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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • 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
• • 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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Citations (5)

• 2020
  • 2020-12-10 EP EP20212931.8A patent/EP4012010A1/de not_active Withdrawn

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