleaning compositions, especially liquid laundry cleaners.
- liquid laundry cleaners as used herein also encompasses gel-type laundry cleaning compositions.
- inventive compositions and especially liquid laundry cleanings that contain inventive compositions, preferably in an amount in the range of from 5 to 50% by weight, referring to their total solids content, are particular efficient in the presence of chlorinated drinking water - hereinafter also referred to as "municipal water". In that context, they serve as scavenger of chlorine.
- a further aspect of the present invention thus relates to a process for hard surfaces and especially for cleaning laundry, hereinafter also referred to as inventive cleaning process and especially as inventive laundering process, respectively.
- inventive cleaning process and especially the inventive laundering process are performed by using an inventive composition, for example as a unit dose.
- Another aspect of the present invention is a process for cleaning laundry or hard surfaces, e.g., dishware, preferably in an automatic dishwasher, hereinafter also referred to as inventive cleaning process.
- inventive cleaning process is characterized in that it is performed under use of an inventive composition.
- hard surface cleaners includes compositions for dishwashing, especially hand dishwash and automatic dishwashing and ware-washing, and compositions for other hard surface cleaning such as, but not limited to compositions for bathroom cleaning, kitchen cleaning, floor cleaning, descaling of pipes, window cleaning, car cleaning including truck cleaning, furthermore, open plant cleaning, cleaning-in-place, metal cleaning, disinfectant cleaning, farm cleaning, high pressure cleaning, but not laundry detergent compositions.
- Dishware as used hereunder includes china, polymer, metal, clay, and glassware.
- a process to clean dishware includes removal of all sorts of soil, like fat, proteins, starch, dyes, and more.
- dishware includes articles used in the preparation, serving, consumption, and disposal of food stuffs including pots, pans, trays, pitchers, bowls, plates, saucers, cups, glasses, forks, knives, spoons, spatulas, and other glass, metal, ceramic, plastic composite articles commonly available in the institutional or household kitchen or dining room.
- dishware can be referred to as food or beverage contacting articles because they have surfaces which are provided for contacting food and/or beverage.
- cleaning composition and/or rinse aid should provide effective sheeting action and low foaming properties.
- a cleaning composition and/or rinse aid of this type may be described as being "food grade”.
- the inventive cleaning process may be carried out at temperatures in the range of from 10 to 90°C.
- the inventive cleaning process is carried out as an automatic dishwashing process, it is preferably carried out at a temperature in the range of from 45 to 65°C, more preferably 50 to 60°C.
- Said temperature refers to the temperature of the water being used in the inventive process.
- the inventive cleaning process is carried out as laundering process it may be carried at a temperature of from 25 to 65°C.
- the inventive process is carried out using water.
- the amount of water is influenced by the type of machine used and by the choice of the program.
- the water used may have a German hardness in the range of from zero to 25° dH, referring to the permanent hardness.
- the inventive cleaning process is preferably performed with a combination of two compositions of which one is an inventive composition, and the other composition comprises at least one non-ionic surfactant and at least one inorganic salt selected from alkali metal sulfates and alkali metal (bi)carbonates.
- inventive cleaning process and especially the inventive laundering process are preferred when said processes are performed with water that contains in the range of from 0.1 to 5 ppm chlorine.
- the chlorine content may be determined by SenSafe Free Chlorine water test strip (part 480002). It is therefore another aspect of the present invention to use inventive compositions for scavenging Cl 2 that is present in water, especially in municipal water.
- inventive manufacturing process comprises the step of combining
- the inventive manufacturing process may be carried out by adding monoethanolamine - in bulk or as aqueous solution - to an aqueous solution of chelating agent (A). It is preferred to support the inventive manufacturing process by a mixing operation, for example shaking or stirring. It is preferred to add monoethanolamine as free base.
- the inventive manufacturing process may by carried out in a wide range of temperatures, for example of from 5 to 95°C. It is preferred to carry out the inventive process at a temperature in the range of from 10 to 40°C.
- Pressure conditions are not critical for the inventive process. It is preferred to carry out the inventive process at ambient pressure.
- the resulting composition may be used as such or be diluted with water.
- the present invention is further illustrated by working examples.
- the local municipal water during the test was 0.4 ppm, determined with SenSafe Free Chlorine strips, commercially available from Industrial Test Systems Inc., In order to obtain more relevant results, sodium hypochlorite (commercially available from Alfa Aesar) was added until the free Cl 2 content was 5 ppm. So-called “spiked water” was obtained.
- a 1-I-beaker was charged with 94 g of (A.1). An amount of 6 g of monoethanolamine (“MEA”) was added under stirring at ambient conditions. Stirring was continued for 10 minutes. IC.1 was obtained.
- MEA monoethanolamine
- Comparative compositions were obtained by replacing monoethanolamine by triethanolamine C-(IC.2), a polyamine (C-IC.3) or a branched polyethylenimine, M w 800 g/mol (GPC), C-IC.4.
- IC.1 0.2 g was diluted with 100 ml of de-ionized water. Then, 20 g of Cl 2 -spiked municipal water (5 ppm free chlorine) was added. The free chlorine content was determined with SenSafe Free Chlorine strips, Industrial Test Systems Inc. It was determined how much inventive formulation was needed to reach an active chlorine level of 1 ppm or less (which is acceptable) within the same period of time.
- Table 1 shows that less IC.1 was needed to reduce the chlorine content compared to (A.1). In addition, Table 1 shows the superiority of monoethanolamine compared to amines other than monoethanolamine Table 1: Test results of inventive compositions and reference compositions formulation Active Material (ppm) required MGDA-Na 3 (A.1) 52 IC.1 19 C-IC.2 61 C-IC.3 90 C-IC.4 28.7
- a model liquid laundering composition was made by mixing the components as below. Table 1.
- L.1 Ingredients of base mixture for a liquid detergent formulation ingredient % by weight De-ionized Water q.s. to 100 Na salt of linear alkylbenzene sulfonic acid 6.72 Sodium Laureth (3EO) sulphate (29.5%) 12.5 C 12 /C 14 -Linear alcohol reacted with 6.5 moles of EO 6.25
- Ethanol 2 Enzyme combination of protease, mannanase and amylase 1.6 NaOH (50%) or citric acid (50%) q.s. to pH 8.
- the resultant formulation yielded good laundering results in chlorinated municipal water.
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Abstract
Compositions containing
(A) at least one chelating agent selected from alkali metal salts of methyl glycine diacetic acid (MGDA),
(B) monoethanolamine,
wherein (A) and (B) are present in a weight ratio of from 3:1 to 8:1, and wherein (A) is calculated as the free acid.
(A) at least one chelating agent selected from alkali metal salts of methyl glycine diacetic acid (MGDA),
(B) monoethanolamine,
wherein (A) and (B) are present in a weight ratio of from 3:1 to 8:1, and wherein (A) is calculated as the free acid.
Description
- The present invention is directed to compositions containing
- (A) at least one chelating agent selected from alkali metal salts of methyl glycine diacetic acid (MGDA),
- (B) monoethanolamine,
- Modern cleaning compositions need to meet many requirements. They need to work under various conditions, for example various temperatures. They need to yield excellent results, in the case of hard surface cleaners and in particular automatic dishwashing formulations they need to provide excellent results with respect to spotting and filming and detergency. In case of laundry care compositions, they need to give excellent cleaning effects at comparably low temperatures. Cleaning compositions need to be environmentally friendly, and they have to work even under conditions where only so-called "hard water" is available, for example water with a comparatively high content of Mg2+ and Ca2+ salts.
- In many areas of the world, drinking water is chlorinated for hygiene purposes. Chlorine (Cl2) is a strong disinfectant and kills germs. In alkaline environment, chlorine undergoes disproportionation to chloride and hypochlorite. However, chlorine also has disadvantages. It has a pungent odor, and it may affect various ingredients in cleaning compositions, for example automatic dishwashing compositions and laundry cleaning compositions and especially in liquid laundry compositions. Chlorine bleach even in ppm levels in wash water can impact the stability and efficiency of components of cleaning agents such as enzymes during the cleaning process and hence negatively impact the cleaning performance of detergent. It can also lead to faster fading for fabrics washed.
- It was therefore an objective of the present invention to provide environmentally friendly cleaning compositions that are less or not at all affected by Cl2 present in the drinking water. It was furthermore an objective to provide a process for making such compositions, and it was an objective to provide applications (uses) of such compositions.
- Accordingly, the compositions defined at the outset have been found, hereinafter also referred to as inventive compositions or compositions according to the present invention.
- Inventive compositions contain
- (A) at least one chelating agent selected from alkali metal salts of methyl glycine diacetic acid (MGDA), hereinafter also referred to as chelating agent (A) or briefly as (A),
- (B) monoethanolamine, hereinafter also referred to as monoethanolamine (B) or briefly as (B),
- Chelating agent (A) and monoethanolamine (B) will be described in more detail below.
- Alkali metal salts may be selected from lithium potassium salts and sodium salts and combinations therefrom. Preferred examples of alkali metal cations are sodium and potassium and combinations of sodium and potassium, and even more preferred in compound according to general formula (I a) and (I b) all M are the same and they are all Na.
- Preferred chelating agents (A) are selected from trisodium salt of MGDA and disodium salt of MGDA and combinations thereof.
- For example, the overall formula (I)
[CH3-CH(COO)-N(CH2-COO)2]M3-xHx (I)
wherein M is selected from ammonium and alkali metal cations, same or different, for example cations of sodium, potassium, and combinations of the foregoing. Even more preferred in compound according to general formula (I) all M are the same and they are all Na,
and x in formula (I) is in the range of from zero to 1.0, preferably 0.015 to 0.5. - MGDA and its respective alkali metal salts are selected from the racemic mixtures, the D-isomers and the L-isomers, and from mixtures of the D- and L-isomers other than the racemic mixtures. Preferably, MGDA and its respective alkali metal salts are selected from the racemic mixture and from mixtures containing in the range of from 55 to 85 mole-% of the L-isomer, the balance being D-isomer. Particularly preferred are mixtures containing in the range of from 60 to 80 mole-% of the L-isomer, the balance being D-isomer. Other particularly preferred embodiments are racemic mixtures.
- In any way, chelating agent (A) may bear a cation other than alkali metal. It is thus possible that minor amounts, such as 0.01 to 5 mol-% of total MGDA, respectively, bear alkali earth metal cations such as Mg2+ or Ca2+, or an Fe2+ or Fe3+ cation.
- In one embodiment of the present invention, chelating agent (A) may contain one or more impurities that may result from the synthesis of the respective chelating agent (A). In the cases of MGDA, such impurities may be selected from propionic acid, lactic acid, alanine, nitrilotriacetic acid (NTA) or the like and their respective alkali metal salts. Such impurities are usually present in minor amounts. "Minor amounts" in this context refer to a total of 0.1 to 5% by weight, referring to chelating agent (A), preferably up to 2.5% by weight. In the context of the present invention, such minor amounts are neglected when determining the composition of the inventive composition.
- Inventive compositions furthermore contain
(B) monethanolamine, H2N-CH2CH2-OH. - In inventive compositions, (A) and (B) are present in a weight ratio of from 3:1 to 8:1, wherein chelating agent (A) is calculated as the free acid. Preferred is a weight ratio of (A) and (B) from 4:1 to 7:1.
- Preferably, inventive compositions are aqueous compositions. In the context of the present invention, aqueous compositions include gels and solutions in which water is comprised as solvent for various ingredients. Aqueous compositions may contain solvents other than water, e.g., propylene glycol, diethylene glycol and the like. Such organic solvents may serve as hydrotropes. Hydrotropes in the context with the present invention are compounds that facilitate the dissolution of compounds that exhibit limited solubility in water. Examples of hydrotropes are organic solvents such as ethanol, isopropanol, ethylene glycol, 1,2-propylene glycol, and further organic solvents that are water-miscible under normal conditions without limitation.
- Further examples of suitable hydrotropes are the sodium salts of toluene sulfonic acid, of xylene sulfonic acid, and of cumene sulfonic acid.
- Preferably, the main solvent by volume in inventive aqueous compositions is water, for example 50 to 90 % by volume or oven up to 100% by volume, referring to the total solvent content. Composition according to any of the preceding claims wherein said composition additionally contains a surfactant, preferably - in cases of laundry cleaners - at least one anionic surfactant (C).
- Examples of anionic surfactants (C) are alkali metal and ammonium salts of C8-C18-alkyl sulfates, of C8-C18-fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated C4-C12-alkylphenols (ethoxylation: 1 to 50 mol of ethylene oxide/mol), C12-C18 sulfo fatty acid alkyl esters, for example of C12-C18 sulfo fatty acid methyl esters, furthermore of C12-C18-alkylsulfonic acids and of C10-C18-alkylarylsulfonic acids. Preference is given to the alkali metal salts of the aforementioned compounds, particularly preferably the sodium salts.
- Further examples of anionic surfactants (C) are soaps, for example the sodium or potassium salts of stearic acid, oleic acid, palmitic acid, ether carboxylates, and alkylether phosphates.
- In a preferred embodiment of the present invention, anionic surfactant (C) is selected from compounds according to general formula (II)
R1-O(CH2CH2O)x-SO3M (II)
wherein - R1
- n-C10-C18-alkyl, especially with an even number of carbon atoms, for example n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, or n-octadecyl, preferably C10-C14-alkyl, and even more preferably n-C12-alkyl,
- x
- being a number in the range of from 1 to 5, preferably 2 to 4 and even more preferably 3.
- M
- being selected from alkali metals, preferably potassium and even more preferably sodium.
- In anionic surfactant (C), x may be an average number and therefore n is not necessarily a whole number, while in individual molecules according to formula (I), x denotes a whole number.
- In one embodiment of the present invention, inventive compositions may contain 0.1 to 60 % by weight of anionic surfactant (C), preferably 5 to 50 % by weight.
- Inventive compositions may comprise ingredients other than the aforementioned. Examples are non-ionic surfactants, fragrances, dyestuffs, biocides, preservatives, enzymes, hydrotropes, builders, viscosity modifiers, polymers, buffers, defoamers, and anti-corrosion additives.
- Preferred inventive compositions may contain one or more non-ionic surfactants.
- Preferred non-ionic surfactants are alkoxylated alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl polyglycosides (APG), hydroxyalkyl mixed ethers and amine oxides.
-
- R2
- is identical or different and selected from hydrogen and linear C1-C10-alkyl, preferably in each case identical and ethyl and particularly preferably hydrogen or methyl,
- R3
- is selected from C8-C22-alkyl, branched or linear, for example n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33 or n-C18H37,
- R4
- is selected from C1-C10-alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl,
- The variables e and f are in the range from zero to 300, where the sum of e and f is at least one, preferably in the range of from 3 to 50. Preferably, e is in the range from 1 to 100 and f is in the range from 0 to 30.
- In one embodiment, compounds of the general formula (III) may be block copolymers or random copolymers, preference being given to block copolymers.
-
- R2
- is identical or different and selected from hydrogen and linear C1-C0-alkyl, preferably identical in each case and ethyl and particularly preferably hydrogen or methyl,
- R5
- is selected from C6-C20-alkyl, branched or linear, in particular n-C8H17, n-C10H21, n-C12H25, n-C13H27, n-C15H31, n-C14H29, n-C16H33, n-C18H37,
- a
- is a number in the range from zero to 10, preferably from 1 to 6,
- b
- is a number in the range from 1 to 80, preferably from 4 to 20,
- d
- is a number in the range from zero to 50, preferably 4 to 25.
- The sum a + b + d is preferably in the range of from 5 to 100, even more preferably in the range of from 9 to 50.
- Compounds of the general formula (III) may be block copolymers or random copolymers, preference being given to block copolymers.
- Further suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Further suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl polyglycosides, especially linear C4-C16-alkyl polyglucosides and branched C8-C14-alkyl polyglycosides such as compounds of general average formula (IV) are likewise suitable.
- R6
- is C1-C4-alkyl, in particular ethyl, n-propyl or isopropyl,
- R7
- is -(CH2)2-R6,
- G1
- is selected from monosaccharides with 4 to 6 carbon atoms, especially from glucose and xylose,
- y
- in the range of from 1.1 to 4, y being an average number,
-
- AO
- is selected from ethylene oxide, propylene oxide and butylene oxide,
- EO
- is ethylene oxide, CH2CH2-O,
- R8
- selected from C8-C18-alkyl, branched or linear, and R5 is defined as above.
- A3O
- is selected from propylene oxide and butylene oxide,
- w
- is a number in the range of from 15 to 70, preferably 30 to 50,
- w1 and w3
- are numbers in the range of from 1 to 5, and
- w2
- is a number in the range of from 13 to 35.
- An overview of suitable further nonionic surfactants can be found in
EP-A 0 851 023 and inDE-A 198 19 187 . - Mixtures of two or more different nonionic surfactants selected from the foregoing may also be present.
- Other surfactants that may be present are selected from amphoteric (zwitterionic) surfactants and anionic surfactants and mixtures thereof.
- Examples of amphoteric surfactants are those that bear a positive and a negative charge in the same molecule under use conditions. Preferred examples of amphoteric surfactants are so-called betaine-surfactants. Many examples of betaine-surfactants bear one quaternized nitrogen atom and one carboxylic acid group per molecule. A particularly preferred example of amphoteric surfactants is cocamidopropyl betaine (lauramidopropyl betaine).
- Examples of amine oxide surfactants are compounds of the general formula (VII)
R9R10R11N→O (VII)
wherein R9, R10, and R11 are selected independently from each other from aliphatic, cycloaliphatic or C2-C4-alkylene C10-C20-alkylamido moieties. Preferably, R9 is selected from C8-C20-alkyl or C2-C4-alkylene C10-C20-alkylamido and R10 and R11 are both methyl. - A particularly preferred example is lauryl dimethyl aminoxide, sometimes also called lauramine oxide. A further particularly preferred example is cocamidylpropyl dimethylaminoxide, sometimes also called cocamidopropylamine oxide.
- In one embodiment of the present invention, inventive compositions may contain 0.1 to 60 % by weight of at least one surfactant, selected from non-ionic surfactants, amphoteric surfactants and amine oxide surfactants.
- In a preferred embodiment, inventive solid compositions for cleaners and especially those for automatic dishwashing do not contain any anionic surfactant.
- Inventive compositions may contain at least one bleaching agent, also referred to as bleach. Bleaching agents may be selected from chlorine bleach and peroxide bleach, and peroxide bleach may be selected from inorganic peroxide bleach and organic peroxide bleach. Preferred are inorganic peroxide bleaches, selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate.
- Examples of organic peroxide bleaches are organic percarboxylic acids, especially organic percarboxylic acids.
- In inventive compositions, alkali metal percarbonates, especially sodium percarbonates, are preferably used in coated form. Such coatings may be of organic or inorganic nature. Examples are glycerol, sodium sulfate, silicate, sodium carbonate, and combinations of at least two of the foregoing, for example combinations of sodium carbonate and sodium sulfate.
- Suitable chlorine-containing bleaches are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.
- Inventive compositions may comprise, for example, in the range from 3 to 10% by weight of chlorine-containing bleach.
- Inventive compositions may comprise one or more bleach catalysts. Bleach catalysts can be selected from bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also cobalt-, iron-, copper- and ruthenium-amine complexes can also be used as bleach catalysts.
- Inventive compositions may comprise one or more bleach activators, for example N-methylmorpholinium-acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT") or nitrile quats (trimethylammonium acetonitrile salts).
- Further examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.
- Examples of fragrances are benzyl salicylate, 2-(4-tert.-butylphenyl) 2-methylpropional, commercially available as Lilial®, and hexyl cinnamaldehyde.
- Examples of dyestuffs are Acid Blue 9, Acid Yellow 3, Acid Yellow 23, Acid Yellow 73, Pigment Yellow 101, Acid Green 1, Solvent Green 7, and Acid Green 25.
- Inventive compositions may comprise one more enzymes. Examples of enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.
- In one embodiment of the present invention, inventive compositions may comprise, for example, up to 5% by weight of enzyme, preference being given to 0.1 to 3% by weight. Said enzyme may be stabilized, for example with the sodium salt of at least one C1-C3-carboxylic acid or C4-C10-dicarboxylic acid. Preferred are formates, acetates, adipates, and succinates.
- Inventive compositions may contain one or more preservatives or biocides. Biocides and preservatives prevent alterations of inventive liquid detergent compositions due to attacks from microorganisms. Examples of biocides and preservatives are BTA (1,2,3-benzotriazole), benzalkonium chlorides, 1,2-benzisothiazolin-3-one ("BIT"), 2-methyl-2H-isothiazol-3-one ("MIT") and 5-chloro-2-methyl-2H-isothiazol-3-one ("CIT"), benzoic acid, sorbic acid, iodopropynyl butylcarbamate ("IPBC"), dichlorodimethylhydantoine ("DCDMH"), bromochlorodimethylhydantoine ("BCDMH"), and dibromodimethylhydantoine ("DBDMH").
- Examples of viscosity modifiers are agar-agar, carragene, tragacanth, gum arabic, alginates, pectins, hydroxyethyl cellulose, hydroxypropyl cellulose, starch, gelatin, locust bean gum, cross-linked poly(meth)acrlyates, for example polyacrlyic acid cross-linked with bis-(meth)acrylamide, furthermore silicic acid, clay such as - but not limited to - montmorrilionite, zeolite, dextrin, and casein.
- Examples of polymers other than polymer (A) are especially polyacrylic acid and its respective alkali metal salts, especially its sodium salt. A suitable polymer is in particular polyacrylic acid, preferably with an average molecular weight Mw in the range from 2,000 to 40,000 g/mol. preferably 2,000 to 10,000 g/mol, in particular 3,000 to 8,000 g/mol, each partially or fully neutralized with alkali, especially with sodium. Suitable as well are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid. Polyacrylic acid and its respective alkali metal salts may serve as soil anti-redeposition agents.
- Further examples of polymers are polyvinylpyrrolidones (PVP). Polyvinylpyrrolidones may serve as dye transfer inhibitors.
- Further examples of polymers are polyethylene terephthalates, polyoxyethylene terephthalates, and polyethylene terephthalates that are end-capped with one or two hydrophilic groups per molecule, hydrophilic groups being selected from CH2CH2CH2-SO3Na, CH2CH(CH2-SO3Na)2, and CH2CH(CH2SO2Na)CH2-SO3Na.
- An example of buffers is N,N,N-triethanolamine.
- in one embodiment of the present invention, inventive compositions contain at least one enzyme, for example a protease,
- Examples of defoamers are silicones.
- Inventive compositions are not only good in cleaning soiled laundry with respect to organic fatty soil such as oil. Inventive liquid detergent compositions are very useful for removing non-bleachable stains such as, but not limited to stains from red wine, tea, coffee, vegetables, and various fruit juices like berry juices from laundry. They still do not leave residues on the clothes.
- In order to be suitable as liquid laundry compositions, inventive compositions may be in bulk form or as unit doses, for example in the form of sachets or pouches. Suitable materials for pouches are water-soluble polymers such as polyvinyl alcohol.
- In a preferred embodiment of the present invention, inventive compositions are liquid or gel-type.
- In one embodiment of the present invention, inventive compositions are liquid or gel-type and have a pH value in the range of from 7 to 9, preferably 7.5 to 8.5.
- In one embodiment of the present invention, inventive compositions are liquid or gel-type at ambient temperature.
- In one embodiment of the present invention, inventive compositions are liquid or gel-type at ambient temperature and have a total solids content in the range of from 8 to 80%, preferably 10 to 50%, determined by drying under vacuum at 80°C.
- Inventive compositions may be used as or for the manufacture of cleaning compositions, for example automatic dishwashing compositions, hand dishwash compositions, and compositions for hard surfaces other than automatic dishwashing compositions. Preferred are laundry cleaning compositions, especially liquid laundry cleaners. The term liquid laundry cleaners as used herein also encompasses gel-type laundry cleaning compositions.
- Cleaning compositions and especially liquid laundry cleanings that contain inventive compositions, preferably in an amount in the range of from 5 to 50% by weight, referring to their total solids content, are particular efficient in the presence of chlorinated drinking water - hereinafter also referred to as "municipal water". In that context, they serve as scavenger of chlorine. A further aspect of the present invention thus relates to a process for hard surfaces and especially for cleaning laundry, hereinafter also referred to as inventive cleaning process and especially as inventive laundering process, respectively. The inventive cleaning process and especially the inventive laundering process are performed by using an inventive composition, for example as a unit dose.
- Another aspect of the present invention is a process for cleaning laundry or hard surfaces, e.g., dishware, preferably in an automatic dishwasher, hereinafter also referred to as inventive cleaning process. The inventive cleaning process is characterized in that it is performed under use of an inventive composition.
- The term "hard surface cleaners" includes compositions for dishwashing, especially hand dishwash and automatic dishwashing and ware-washing, and compositions for other hard surface cleaning such as, but not limited to compositions for bathroom cleaning, kitchen cleaning, floor cleaning, descaling of pipes, window cleaning, car cleaning including truck cleaning, furthermore, open plant cleaning, cleaning-in-place, metal cleaning, disinfectant cleaning, farm cleaning, high pressure cleaning, but not laundry detergent compositions.
- Dishware as used hereunder includes china, polymer, metal, clay, and glassware. A process to clean dishware includes removal of all sorts of soil, like fat, proteins, starch, dyes, and more.
- More specifically, the term "dishware" includes articles used in the preparation, serving, consumption, and disposal of food stuffs including pots, pans, trays, pitchers, bowls, plates, saucers, cups, glasses, forks, knives, spoons, spatulas, and other glass, metal, ceramic, plastic composite articles commonly available in the institutional or household kitchen or dining room. In general, such dishware can be referred to as food or beverage contacting articles because they have surfaces which are provided for contacting food and/or beverage. When used in these ware-washing applications, cleaning composition and/or rinse aid should provide effective sheeting action and low foaming properties. In addition to having the desirable properties described above, it may also be useful for cleaning compositions and/or rinse aids to be biodegradable, environmentally friendly, and generally nontoxic. A cleaning composition and/or rinse aid of this type may be described as being "food grade".
- The inventive cleaning process may be carried out at temperatures in the range of from 10 to 90°C. In embodiments wherein the inventive cleaning process is carried out as an automatic dishwashing process, it is preferably carried out at a temperature in the range of from 45 to 65°C, more preferably 50 to 60°C. Said temperature refers to the temperature of the water being used in the inventive process. In embodiments wherein the inventive cleaning process is carried out as laundering process it may be carried at a temperature of from 25 to 65°C.
- The inventive process is carried out using water. In embodiments wherein the inventive cleaning process is carried out as an automatic dishwashing or laundering process, the amount of water is influenced by the type of machine used and by the choice of the program.
- The water used may have a German hardness in the range of from zero to 25° dH, referring to the permanent hardness.
- In embodiments wherein the inventive cleaning process is carried out as an automatic dishwashing process, the inventive cleaning process is preferably performed with a combination of two compositions of which one is an inventive composition, and the other composition comprises at least one non-ionic surfactant and at least one inorganic salt selected from alkali metal sulfates and alkali metal (bi)carbonates.
- The inventive cleaning process and especially the inventive laundering process are preferred when said processes are performed with water that contains in the range of from 0.1 to 5 ppm chlorine. The chlorine content may be determined by SenSafe Free Chlorine water test strip (part 480002). It is therefore another aspect of the present invention to use inventive compositions for scavenging Cl2 that is present in water, especially in municipal water.
- Another aspect of the present invention is related to a process for making inventive compositions, hereinafter also referred to as inventive manufacturing process. The inventive manufacturing process comprises the step of combining
- (A) an aqueous solution of at least one chelating agent selected from alkali metal salts of methyl glycine diacetic acid (MGDA), and
- (B) monoethanolamine
- The inventive manufacturing process may be carried out by adding monoethanolamine - in bulk or as aqueous solution - to an aqueous solution of chelating agent (A). It is preferred to support the inventive manufacturing process by a mixing operation, for example shaking or stirring. It is preferred to add monoethanolamine as free base.
- The inventive manufacturing process may by carried out in a wide range of temperatures, for example of from 5 to 95°C. It is preferred to carry out the inventive process at a temperature in the range of from 10 to 40°C.
- Pressure conditions are not critical for the inventive process. It is preferred to carry out the inventive process at ambient pressure.
- The resulting composition may be used as such or be diluted with water.
- The present invention is further illustrated by working examples.
- The local municipal water during the test was 0.4 ppm, determined with SenSafe Free Chlorine strips, commercially available from Industrial Test Systems Inc., In order to obtain more relevant results, sodium hypochlorite (commercially available from Alfa Aesar) was added until the free Cl2 content was 5 ppm. So-called "spiked water" was obtained.
- Unless indicated otherwise, percentages refer to weight %, and ppm refer to weight-ppm. (A.1) MGDA-Na3, as aqueous solution, 40% by weight, available from BASF Corp.
- A 1-I-beaker was charged with 94 g of (A.1). An amount of 6 g of monoethanolamine ("MEA") was added under stirring at ambient conditions. Stirring was continued for 10 minutes. IC.1 was obtained.
- Comparative compositions were obtained by replacing monoethanolamine by triethanolamine C-(IC.2), a polyamine (C-IC.3) or a branched polyethylenimine, Mw 800 g/mol (GPC), C-IC.4.
- 0.2 g of IC.1 was diluted with 100 ml of de-ionized water. Then, 20 g of Cl2-spiked municipal water (5 ppm free chlorine) was added. The free chlorine content was determined with SenSafe Free Chlorine strips, Industrial Test Systems Inc. It was determined how much inventive formulation was needed to reach an active chlorine level of 1 ppm or less (which is acceptable) within the same period of time.
- Table 1 shows that less IC.1 was needed to reduce the chlorine content compared to (A.1). In addition, Table 1 shows the superiority of monoethanolamine compared to amines other than monoethanolamine
Table 1: Test results of inventive compositions and reference compositions formulation Active Material (ppm) required MGDA-Na3 (A.1) 52 IC.1 19 C-IC.2 61 C-IC.3 90 C-IC.4 28.7 - A model liquid laundering composition was made by mixing the components as below.
Table 1. L.1 Ingredients of base mixture for a liquid detergent formulation ingredient % by weight De-ionized Water q.s. to 100 Na salt of linear alkylbenzene sulfonic acid 6.72 Sodium Laureth (3EO) sulphate (29.5%) 12.5 C12/C14-Linear alcohol reacted with 6.5 moles of EO 6.25 Coconut Fatty acid 1.8 Diluted IC.1 3 1,2 propyleneglycol 6 Ethanol 2 Enzyme combination of protease, mannanase and amylase 1.6 NaOH (50%) or citric acid (50%) q.s. to pH 8. - For the performance test in a household washing machine (Whirlpool Top loader machine), 90°F wash and cold rinse, medium program (64 L wash volume and 12 minute wash time), 2.5-2.6k g ballast fabric (mixed blend / cotton), four multi-stain monitors (ASTM modified multi-stain monitors on Cotton and cotton/polyester blend.
- The resultant formulation yielded good laundering results in chlorinated municipal water.
Claims (12)
- Composition containing(A) at least one chelating agent selected from alkali metal salts of methyl glycine diacetic acid (MGDA),(B) monoethanolamine,wherein chelating agent (A) and (B) are present in a weight ratio of from 3:1 to 8:1, and wherein chelating agent (A) is calculated as the free acid.
- Composition according to claim 1 wherein chelating agent (A) is selected from the trisodium salt of MGDA and the disodium salt of MGDA and combinations thereof.
- Composition according to claim 1 or 2 wherein chelating agent (A) and (B) are present in a weight ratio of from 4:1 to 7:1.
- Composition according to any of the preceding claims wherein chelating agent (A) is provided as mixture of enantiomers, said mixture containing predominantly the respective L-enantiomer with an enantiomeric excess (ee) in the range of from 10 to 75 %.
- Composition according to any of the preceding claims wherein said composition is an aqueous composition.
- Composition according to any of the preceding claims wherein said composition additionally contains a surfactant.
- Composition according to any of the preceding claims wherein said composition is liquid or gel-type at ambient temperature.
- Process for cleaning hard surfaces or laundry wherein said process is performed under use of a composition according to any of claims 1 to 7.
- Process according to claim 8 wherein said process is performed with water that contains in the range of from 0.1 to 5 ppm chlorine.
- Process according to claim 8 or 9 wherein said process is automatic dishwashing.
- Use of a composition according to any of claims 1 to 7 for scavenging chlorine in water.
- Process for making a composition according to any of claims 1 to 7 comprising the step of combining an aqueous solution of(A) at least one chelating agent selected from alkali metal salts of methyl glycine diacetic acid (MGDA), and(B) monoethanolaminewith chelating agent (A) and (B) in a weight ratio of from 3:1 to 8:1, wherein chelating agent (A) is calculated as the free acid.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0851023A2 (en) | 1996-12-23 | 1998-07-01 | Unilever N.V. | Machine dishwashing tablets containing a peracid |
DE19819187A1 (en) | 1998-04-30 | 1999-11-11 | Henkel Kgaa | Solid dishwasher detergent with phosphate and crystalline layered silicates |
JP2009161581A (en) * | 2007-12-28 | 2009-07-23 | Lion Corp | Liquid detergent composition |
WO2017174358A1 (en) * | 2016-04-06 | 2017-10-12 | Henkel Ag & Co. Kgaa | Liquid detergent composition containing dye transfer inhibitors and optical brighteners |
CN110257180A (en) * | 2019-04-16 | 2019-09-20 | 广东优凯科技有限公司 | Dish washing detergent for dish-washing machine |
-
2020
- 2020-12-10 EP EP20212931.8A patent/EP4012010A1/en not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0851023A2 (en) | 1996-12-23 | 1998-07-01 | Unilever N.V. | Machine dishwashing tablets containing a peracid |
DE19819187A1 (en) | 1998-04-30 | 1999-11-11 | Henkel Kgaa | Solid dishwasher detergent with phosphate and crystalline layered silicates |
JP2009161581A (en) * | 2007-12-28 | 2009-07-23 | Lion Corp | Liquid detergent composition |
WO2017174358A1 (en) * | 2016-04-06 | 2017-10-12 | Henkel Ag & Co. Kgaa | Liquid detergent composition containing dye transfer inhibitors and optical brighteners |
CN110257180A (en) * | 2019-04-16 | 2019-09-20 | 广东优凯科技有限公司 | Dish washing detergent for dish-washing machine |
Non-Patent Citations (1)
Title |
---|
"Trilon M types", 1 May 2007 (2007-05-01), pages 1 - 14, XP055362624, Retrieved from the Internet <URL:https://web.archive.org/web/20190713091330/http://site.saveoncitric.com/trilon_m_info.pdf> [retrieved on 20210517] * |
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