EP3898920A1 - Bleach activators containing two quarternary ammonium groups - Google Patents

Bleach activators containing two quarternary ammonium groups

Info

Publication number
EP3898920A1
EP3898920A1 EP19818025.9A EP19818025A EP3898920A1 EP 3898920 A1 EP3898920 A1 EP 3898920A1 EP 19818025 A EP19818025 A EP 19818025A EP 3898920 A1 EP3898920 A1 EP 3898920A1
Authority
EP
European Patent Office
Prior art keywords
linear
branched
carbon atoms
compound
alkyl
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.)
Withdrawn
Application number
EP19818025.9A
Other languages
German (de)
French (fr)
Inventor
Sascha Schaefer
Svenja NEUHAUS
Antje Gebert-Schwarzwaelder
Nora SCHMIDT
Christa JUNKES
Arne Jansen
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3898920A1 publication Critical patent/EP3898920A1/en
Withdrawn legal-status Critical Current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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3927—Quarternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives

Definitions

  • the present invention relates to a compound of formula (I) and additionally to a method to manufacture the compound of formula (I). Furthermore, the invention is directed to a use of the compound of formula (I) as a bleach activator and to a laundry detergent composition, an automatic dishwashing composition, and an industrial cotton bleach composition, which comprise at least one compound of formula (I) according to the invention.
  • Bleachable stains or colored materials on textiles or on hard surfaces can be discolored, oxidized and ultimately removed using highly active bleach activators in combination with a source of hydrogen peroxide.
  • TAED tetraacetylethylenediamine
  • Some commonly used bleach activators such as tetraacetylethylenediamine (TAED) show a low water solubility at low temperatures. Low temperature washing and cleaning of laundry and hard surfaces requires more reactive bleach activators, which aliphatic activators cannot achieve.
  • Commonly used activators like TAED provide only less reactive bleach-active compounds such as peracids and are less efficient in the generation of the same. Benzylic peracids have a much higher activity towards bleachable stains and colored materials, which makes them more sustainable and allow formulations, which are more compact.
  • quaternary ammonium groups-containing lactam-based compounds can be applied as bleach activators, preferably in laundry detergents, automatic dishwashing agents or industrial cotton bleach compositions. These compounds provide higher solubility in water, preferably at low temperatures, and higher affinity towards fibers, preferably cotton fibers, in comparison with non- charged or anionic bleach activators. Furthermore, they provide a higher bleaching activity compared to aliphatic bleach activators such as TAED. Thereby, lower dosages of bleach activators are required in a composition, to achieve the same bleaching effect.
  • the present invention relates in a first aspect to a compound of formula (I)
  • a 1 , A 2 and A 3 are independently selected from O, S, or Se;
  • Z 1 and Z 2 are independently selected from linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P and/or which can be substituted by at least one substituent, preferably selected from hydroxy-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto- , sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one
  • R 1 to R 10 are independently selected from hydrogen, linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain
  • R 5 ⁇ R 6 , and R 7 and/or R 8 , R 9 , and R 10 form together with the N atom to which they are attached a hydrocarbon ring with up to 8 carbon atoms, wherein the ring can contain at least one double bond, and/or wherein the ring can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se
  • R 1 to R 4 are as defined above;
  • n is an integer from 0 to 12;
  • X is selected from chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate, or phosphate, wherein 2 X- can be X 2- , or 2/3 X 3- .
  • the invention relates to a method of manufacturing a compound of formula (I) according to the invention, comprising or consisting of the steps: a) reacting a compound of formula (IV)
  • A is selected from O, S, or Se
  • R 1 to R 4 are independently selected from hydrogen, linear or branched alkyl, cycloalkyl or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least
  • n is an integer from 0 to 12; with at least one compound of formula (V), preferably in stoichiometric excess of the at least one compound of formula (V) in relation to the compound of formula (IV),
  • A is selected from O, S, or Se;
  • Z is selected from linear or branched alkyl, cycloalkyl or aryl or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P and/or which can be substituted by at least one substituent, preferably selected from hydroxy-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo- , carbonyl-, carboxyl-, linear and branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S
  • R 17 is Cl, Br or I
  • R 18 is linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O
  • R 19 to R 21 are independently selected from hydrogen, linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can
  • R 19 to R 21 form together with the N atom to which they are attached a hydrocarbon ring with up to 8 carbon atoms, wherein the ring can contain at least one double bond, and/or the ring can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P; to obtain at least one compound of formula (I), (II) or (III).
  • the invention relates to a use of the compound according to the invention, as a bleach activator.
  • the invention relates to a laundry detergent composition, to an automatic dishwashing composition and to an industrial cotton bleaching composition comprising at least one compound according to the invention and a bleach.
  • One or more relates to“at least one” and comprises 1 , 2, 3, 4, 5, 6, 7, 8, 9 or more of the referenced species.
  • “at least one” means“one or more”, i.e. 1 , 2, 3, 4, 5, 6, 7, 8, 9 or more.
  • “At least one”, as used herein in relation to any component, refers to the number of chemically different atoms or molecules, i.e. to the number of different types of the referenced species, but not to the total number of atoms or molecules.
  • “at least one compound of formula (I)” means that at least one type of compound of formula (I) falling within the definition can be part of the composition, but that also two or more different compounds according to formula (I) can be present, but does not mean that several compounds of only one type of compound may be present.
  • Up to x carbon atoms for example“up to 30 carbon atoms” according to the invention refers to hydrocarbon groups with a minimum of 1 and a maximum of 30 carbon atoms, the numbers being integers. The possibility of 0 carbon atoms is excluded, when using the wording of “up to x carbon atoms”. In case of branched or cyclic hydrocarbon groups the lower limit is 3 carbon atoms.
  • R 1 to R 21 are chosen from hydrocarbon groups or are substituted by a hydrocarbon group, for example linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, they can contain heteroatoms, such as O, S, N, Si, Se, or P.
  • Groups based on hydrogen and carbon atoms, which already contain at least one heteroatom, such as ester- or carboxyl groups, are not included in the definition of hydrocarbon groups according to the invention.
  • X- represents chloride, bromide, iodide, tosylate, mesylate, or triflate.
  • 2 X- is X 2- , a doubly negatively charged ion, such as sulfate or carbonate, or 2 X- can represent 2/3 of a triply negatively charged ion X 3- , such as phosphate, which is then shared between several cations, for example two phosphate ions are the counter ions for the three cations of the compounds of formula (I).
  • the expression "essentially free of means that the respective compound can be contained in the composition in principle, but then be present in a quantity that does not interfere with a function of the other components.
  • the property "essentially free of a particular compound is preferably considered to be a total weight of less than 0.1 wt.-%, more preferably less than 0.001 wt.-%, in particular free of this particular compound, based on the total weight of the composition.
  • Numeric ranges specified in the format "in/from x to y" include the values specified. If several preferred numeric ranges are specified in this format, it goes without saying that all ranges resulting from the combination of the different endpoints will also be included.
  • Molecular weight data referto the weight-average molecular weight in g/mol, unless the number-average molecular weight is explicitly mentioned. It is preferably determined by GPC using polystyrene standards.
  • the compound according to the invention is a compound of formula (II):
  • a 1 , A 2 and A 3 are independently selected from O, S, or Se;
  • R 1 to R 16 are independently selected from hydrogen, linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo- , carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-,
  • R 5 ⁇ R 6 , and R 7 and/or R 8 , R 9 , and R 10 form together with the N atom to which they are attached a hydrocarbon ring with up to 8 carbon atoms, wherein the ring can contain at least one double bond, and/or the ring can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P
  • R 1 to R 4 and R 11 to R 16 are as defined above;
  • n is an integer from 0 to 12;
  • X is selected from chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate, or phosphate, wherein 2 X- can be X 2- , or 2/3 X 3- .
  • the compound according to the invention is a compound of formula (II), wherein
  • a 1 , A 2 and A 3 are the same, preferably O; and/or
  • n is 1 or 2, preferably 1 ;
  • R 1 to R 4 and R 11 to R 16 are independently selected from linear or branched C1 -C4 alkyl and hydrogen, preferably hydrogen; or
  • R 5 , R 6 , and R 7 and/or R 8 , R 9 , and R 10 form together with the N atom to which they are attached a hydrocarbon ring with up to 8 carbon atoms, preferably with 5 carbon atoms, wherein the ring preferably contains at least one double bond, more preferably 3 double bonds, wherein the ring is preferably pyridine, and/or the ring, preferably the pyridine, can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-,
  • R 1 to R 4 and R 11 to R 16 are as defined above; and/or
  • X- is selected from chloride, bromide, or iodide.
  • the compound according to the invention is a compound of formula
  • the invention relates to a method to manufacture the compound according to the invention, comprising or consisting of the steps: a) reacting a compound of formula (IV)
  • A is selected from O, S, or Se, preferably O;
  • R 1 to R 4 are independently selected from hydrogen, linear or branched alkyl, cycloalkyl or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cyclo
  • n is an integer from 0 to 12, preferably 1 or 2, more preferably 1 ; with at least one compound of formula (V), preferably in stoichiometric excess of the at least one compound of formula (V) in relation to the compound of formula (IV), more preferably more than two equivalents of the at least one compound of formula (V) in relation to the compound of formula (IV) (V),
  • A is selected from O, S, or Se, preferably O;
  • Z is selected from linear or branched alkyl, cycloalkyl or aryl or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P and/or which can be substituted by at least one substituent, preferably selected from hydroxy-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear and branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl
  • R 17 is Cl, Br or I
  • R 18 is linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or
  • A, Z, n, R 1 to R 4 , and R 18 are as defined above; b) reacting the at least one compound of formula (VI) with at least one compound of formula (VII), preferably in stoichiometric excess of the at least one compound of formula (VII) in relation to the compound of formula (VI), more preferably more than two equivalents of the at least one compound of formula (VII) in relation to the compound of formula (VI);
  • R 19 to R 21 are independently selected from hydrogen, linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-,
  • R 19 to R 21 form together with the N atom to which they are attached a hydrocarbon ring with up to 8 carbon atoms, preferably with 5 carbon atoms, wherein the ring can contain at least one double bond, preferably 3 double bonds, wherein the ring is preferably pyridine, and/or the ring can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro, fluoro-, chloro, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N,
  • the at least one compound of formula (V) is only one compound of formula
  • the at least one compound of formula (VI) is only one compound of formula
  • the at least one compound of formula (VII) is only one compound of formula
  • bleach activators are also known under the name“peracid precursors”.
  • the compound according to the invention is comprised in laundry detergent compositions, automatic dishwashing compositions or industrial cotton bleaching compositions.
  • the at least one compound according to the invention is contained in the composition in 0.1 to 50 wt.-%, preferably 0.25 to 25 wt.-%, more preferably 1 to 10 wt.-%, based on the total weight of the composition.
  • the composition according to the invention has a pH value of from 4 to 14, preferably 6 to 12, more preferably 7 to 10.
  • the laundry detergent compositions, automatic dishwashing compositions or industrial cotton bleaching compositions according to the present invention comprise at least one compound according to the invention and further contain a bleach.
  • the bleach can be any type of hydrogen peroxide source.
  • Source of hydrogen peroxide include any convenient compound or mixture, which under typical use conditions provides an effective amount of hydrogen peroxide.
  • Levels of the source of hydrogen peroxide in the bleaching composition can vary widely and are in some embodiments from about 0.5 wt.-% to about 60 wt.-%, and in some embodiments, from about 0.5 wt.-% to about 25 wt.-% of the composition.
  • the source of hydrogen peroxide can be any hydrogen peroxide source known in the art, including, but not limited to, hydrogen peroxide itself.
  • the source of hydrogen peroxide can be a perborate, e.g., sodium perborate (any hydrate, including the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide.
  • a perborate e.g., sodium perborate (any hydrate, including the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide.
  • any convenient hydrogen peroxide sources can also be used.
  • the percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometer to about 1 ,000 micrometer, not more than about 10 wt.-% of said particles being smaller than about 200 micrometer and not more than about 10 wt.-% of said particles being larger than about 1 ,250 micrometer.
  • the percarbonate can be coated with silicate, borate or water-soluble surfactants.
  • composition according to the invention can further contain bleach activators different from the compound according to formula (I), which can be chosen from conventional compounds known in the art.
  • Typical conventional bleach activators include nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylenediamine (TAED), and combinations thereof.
  • compositions according to the invention are essentially free of any further bleach activator different from the compound according to formula (I).
  • compositions according to the invention are essentially free of tetraacetylethylenediamine (TAED).
  • compositions according to the invention may further comprise components selected from surfactants, acidifiers, alkalizing agents, anti-crease compounds, antibacterial/antimicrobial substances, antioxidants, antideposition agents, antistatic agents, bitter substances, bleach stabilizers, builder substances, corrosion inhibitors, ironing aids, cobuilders, further fragrances or pro-fragrances, shrinkage inhibitors, electrolytes, emulsifiers, enzymes, enzyme stabilizers, protease inhibitors, colorants, dyes, dye transfer inhibitors, fluorescent agents, fungicides, germicides, metal sequestering agents, odor-complexing substances, auxiliary agents, hydrotropics, rinse aids, complexing agents, preservatives, optical brighteners, perfume carriers, pearl-luster agents, pH control agents, phobing and impregnating agents, polymers, swelling and sliding fasteners, foam inhibitors, layered silicates, dirt- repellent substances, organic solvents, silicone oils, soil-release active substances, UV-protective substances, viscos
  • the optional components can be comprised in the composition according to the invention in amounts of from 0.01 to 60 wt.-%, preferably of from 0.1 to 40 wt.-%, more preferably of from 1 to 25 wt.-%.
  • liquid compositions are concerned, they contain a solvent system.
  • the solvent system of compositions according to the invention can be a solvent system containing water alone or mixtures of organic solvents, preferably alcohols, either without or preferably with water.
  • Preferred organic solvents include every solvent, which is suitable in the field of laundry detergents, dishwashing agents or bleaching compositions.
  • Solvent systems can be absent, for example from anhydrous solid embodiments of the invention.
  • solvent systems are present at levels in the range of 0.1 wt.-% to 98 wt.-%, preferably of 1 wt.-% to 50 wt.-%, more preferably of 2 wt.-% to 25 wt.-%.
  • compositions are aqueous compositions, more preferably aqueous, liquid compositions.
  • compositions according to the invention further comprise at least one surfactant selected from anionic surfactants, cationic surfactants, amphoteric surfactants, or non-ionic surfactants.
  • Suitable non-ionic surfactants are in particular, but without being limited to, ethoxylation and/or propoxylation products of alkyl glycosides and/or linear or branched alcohols each with 8 to 18 C atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Furthermore, corresponding ethoxylation and/or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the above-mentioned long-chain alcohol derivatives with regard to the alkyl moiety, and of alkylphenols with 5 to 12 C atoms in the alkyl radical are useful.
  • non-ionic surfactants such as fatty alcohol polyglycol ethers, alkyl polyglucoside, or fatty acid glucamide, are useful, in particular in amounts of 0.1 -25 wt.-%, based on the total weight of the composition.
  • Suitable anionic surfactants are preferably soaps and soaps containing sulphate or sulphonate groups with preferably alkali ions as cations.
  • Suitable soaps are preferably the alkali salts of saturated or unsaturated fatty acids with 8 to 18 carbon atoms. These fatty acids can also be used in incompletely neutralized form.
  • the useful sulfate-type surfactants include the salts of the sulfuric acid half-esters of fatty alcohols with 8 to 18 carbon atoms and the sulfation products of said non-ionic surfactants with a low degree of ethoxylation.
  • the useful surfactants of the sulfonate-type include, for example, linear alkylbenzene sulfonates with 8 to 14 carbon atoms in the alkyl moiety, alkane sulfonates with 8 to 18 carbon atoms, and olefin sulfonates with 8 to 18 C atoms, which are formed during the reaction of corresponding mono olefins with sulfur trioxide, as well as alpha-sulfo fatty acid esters, which are formed during the sulfonation of fatty acid methyl or ethyl esters.
  • alkylbenzene sulfonate or alkylsulfate is present in the composition according to the invention, preferably in amounts of 0.1 to 40 wt.-%, based on the total weight of the composition.
  • Cationic surfactants are preferably selected from, but without being limited to, esterquats and/or quaternary ammonium compounds (QAV) according to the general formula (R I )(R")(R III )(R IV )N + X- in which R' to R IV represent identical or different C1 to C22 alkyl radicals, C7 to C28 arylalkyl radicals or heterocyclic radicals, wherein two or, in the case of an aromatic integration, such as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, for example a pyridinium or imidazolinium compound, and X- represents halide ions, sulfate ions, hydroxide ions or similar anions.
  • QAV quaternary ammonium compounds
  • QAV can be produced by reaction of tertiary amines with alkylating agents, e.g. methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents e.g. methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents e.g. methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents e.g. methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • the alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly simple. Quaternization of tertiary amines with two long radicals
  • QAVs which can be used, include benzalkonium chloride (N-alkyl-N,N-dimethyl-benzylammonium chloride), benzalkone B (m,p- dichlorobenzyldimethyl-Ci2-alkylammonium chloride, benzoxonium chloride (benzyl-dodecyl-bis-(2- hydroxyethyl)-ammonium chloride), cetrimonium bromide (N-hexadecyl-N,N-trimethyl-ammonium bromide), benzetonium chloride (N,N dimethyl-N [2-[2-[p-(1 ,1 ,3,3-tetramethylbutyl)phenoxy]-ethoxy]- ethyl]-benzylammonium chloride), dialkyldimethylammonium chlorides such as di-n-decyl- dimethylammonium chloride, didecyldimethylammonium bromide, di
  • esterquats are methyl N-(2-hydroxyethyl)-N,N-di(talgacyl-oxyethyl)ammonium-metho-sulfate, bis-(palmitoyl)-ethyl-hydroxyethyl-methyl-ammonium-methosulfate or methyl-N,N-bis(acyl-oxyethyl)-N- (2-hydroxyethyl)ammonium-methosulfate.
  • esterquats are used in amounts of 0.1 to 30 wt.-%, based on the total weight of the composition.
  • Suitable amphoteric/zwitterionic surfactants include amine oxides and betaines.
  • Suitable surfactants can also be fatty amine ethoxylates, preferably in amounts of 0.01 to 4 wt.-%, based on the total weight of the composition.
  • composition according to the invention may further comprise water-soluble and water-insoluble, organic and inorganic builder substances.
  • Water-soluble organic builder substances include for example, but without being limited to, polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid as well as polyaspartic acid, polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylene- phosphonic acid) and 1 -hydroxyethane-1 ,1 -diphosphonic acid, polymeric hydroxy compounds such as dextrin, polymeric (poly)carboxylic acids, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small amounts of polymerizable substances without carboxylic acid functionality when polymerized.
  • Suitable, but less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50 wt.-%.
  • the organic builder substances can be used, preferably for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 wt.-% aqueous solutions. All acids mentioned are usually used in the form of their water-soluble salts, in particular their alkali salts.
  • Organic builder substances can be comprised in compositions according to the invention, in amounts of up to 40 wt.-%, preferably up to 25 wt.-% and more preferably from 0.1 wt.-% to 8 wt.-%. Amounts near this upper limit are preferably used in pasty or liquid, in particular water-containing agents according to the invention. Laundry after-treatment agents, such as fabric softeners, may also be free of organic builder. It may be preferred that the composition comprises low levels of phosphate salt and/or zeolite, for example from 0.1 to 10 wt.-%, preferably from 1 to 5 wt.-%. Optionally, the composition may be free of strong builder.
  • Alkali silicates and aluminum silicates and polyphosphates, preferably sodium triphosphate are particularly suitable as water-soluble inorganic builder materials.
  • water-insoluble, water-dispersible inorganic builder materials crystalline or amorphous alkali metal aluminum silicates, if desired, can be used in quantities of up to 50 wt.-%, preferably not more than 40 wt.-%, and in liquid media, in particular from 1 wt.-% to 5 wt.-%.
  • crystalline sodium aluminum silicates in detergent quality in particular zeolites A, P and, where appropriate, X, are preferred. Quantities near this upper limit are preferably used in solid, particulate agents.
  • suitable aluminum silicates have no particles with a grain size of more than 30 pm and preferably consist of at least 80 wt.-% of particles with a size of less than 10 pm.
  • the builder materials are selected from zeolites, polycarboxylates or sodium citrate.
  • builder substances if desired, can be present in compositions according to the invention in amounts of up to 60 wt.-%, preferably of 1 wt.-% to 40 wt.-%.
  • Laundry after treatment agents such as softeners, are preferably free of inorganic builder substances.
  • the composition according to the invention is a liquid at 25 °C
  • composition according to the invention is a solid at 25 °C.
  • compositions relate to compositions, which are fluid or flowable at standard conditions (approx. 20-25 °C, approx. 1013 mbar at sea level).
  • Liquid compositions also comprise gellike and paste-like compositions. “Solid” is understood to mean all solid presentation forms, for example powders, granulates or extrudates.
  • a powdery composition for example, can exist as a free-flowing powder, in particular with a bulk density of 300 g/L to 1200 g/L, especially 500 g/L to 900 g/L or 600 g/L to 850 g/L.
  • compositions according to the invention are preferably in the form of a molded object, in particular a compacted material, principally a tablet.
  • a molded object in particular a compacted material, principally a tablet.
  • the molded object can also be a granulate for example that is comprised in a bag or in a cast shape.
  • compositions according to the invention can be presented as one-phase or multi-phase products.
  • Compositions in particular automatic dishwashing compositions or laundry detergents, in particular with one, two, three or four phases, are preferred.
  • Automatic dishwashing compositions in the form of a prefabricated unit dose with two or more phases are particularly preferred.
  • tablets with two or more phases are particularly preferred, for example two-layer tablets, in particular two-layer tablets with a recess and a molded object in the recess.
  • compositions according to the invention are preferably prefabricated as unit doses. These unit doses preferably contain the necessary quantity of washing or cleaning active substances for one cleaning cycle. Preferred unit doses weigh between 12 and 30 g, preferably between 14 and 26 g and especially between 15 and 22 g.
  • the volume of the abovementioned unit doses and their three-dimensional shape are preferably chosen such that the prefabricated units can be dosed by being placed in the dosing chamber of a dishwasher. Consequently, the volume of the unit dose is preferably between 10 and 35 ml_, more preferably between 12 and 30 ml_ and most preferably between 15 and 25 ml_.
  • the compositions according to the invention, in particular the prefabricated unit doses have, in a preferred embodiment, a water-soluble coating.
  • Lactose and ovalbumin were mixed in 3:1 ratio (total 0.5 g), solved in distilled water and stirred for 10 min at room temperature. The mixture was then freeze-dried, ground in a mortar and heated in an oven at 160°C for 20 min and afforded after cooling to room temperature a yellow-brown powder.
  • Sodium percarbonate stock solution was prepared by dissolving 0.375 g in 100 mL water.
  • Activator stock solution was prepared by dissolving 0.05 g in 100 mL water. Table 3: Preparation of respective solutions
  • a test solution was prepared by dissolving 2.5 mg Morin in 100 ml_ water followed by adjustment of the pH value to 10-1 1 by addition of a suitable amount of NaOH. Then 98.0 mg sodium percarbonate was added followed by 13.1 mg of TAED or the compound of Example 1 . The resulting yellow solution was then stirred at room temperature and checked visually over time until the yellow color fully disappeared and a transparent solution was obtained.

Landscapes

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

Abstract

The present invention relates to a compound of formula (I) and additionally to a method to manufacture the compound of formula (I). Furthermore, the invention is directed to a use of the compound of formula (I) as a bleach activator and to a laundry detergent composition, an automatic dishwashing composition, and an industrial cotton bleach composition, which comprise at least one compound of formula (I) according to the invention.

Description

Bleach activators containing two quarternary ammonium groups
The present invention relates to a compound of formula (I) and additionally to a method to manufacture the compound of formula (I). Furthermore, the invention is directed to a use of the compound of formula (I) as a bleach activator and to a laundry detergent composition, an automatic dishwashing composition, and an industrial cotton bleach composition, which comprise at least one compound of formula (I) according to the invention.
Bleachable stains or colored materials on textiles or on hard surfaces can be discolored, oxidized and ultimately removed using highly active bleach activators in combination with a source of hydrogen peroxide.
Some commonly used bleach activators such as tetraacetylethylenediamine (TAED) show a low water solubility at low temperatures. Low temperature washing and cleaning of laundry and hard surfaces requires more reactive bleach activators, which aliphatic activators cannot achieve. Commonly used activators like TAED provide only less reactive bleach-active compounds such as peracids and are less efficient in the generation of the same. Benzylic peracids have a much higher activity towards bleachable stains and colored materials, which makes them more sustainable and allow formulations, which are more compact.
Therefore, there is a need for new, more reactive bleach activator compounds, which can be used in particular in laundry or dishwashing detergents or industrial applications to bleach cotton.
Surprisingly, it was found that quaternary ammonium groups-containing lactam-based compounds can be applied as bleach activators, preferably in laundry detergents, automatic dishwashing agents or industrial cotton bleach compositions. These compounds provide higher solubility in water, preferably at low temperatures, and higher affinity towards fibers, preferably cotton fibers, in comparison with non- charged or anionic bleach activators. Furthermore, they provide a higher bleaching activity compared to aliphatic bleach activators such as TAED. Thereby, lower dosages of bleach activators are required in a composition, to achieve the same bleaching effect.
Therefore, the present invention relates in a first aspect to a compound of formula (I)
wherein A1 , A2 and A3 are independently selected from O, S, or Se;
Z1 and Z2 are independently selected from linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P and/or which can be substituted by at least one substituent, preferably selected from hydroxy-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto- , sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P;
R1 to R10 are independently selected from hydrogen, linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P;
or
R5· R6, and R7 and/or R8, R9, and R10 form together with the N atom to which they are attached a hydrocarbon ring with up to 8 carbon atoms, wherein the ring can contain at least one double bond, and/or wherein the ring can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P, and
R1 to R4 are as defined above;
n is an integer from 0 to 12; and
X is selected from chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate, or phosphate, wherein 2 X- can be X2-, or 2/3 X3-.
In a second aspect, the invention relates to a method of manufacturing a compound of formula (I) according to the invention, comprising or consisting of the steps: a) reacting a compound of formula (IV)
wherein A is selected from O, S, or Se;
R1 to R4 are independently selected from hydrogen, linear or branched alkyl, cycloalkyl or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P; and
n is an integer from 0 to 12; with at least one compound of formula (V), preferably in stoichiometric excess of the at least one compound of formula (V) in relation to the compound of formula (IV),
wherein
A is selected from O, S, or Se;
Z is selected from linear or branched alkyl, cycloalkyl or aryl or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P and/or which can be substituted by at least one substituent, preferably selected from hydroxy-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo- , carbonyl-, carboxyl-, linear and branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P;
R17 is Cl, Br or I; and
R18 is linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P, which is substituted by Cl, Br, or I; to obtain at least one compound of formula (VI)
wherein A, Z, n, R1 to R4, and R18 are as defined above; b) reacting the at least one compound of formula (VI) with at least one compound of formula (VII), preferably in stoichiometric excess of the at least one compound of formula (VII) in relation to the compound of formula (VI)
wherein R19 to R21 are independently selected from hydrogen, linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P;
or
R19 to R21 form together with the N atom to which they are attached a hydrocarbon ring with up to 8 carbon atoms, wherein the ring can contain at least one double bond, and/or the ring can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P; to obtain at least one compound of formula (I), (II) or (III).
In a third aspect, the invention relates to a use of the compound according to the invention, as a bleach activator. In a fourth, fifth and sixth aspect, the invention relates to a laundry detergent composition, to an automatic dishwashing composition and to an industrial cotton bleaching composition comprising at least one compound according to the invention and a bleach.
One or more”, as used herein, relates to“at least one” and comprises 1 , 2, 3, 4, 5, 6, 7, 8, 9 or more of the referenced species. Similarly,“at least one” means“one or more”, i.e. 1 , 2, 3, 4, 5, 6, 7, 8, 9 or more. “At least one”, as used herein in relation to any component, refers to the number of chemically different atoms or molecules, i.e. to the number of different types of the referenced species, but not to the total number of atoms or molecules. For example,“at least one compound of formula (I)” means that at least one type of compound of formula (I) falling within the definition can be part of the composition, but that also two or more different compounds according to formula (I) can be present, but does not mean that several compounds of only one type of compound may be present.
“Up to x carbon atoms”, for example“up to 30 carbon atoms” according to the invention refers to hydrocarbon groups with a minimum of 1 and a maximum of 30 carbon atoms, the numbers being integers. The possibility of 0 carbon atoms is excluded, when using the wording of “up to x carbon atoms”. In case of branched or cyclic hydrocarbon groups the lower limit is 3 carbon atoms.
Numeric values specified without decimal places refer to the full value specified with one decimal place. For example, "99 %" means "99.0 %", if not stated otherwise.
The expressions "approx." or "about", in conjunction with a numerical value, refer to a variance of ± 10 % relative to the given numerical value, preferably ± 5 %, more preferably ± 1 %, if not explicitly stated otherwise.
All percentages given herein in relation to the compositions relate to weight-% (wt.-%) relative to the total weight of the respective composition, if not explicitly stated otherwise.
If any of R1 to R21 are chosen from hydrocarbon groups or are substituted by a hydrocarbon group, for example linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, they can contain heteroatoms, such as O, S, N, Si, Se, or P. Groups based on hydrogen and carbon atoms, which already contain at least one heteroatom, such as ester- or carboxyl groups, are not included in the definition of hydrocarbon groups according to the invention.
Preferably, X- represents chloride, bromide, iodide, tosylate, mesylate, or triflate. Furthermore, it is possible that 2 X- is X2-, a doubly negatively charged ion, such as sulfate or carbonate, or 2 X- can represent 2/3 of a triply negatively charged ion X3-, such as phosphate, which is then shared between several cations, for example two phosphate ions are the counter ions for the three cations of the compounds of formula (I). The expression "essentially free of means that the respective compound can be contained in the composition in principle, but then be present in a quantity that does not interfere with a function of the other components. In the context of the present invention, therefore, the property "essentially free of a particular compound is preferably considered to be a total weight of less than 0.1 wt.-%, more preferably less than 0.001 wt.-%, in particular free of this particular compound, based on the total weight of the composition.
Numeric ranges specified in the format "in/from x to y" include the values specified. If several preferred numeric ranges are specified in this format, it goes without saying that all ranges resulting from the combination of the different endpoints will also be included.
Molecular weight data referto the weight-average molecular weight in g/mol, unless the number-average molecular weight is explicitly mentioned. It is preferably determined by GPC using polystyrene standards.
These and other aspects, features, embodiments, and advantages of the invention become apparent to the skilled person in the following detailed description and claims. Each feature or embodiment from one aspect of the invention can be used in any other aspect of the invention. Additionally, each feature or embodiment of the compound, method, use or composition can be combined with any other feature or embodiment of the compound, method, use or composition. Furthermore, the examples contained herein are intended to describe and illustrate the invention, but do not restrict it and in particular, the invention is not limited to these examples.
In a preferred embodiment, the residues
formula (I)
are the same group.
In another preferred embodiment, the residues
formula (I)
are the same group. However, it is also possible that the two residues
formula (I) or the two residues of
formula (I)
are different groups.
In a preferred embodiment, the compound according to the invention is a compound of formula (II):
wherein
A1 , A2 and A3 are independently selected from O, S, or Se;
R1 to R16 are independently selected from hydrogen, linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo- , carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P;
or
R5· R6, and R7 and/or R8, R9, and R10 form together with the N atom to which they are attached a hydrocarbon ring with up to 8 carbon atoms, wherein the ring can contain at least one double bond, and/or the ring can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P, and
R1 to R4 and R11 to R16 are as defined above;
n is an integer from 0 to 12; and
X is selected from chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate, or phosphate, wherein 2 X- can be X2-, or 2/3 X3-.
In a further preferred embodiment, the compound according to the invention is a compound of formula (II), wherein
A1 , A2 and A3 are the same, preferably O; and/or
n is 1 or 2, preferably 1 ; and/or
i) R1 to R4 and R11 to R16 are independently selected from linear or branched C1 -C4 alkyl and hydrogen, preferably hydrogen; or
ii) R5, R6, and R7 and/or R8, R9, and R10 form together with the N atom to which they are attached a hydrocarbon ring with up to 8 carbon atoms, preferably with 5 carbon atoms, wherein the ring preferably contains at least one double bond, more preferably 3 double bonds, wherein the ring is preferably pyridine, and/or the ring, preferably the pyridine, can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P, preferably the ring, more preferably the pyridine, is substituted by linear or branched C1 -C6 alkyl, more preferably by methyl, and
R1 to R4 and R11 to R16 are as defined above; and/or
X- is selected from chloride, bromide, or iodide.
In a further preferred embodiment, the compound according to the invention is a compound of formula
According to aspect 2, the invention relates to a method to manufacture the compound according to the invention, comprising or consisting of the steps: a) reacting a compound of formula (IV)
wherein
A is selected from O, S, or Se, preferably O;
R1 to R4 are independently selected from hydrogen, linear or branched alkyl, cycloalkyl or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P, preferably R1 to R4 are independently selected from linear or branched C1 -C4 alkyl and hydrogen, more preferably R1 to R4 are hydrogen; and
n is an integer from 0 to 12, preferably 1 or 2, more preferably 1 ; with at least one compound of formula (V), preferably in stoichiometric excess of the at least one compound of formula (V) in relation to the compound of formula (IV), more preferably more than two equivalents of the at least one compound of formula (V) in relation to the compound of formula (IV) (V),
wherein
A is selected from O, S, or Se, preferably O;
Z is selected from linear or branched alkyl, cycloalkyl or aryl or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P and/or which can be substituted by at least one substituent, preferably selected from hydroxy-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear and branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P, preferably Z is selected from linear or branched C1 - C6 alkyl or aryl, more preferably Z is aryl;
R17 is Cl, Br or I; and
R18 is linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P, preferably R18 is linear or branched C1 -C4 alkyl, which is substituted by Cl, Br, or I; wherein the reaction solution preferably further contains an amine compound, more preferably triethylamine; to obtain at least one compound of formula (VI)
wherein A, Z, n, R1 to R4, and R18 are as defined above; b) reacting the at least one compound of formula (VI) with at least one compound of formula (VII), preferably in stoichiometric excess of the at least one compound of formula (VII) in relation to the compound of formula (VI), more preferably more than two equivalents of the at least one compound of formula (VII) in relation to the compound of formula (VI);
wherein R19 to R21 are independently selected from hydrogen, linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P;
or
R19 to R21 form together with the N atom to which they are attached a hydrocarbon ring with up to 8 carbon atoms, preferably with 5 carbon atoms, wherein the ring can contain at least one double bond, preferably 3 double bonds, wherein the ring is preferably pyridine, and/or the ring can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro, fluoro-, chloro, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P, preferably the ring, more preferably pyridine, is substituted by C1 -C4 alkyl or hydrogen, more preferably by methyl; to obtain at least one compound of formula (I), (II) or (III).
In a preferred embodiment, the at least one compound of formula (V) is only one compound of formula
(V). However, two or more compounds of formula (V) can be present, preferably compounds of formula
(V), which differ in at least one residue, more preferably in R18 or R18-Z.
In a preferred embodiment, the at least one compound of formula (VI) is only one compound of formula
(VI). However, two or more compounds of formula (VI) can be present, preferably compounds of formula
(VI), which differ in at least one residue, more preferably in R18 or R18-Z.
In a preferred embodiment, the at least one compound of formula (VII) is only one compound of formula
(VII). However, two or more compounds of formula (VII) can be present, preferably compounds of formula (VII), which differ in at least one residue, more preferably in R19, R20 and/or R21.
In a preferred embodiment, with the method according to the invention, only one compound of formula (I), (II) or (III) is obtained. However, two or more compounds according to formula (I), (II) or (III) can be obtained by the method.
According to aspect 3 of the invention, these compounds can be used as bleach activators. Bleach activators are also known under the name“peracid precursors”.
Preferably, the compound according to the invention is comprised in laundry detergent compositions, automatic dishwashing compositions or industrial cotton bleaching compositions.
In a preferred embodiment, the at least one compound according to the invention is contained in the composition in 0.1 to 50 wt.-%, preferably 0.25 to 25 wt.-%, more preferably 1 to 10 wt.-%, based on the total weight of the composition.
In a further preferred embodiment, the composition according to the invention has a pH value of from 4 to 14, preferably 6 to 12, more preferably 7 to 10.
The laundry detergent compositions, automatic dishwashing compositions or industrial cotton bleaching compositions according to the present invention comprise at least one compound according to the invention and further contain a bleach. Preferably, the bleach can be any type of hydrogen peroxide source. Source of hydrogen peroxide include any convenient compound or mixture, which under typical use conditions provides an effective amount of hydrogen peroxide. Levels of the source of hydrogen peroxide in the bleaching composition can vary widely and are in some embodiments from about 0.5 wt.-% to about 60 wt.-%, and in some embodiments, from about 0.5 wt.-% to about 25 wt.-% of the composition. The source of hydrogen peroxide can be any hydrogen peroxide source known in the art, including, but not limited to, hydrogen peroxide itself. For example, the source of hydrogen peroxide can be a perborate, e.g., sodium perborate (any hydrate, including the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide. Mixtures of any convenient hydrogen peroxide sources can also be used.
In some embodiments, the percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometer to about 1 ,000 micrometer, not more than about 10 wt.-% of said particles being smaller than about 200 micrometer and not more than about 10 wt.-% of said particles being larger than about 1 ,250 micrometer. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants.
The composition according to the invention can further contain bleach activators different from the compound according to formula (I), which can be chosen from conventional compounds known in the art. Typical conventional bleach activators include nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylenediamine (TAED), and combinations thereof.
In a preferred embodiment, the compositions according to the invention are essentially free of any further bleach activator different from the compound according to formula (I). In particular, the compositions according to the invention are essentially free of tetraacetylethylenediamine (TAED).
Optionally, the compositions according to the invention may further comprise components selected from surfactants, acidifiers, alkalizing agents, anti-crease compounds, antibacterial/antimicrobial substances, antioxidants, antideposition agents, antistatic agents, bitter substances, bleach stabilizers, builder substances, corrosion inhibitors, ironing aids, cobuilders, further fragrances or pro-fragrances, shrinkage inhibitors, electrolytes, emulsifiers, enzymes, enzyme stabilizers, protease inhibitors, colorants, dyes, dye transfer inhibitors, fluorescent agents, fungicides, germicides, metal sequestering agents, odor-complexing substances, auxiliary agents, hydrotropics, rinse aids, complexing agents, preservatives, optical brighteners, perfume carriers, pearl-luster agents, pH control agents, phobing and impregnating agents, polymers, swelling and sliding fasteners, foam inhibitors, layered silicates, dirt- repellent substances, organic solvents, silicone oils, soil-release active substances, UV-protective substances, viscosity regulators, thickeners, discoloration inhibitors, greying inhibitors, structurants, vitamins, and/or fabric softeners.
The optional components can be comprised in the composition according to the invention in amounts of from 0.01 to 60 wt.-%, preferably of from 0.1 to 40 wt.-%, more preferably of from 1 to 25 wt.-%. In case, liquid compositions are concerned, they contain a solvent system.
The solvent system of compositions according to the invention can be a solvent system containing water alone or mixtures of organic solvents, preferably alcohols, either without or preferably with water. Preferred organic solvents include every solvent, which is suitable in the field of laundry detergents, dishwashing agents or bleaching compositions. Solvent systems can be absent, for example from anhydrous solid embodiments of the invention.
In one embodiment, solvent systems are present at levels in the range of 0.1 wt.-% to 98 wt.-%, preferably of 1 wt.-% to 50 wt.-%, more preferably of 2 wt.-% to 25 wt.-%.
In a preferred embodiment, the compositions are aqueous compositions, more preferably aqueous, liquid compositions.
In a preferred embodiment, compositions according to the invention further comprise at least one surfactant selected from anionic surfactants, cationic surfactants, amphoteric surfactants, or non-ionic surfactants.
Suitable non-ionic surfactants are in particular, but without being limited to, ethoxylation and/or propoxylation products of alkyl glycosides and/or linear or branched alcohols each with 8 to 18 C atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Furthermore, corresponding ethoxylation and/or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the above-mentioned long-chain alcohol derivatives with regard to the alkyl moiety, and of alkylphenols with 5 to 12 C atoms in the alkyl radical are useful.
Preferably, non-ionic surfactants, such as fatty alcohol polyglycol ethers, alkyl polyglucoside, or fatty acid glucamide, are useful, in particular in amounts of 0.1 -25 wt.-%, based on the total weight of the composition.
Suitable anionic surfactants, without being limited to, are preferably soaps and soaps containing sulphate or sulphonate groups with preferably alkali ions as cations. Suitable soaps are preferably the alkali salts of saturated or unsaturated fatty acids with 8 to 18 carbon atoms. These fatty acids can also be used in incompletely neutralized form. The useful sulfate-type surfactants include the salts of the sulfuric acid half-esters of fatty alcohols with 8 to 18 carbon atoms and the sulfation products of said non-ionic surfactants with a low degree of ethoxylation. The useful surfactants of the sulfonate-type include, for example, linear alkylbenzene sulfonates with 8 to 14 carbon atoms in the alkyl moiety, alkane sulfonates with 8 to 18 carbon atoms, and olefin sulfonates with 8 to 18 C atoms, which are formed during the reaction of corresponding mono olefins with sulfur trioxide, as well as alpha-sulfo fatty acid esters, which are formed during the sulfonation of fatty acid methyl or ethyl esters. In a preferred embodiment, alkylbenzene sulfonate or alkylsulfate is present in the composition according to the invention, preferably in amounts of 0.1 to 40 wt.-%, based on the total weight of the composition.
Cationic surfactants are preferably selected from, but without being limited to, esterquats and/or quaternary ammonium compounds (QAV) according to the general formula (RI)(R")(RIII)(RIV)N+ X- in which R' to RIV represent identical or different C1 to C22 alkyl radicals, C7 to C28 arylalkyl radicals or heterocyclic radicals, wherein two or, in the case of an aromatic integration, such as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, for example a pyridinium or imidazolinium compound, and X- represents halide ions, sulfate ions, hydroxide ions or similar anions. QAV can be produced by reaction of tertiary amines with alkylating agents, e.g. methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide. The alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly simple. Quaternization of tertiary amines with two long radicals and one methyl group can also be carried out under mild conditions with the aid of methyl chloride. Amines, which have three long alkyl radicals or hydroxy-substituted alkyl radicals are little reactive and are quaternized e.g. with dimethyl sulfate. QAVs, which can be used, include benzalkonium chloride (N-alkyl-N,N-dimethyl-benzylammonium chloride), benzalkone B (m,p- dichlorobenzyldimethyl-Ci2-alkylammonium chloride, benzoxonium chloride (benzyl-dodecyl-bis-(2- hydroxyethyl)-ammonium chloride), cetrimonium bromide (N-hexadecyl-N,N-trimethyl-ammonium bromide), benzetonium chloride (N,N dimethyl-N [2-[2-[p-(1 ,1 ,3,3-tetramethylbutyl)phenoxy]-ethoxy]- ethyl]-benzylammonium chloride), dialkyldimethylammonium chlorides such as di-n-decyl- dimethylammonium chloride, didecyldimethylammonium bromide, dioctyl-dimethylammonium chloride, 1 -cetylpyridinium chloride and thiazoline iodide and mixtures thereof. Preferred QAVs are benzalkonium chlorides with C8 to C22 alkyl radicals, in particular C12 to C14 alkylbenzyl-dimethylammonium chloride.
Preferred esterquats are methyl N-(2-hydroxyethyl)-N,N-di(talgacyl-oxyethyl)ammonium-metho-sulfate, bis-(palmitoyl)-ethyl-hydroxyethyl-methyl-ammonium-methosulfate or methyl-N,N-bis(acyl-oxyethyl)-N- (2-hydroxyethyl)ammonium-methosulfate. Preferably, esterquats are used in amounts of 0.1 to 30 wt.-%, based on the total weight of the composition.
Suitable amphoteric/zwitterionic surfactants include amine oxides and betaines.
Suitable surfactants can also be fatty amine ethoxylates, preferably in amounts of 0.01 to 4 wt.-%, based on the total weight of the composition.
The composition according to the invention may further comprise water-soluble and water-insoluble, organic and inorganic builder substances. Water-soluble organic builder substances include for example, but without being limited to, polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid as well as polyaspartic acid, polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylene- phosphonic acid) and 1 -hydroxyethane-1 ,1 -diphosphonic acid, polymeric hydroxy compounds such as dextrin, polymeric (poly)carboxylic acids, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small amounts of polymerizable substances without carboxylic acid functionality when polymerized. Suitable, but less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50 wt.-%. The organic builder substances can be used, preferably for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 wt.-% aqueous solutions. All acids mentioned are usually used in the form of their water-soluble salts, in particular their alkali salts.
Organic builder substances can be comprised in compositions according to the invention, in amounts of up to 40 wt.-%, preferably up to 25 wt.-% and more preferably from 0.1 wt.-% to 8 wt.-%. Amounts near this upper limit are preferably used in pasty or liquid, in particular water-containing agents according to the invention. Laundry after-treatment agents, such as fabric softeners, may also be free of organic builder. It may be preferred that the composition comprises low levels of phosphate salt and/or zeolite, for example from 0.1 to 10 wt.-%, preferably from 1 to 5 wt.-%. Optionally, the composition may be free of strong builder.
Alkali silicates and aluminum silicates and polyphosphates, preferably sodium triphosphate, are particularly suitable as water-soluble inorganic builder materials. As water-insoluble, water-dispersible inorganic builder materials, crystalline or amorphous alkali metal aluminum silicates, if desired, can be used in quantities of up to 50 wt.-%, preferably not more than 40 wt.-%, and in liquid media, in particular from 1 wt.-% to 5 wt.-%. Among these, crystalline sodium aluminum silicates in detergent quality, in particular zeolites A, P and, where appropriate, X, are preferred. Quantities near this upper limit are preferably used in solid, particulate agents. In particular, suitable aluminum silicates have no particles with a grain size of more than 30 pm and preferably consist of at least 80 wt.-% of particles with a size of less than 10 pm.
In preferred embodiments, the builder materials are selected from zeolites, polycarboxylates or sodium citrate.
In further preferred embodiments, builder substances, if desired, can be present in compositions according to the invention in amounts of up to 60 wt.-%, preferably of 1 wt.-% to 40 wt.-%. Laundry after treatment agents, such as softeners, are preferably free of inorganic builder substances.
In a preferred embodiment, the composition according to the invention is a liquid at 25 °C
In another preferred embodiment, the composition according to the invention is a solid at 25 °C.
„Liquid compositions” as used herein, relate to compositions, which are fluid or flowable at standard conditions (approx. 20-25 °C, approx. 1013 mbar at sea level). Liquid compositions also comprise gellike and paste-like compositions. “Solid” is understood to mean all solid presentation forms, for example powders, granulates or extrudates.
In a preferred embodiment, a powdery composition, for example, can exist as a free-flowing powder, in particular with a bulk density of 300 g/L to 1200 g/L, especially 500 g/L to 900 g/L or 600 g/L to 850 g/L.
The compositions according to the invention, in particular the automatic dishwashing compositions or laundry detergents, are preferably in the form of a molded object, in particular a compacted material, principally a tablet. For the molded object, however, it can also be a granulate for example that is comprised in a bag or in a cast shape.
Compositions according to the invention can be presented as one-phase or multi-phase products. Compositions, in particular automatic dishwashing compositions or laundry detergents, in particular with one, two, three or four phases, are preferred. Automatic dishwashing compositions in the form of a prefabricated unit dose with two or more phases are particularly preferred. In particular, tablets with two or more phases are particularly preferred, for example two-layer tablets, in particular two-layer tablets with a recess and a molded object in the recess.
Compositions according to the invention, preferably laundry detergents or automatic dishwashing compositions, are preferably prefabricated as unit doses. These unit doses preferably contain the necessary quantity of washing or cleaning active substances for one cleaning cycle. Preferred unit doses weigh between 12 and 30 g, preferably between 14 and 26 g and especially between 15 and 22 g.
The volume of the abovementioned unit doses and their three-dimensional shape are preferably chosen such that the prefabricated units can be dosed by being placed in the dosing chamber of a dishwasher. Consequently, the volume of the unit dose is preferably between 10 and 35 ml_, more preferably between 12 and 30 ml_ and most preferably between 15 and 25 ml_. The compositions according to the invention, in particular the prefabricated unit doses, have, in a preferred embodiment, a water-soluble coating.
EXAMPLES
Preparation example 1 :
1 ,3-bis{[4-(chloromethyl)phenyl]carbonyl}imidazolidin-2-one
A solution of 2-imidazolidone (1 eq.) and triethylamine (2.25 eq.) in toluene (50 ml_) and dioxane (25 ml_) was heated to reflux (1 10 °C) under nitrogen in a four-necked round bottomed flask equipped with a reflux condenser. A solution of 4-chloromethyl benzoyl chloride (2.05 eq.) in dioxane (25 ml_) was added slowly to the reaction flask. The mixture was stirred at reflux for 4 h, cooled to room temperature, and filtered. The filtrate was stored in a refrigerator for 12 h. The precipitate was filtered, washed with 5 % aq. NaHCC>3 solution and dried at 40 °C for 12 h to afford the desired compound (22.4 g, 57.5 mmol, 57 %) as a colorless powder. mp.: 141 °C-158°C. FTIR (film): v = 2958, 2912, 2854, 1759, 1671 , 1369, 1304, 1234, 1 162, 1 1 18, 924, 879, 869, 844, 828, 790, 748, 729, 704, 674, 623, 473 cm 1. 1H-NMR (400 MHz, CDC ): d = 4.10 (s, 4H), 4.52 (s, 4H), 7.39 (pd, J = 8.3 Hz, 4H), 7.60 (pd, J = 8.3 Hz, 4H) ppm. 13C-NMR (CDCIs, 100.6 MHz): d = 40.9 (t, 2C), 45.7 (t, 2C), 128.4 (d, 4C), 129.9 (d, 4C), 133.6 (s, 2C), 141 .9 (s, 2C), 151 .4 (s, 2C), 170.0 (s).
Example 1 :
1 ,3-bis{[4-(3-methylpyridinium)methyl)phenyl]carbonyl}imidazolidin-2-one dichloride
1 ,3-bis{[4-(chloromethyl)phenyl]carbonyl}imidazolidin-2-one (1 eq.) was dissolved in 100 ml_ acetonitrile under nitrogen. Then 3-picoline (2.6 eq.) was added dropwise to the solution, and the mixture was stirred at reflux (80 °C) for 4 h. The solution was then cooled to room temperature, and the solvent was evaporated using a rotary evaporator. The resulting solid was suspended in 100 ml_ acetone and the mixture was heated to 50-60 °C for 1 hour to remove impurities. This procedure was repeated until no more starting material and impurities were visible in the 1H-NMR spectrum. The product was collected and dried overnight at 40°C. The desired compound (20.59 g, 35.7 mmol, 64 %) was obtained as a colorless solid. mp.: 124°C-132°C. FTIR (film): v = 3051 , 3004, 2912, 1749, 1668, 1506, 1369, 1300, 1244, 1215, 1 152, 862, 736, 706, 650, 466, 431 cm 1. 1H-NMR (400 MHz, MeOD-ds): d = 2.59 (s, 6H), 4.09 (s, 4H), 5.85 (s, 4H), 7.52 (pd, J = 8.3 Hz, 4H), 7.69 (pd, J = 8.3 Hz, 4H) 8.01 (dd, J = 6.0 Hz, 8.1 Hz, 2H), 8.49 (d, J = 8.1 Hz, 2H), 8.91 (d, J = 6.0 Hz, 2H), 9.02 (s, 2H) ppm. 13C-NMR (MeOD-ds, 100.6 MHz): d = 18.5 (q, 2C), 41 .5 (t, 2C), 64.8 (t, 2C), 129.0 (d, 2C), 129.1 (d, 4C), 130.7 (d, 4C), 137.0 (s, 2C), 137.9 (s, 2C), 141 .6 (s, 2C), 143.3 (d, 2C), 145.7 (d, 2C), 147.9 (d, 2C), 152.7 (s, 2C), 170.8 (s). MS (ESI positive mode, +3.5 kV): 222 (30%), 253 ([M-2CI ]2+, 100%), 448 (13%). Example 2: Washing trial
Table 1 : Washing mixture (formula, given in wt.-%)
Textile fabrics of cotton and polyester, which had been stained with a total of 82 different standardized soils, were washed at 30 °C in the washing machine (five repetitions) with washing liquors containing in each case 3.8 g/L of a detergent W1 or W2 of a composition indicated in Table 1 , and then dried. The resulting brightness values (Y values) were determined. The agents with an active ingredient combination according to the invention were superior to the agent without this active ingredient combination with a DU-value indicated in Table 2.
Table 2: Results of washing test
Example 3: Performance on burnt-in soil
Lactose and ovalbumin were mixed in 3:1 ratio (total 0.5 g), solved in distilled water and stirred for 10 min at room temperature. The mixture was then freeze-dried, ground in a mortar and heated in an oven at 160°C for 20 min and afforded after cooling to room temperature a yellow-brown powder. Sodium percarbonate stock solution was prepared by dissolving 0.375 g in 100 mL water. Activator stock solution was prepared by dissolving 0.05 g in 100 mL water. Table 3: Preparation of respective solutions
According to table 3 the respective mixtures were prepared in glass vials and heated to 60°C in a mechanical shaker over 48 h. The dissolution rate was followed visually.
Evaluation: 0 (no dissolution of soil) -> + -> ++ -> +++ -> ++++ (soil fully dissolved)
Table 4: Results of dissolution experiment
Example 4: Morin discoloration test
A test solution was prepared by dissolving 2.5 mg Morin in 100 ml_ water followed by adjustment of the pH value to 10-1 1 by addition of a suitable amount of NaOH. Then 98.0 mg sodium percarbonate was added followed by 13.1 mg of TAED or the compound of Example 1 . The resulting yellow solution was then stirred at room temperature and checked visually over time until the yellow color fully disappeared and a transparent solution was obtained.
Table 5: Time until full discoloration
In the experiment with the compound of Example 1 as activator a fully transparent solution was observed after 320 min. At this point in time the TAED containing solution still showed a strong yellow color. Transparency was observed in the latter after the reaction was allowed to continue stirring overnight.

Claims

Claims
wherein
A1 , A2 and A3 are independently selected from O, S, or Se;
Z1 and Z2 are independently selected from linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P and/or which can be substituted by at least one substituent, preferably selected from hydroxy-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo- , carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P;
R1 to R10 are independently selected from hydrogen, linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P;
or
R5· R6, and R7 and/or R8, R9, and R10 form together with the N atom to which they are attached a hydrocarbon ring with up to 8 carbon atoms, wherein the ring can contain at least one double bond, and/or wherein the ring can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P, and
R1 to R4 are as defined above;
n is an integer from 0 to 12; and
X- is selected from chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate, or phosphate, wherein 2 X- can be X2~, or 2/3 X3-.
2. The compound of claim 1 having following formula (II):
wherein
A1 , A2 and A3 are independently selected from O, S, or Se;
R1 to R16 are independently selected from hydrogen, linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo- , carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P;
or
R5· R6, and R7 and/or R8, R9, and R10 form together with the N atom to which they are attached a hydrocarbon ring with up to 8 carbon atoms, wherein the ring can contain at least one double bond, and/or the ring can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P, and
R1 to R4 and R11 to R16 are as defined above;
n is an integer from 0 to 12; and
X- is selected from chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate, or phosphate, wherein 2 X- can be X2-, or 2/3 X3-.
3. The compound of claim 2, wherein
A1 , A2 and A3 are the same, preferably O; and/or
n is 1 or 2, preferably 1 ; and/or
i) R1 to R4 and R11 to R16 are independently selected from linear or branched C1 -C4 alkyl and hydrogen, preferably hydrogen; or
ii) R5, R6, and R7 and/or R8, R9, and R10 form together with the N atom to which they are attached a hydrocarbon ring with up to 8 carbon atoms, preferably with 5 carbon atoms, wherein the ring preferably contains at least one double bond, more preferably 3 double bonds, wherein the ring is preferably pyridine, and/or the ring, preferably the pyridine, can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P, preferably the ring, more preferably the pyridine, is substituted by linear or branched C1 -C6 alkyl, more preferably by methyl, and
R1 to R4 and R11 to R16 are as defined above; and/or
X- is selected from chloride, bromide, or iodide.
5. Method of manufacturing a compound according to any of claims 1 to 4, comprising or consisting of the steps:
a) reacting a compound of formula (IV)
wherein
A is selected from O, S, or Se, preferably O;
R1 to R4 are independently selected from hydrogen, linear or branched alkyl, cycloalkyl or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P, preferably R1 to R4 are independently selected from linear or branched C1 -C4 alkyl and hydrogen, more preferably R1 to R4 are hydrogen; and
n is an integer from 0 to 12, preferably 1 or 2, more preferably 1 ; with at least one compound of formula (V), preferably in stoichiometric excess of the at least one compound of formula (V) in relation to the compound of formula (IV), more preferably more than two equivalents of the at least one compound of formula (V) in relation to the compound of formula (IV) (V),
wherein
A is selected from O, S, or Se, preferably O;
Z is selected from linear or branched alkyl, cycloalkyl or aryl or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P and/or which can be substituted by at least one substituent, preferably selected from hydroxy-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear and branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P, preferably Z is selected from linear or branched C1 - C6 alkyl or aryl, more preferably Z is aryl;
R17 is Cl, Br or I; and
R18 is linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P, preferably R18 is linear or branched C1 -C4 alkyl, which is substituted by Cl, Br, or I; wherein the reaction solution preferably further contains an amine compound, more preferably triethylamine; to obtain at least one compound of formula (VI)
wherein A, Z, n, R1 to R4, and R18 are as defined above; b) reacting the at least one compound of formula (VI) with at least one compound of formula (VII), preferably in stoichiometric excess of the at least one compound of formula (VII) in relation to the compound of formula (VI), more preferably more than two equivalents of the at least one compound of formula (VII) in relation to the compound of formula (VI);
wherein R19 to R21 are independently selected from hydrogen, linear or branched alkyl, cycloalkyl, or aryl, or linear or branched alkylcycloalkyl or alkylaryl having up to 30 carbon atoms, respectively, preferably up to 15 carbon atoms, more preferably up to 10 carbon atoms, and which can contain at least one heteroatom selected from O, S, N, Si, Se or P, and/or which can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P;
or
R19 to R21 form together with the N atom to which they are attached a hydrocarbon ring with up to 8 carbon atoms, preferably with 5 carbon atoms, wherein the ring can contain at least one double bond, preferably 3 double bonds, wherein the ring is preferably pyridine, and/or the ring can be substituted by at least one substituent, preferably selected from hydroxyl-, linear or branched C1 -C6 alkoxy-, amino-, nitro-, fluoro-, chloro-, bromo-, iodo-, carbonyl-, carboxyl-, linear or branched C1 -C6 ester- or ether-, mercapto-, sulfonyl-, cyano-, or linear or branched C1 -C6 alkyl-, alkenyl- or alkynyl-, cycloalkyl-, or aryl groups, whereby the hydrocarbon groups can contain at least one heteroatom selected from O, S, N, Si, Se or P, preferably the ring, more preferably pyridine, is substituted by C1 -C4 alkyl or hydrogen, more preferably by methyl; to obtain at least one compound of formula (I), (II) or (III).
6. Use of a compound according to any of claims 1 to 4 as a bleach activator.
7. A laundry detergent composition comprising at least one compound according to any of claims 1 to 4 and a bleach and optionally further components selected from surfactants, acidifiers, alkalizing agents, anti-crease compounds, antibacterial/antimicrobial substances, antioxidants, antideposition agents, antistatic agents, bitter substances, bleach stabilizers, builder substances, corrosion inhibitors, ironing aids, cobuilders, further fragrances or pro-fragrances, shrinkage inhibitors, electrolytes, emulsifiers, enzymes, enzyme stabilizers, protease inhibitors, colorants, dyes, dye transfer inhibitors, fluorescent agents, fungicides, germicides, metal sequestering agents, odor-complexing substances, auxiliary agents, hydrotropics, rinse aids, complexing agents, preservatives, optical brighteners, perfume carriers, pearl-luster agents, pH control agents, phobing and impregnating agents, polymers, swelling and sliding fasteners, foam inhibitors, layered silicates, dirt-repellent substances, organic solvents, silicone oils, soil-release active substances, UV-protective substances, viscosity regulators, thickeners, discoloration inhibitors, greying inhibitors, structurants, vitamins, and/or fabric softeners.
8. An automatic dishwashing composition comprising at least one compound according to any of claims 1 to 4 and a bleach and optionally further components selected from surfactants, acidifiers, alkalizing agents, anti-crease compounds, antibacterial/antimicrobial substances, antioxidants, antideposition agents, antistatic agents, bitter substances, bleach stabilizers, builder substances, corrosion inhibitors, ironing aids, cobuilders, further fragrances or pro-fragrances, shrinkage inhibitors, electrolytes, emulsifiers, enzymes, enzyme stabilizers, protease inhibitors, colorants, dyes, dye transfer inhibitors, fluorescent agents, fungicides, germicides, metal sequestering agents, odor-complexing substances, auxiliary agents, hydrotropics, rinse aids, complexing agents, preservatives, optical brighteners, perfume carriers, pearl-luster agents, pH control agents, phobing and impregnating agents, polymers, swelling and sliding fasteners, foam inhibitors, layered silicates, dirt-repellent substances, organic solvents, silicone oils, soil-release active substances, UV-protective substances, viscosity regulators, thickeners, discoloration inhibitors, greying inhibitors, structurants, vitamins, and/or fabric softeners.
9. An industrial cotton bleaching composition comprising at least one compound according to any of claims 1 to 4 and a bleach and optionally further components selected from surfactants, acidifiers, alkalizing agents, anti-crease compounds, antibacterial/antimicrobial substances, antioxidants, antideposition agents, antistatic agents, bitter substances, bleach stabilizers, builder substances, corrosion inhibitors, ironing aids, cobuilders, further fragrances or pro-fragrances, shrinkage inhibitors, electrolytes, emulsifiers, enzymes, enzyme stabilizers, protease inhibitors, colorants, dyes, dye transfer inhibitors, fluorescent agents, fungicides, germicides, metal sequestering agents, odor-complexing substances, auxiliary agents, hydrotropics, rinse aids, complexing agents, preservatives, optical brighteners, perfume carriers, pearl-luster agents, pH control agents, phobing and impregnating agents, polymers, swelling and sliding fasteners, foam inhibitors, layered silicates, dirt-repellent substances, organic solvents, silicone oils, soil-release active substances, UV-protective substances, viscosity regulators, thickeners, discoloration inhibitors, greying inhibitors, structurants, vitamins, and/or fabric softeners.
10. The composition according to any of claims 7 to 9, wherein the compound of formula (I) is contained in 0.1 to 50 wt.-%, preferably 0.25 to 25 wt.-%, more preferably 1 to 10 wt.-%, based on the total weight of the composition.
1 1 . The composition according to any of claims 7 to 10, wherein the composition has a pH value of from 4 to 14, preferably 6 to 12, more preferably 7 to 10.
EP19818025.9A 2018-12-21 2019-12-09 Bleach activators containing two quarternary ammonium groups Withdrawn EP3898920A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102018133517 2018-12-21
PCT/EP2019/084202 WO2020126608A1 (en) 2018-12-21 2019-12-09 Bleach activators containing two quarternary ammonium groups

Publications (1)

Publication Number Publication Date
EP3898920A1 true EP3898920A1 (en) 2021-10-27

Family

ID=68848268

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19818025.9A Withdrawn EP3898920A1 (en) 2018-12-21 2019-12-09 Bleach activators containing two quarternary ammonium groups

Country Status (2)

Country Link
EP (1) EP3898920A1 (en)
WO (1) WO2020126608A1 (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3775333A (en) * 1972-06-30 1973-11-27 American Cyanamid Co N-acyl azolinones as peroxygen bleach activators
WO1998016608A2 (en) * 1996-10-15 1998-04-23 The Procter & Gamble Company Asymmetrical cationic bleach activators and compositions employing the same
US7179779B1 (en) * 2006-01-06 2007-02-20 North Carolina State University Cationic bleach activator with enhanced hydrolytic stability
CN104557708B (en) * 2015-01-30 2017-04-26 江南大学 One-bath synthesis method and application of cationic bleach activator

Also Published As

Publication number Publication date
WO2020126608A1 (en) 2020-06-25

Similar Documents

Publication Publication Date Title
EP0464880B1 (en) Bleaching composition
CA1324379C (en) Quaternary ammonium or phosphonium peroxycarbonic acid precursors and their use in detergent bleach compositions
US4818426A (en) Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions
EP0690839B1 (en) Peroxyacids
US3597416A (en) Soil anti-redeposition agents,their use and detergent compositions containing same
EP0564251B1 (en) Amido peroxycarboxylic acids
MXPA06013992A (en) Organic activator.
JPH0762155B2 (en) Bleaching composition
US20140323381A1 (en) Acyl hydrazones as bleach-boosting active substances
IE61235B1 (en) Softening detergent compositions containing amide softening agent
BRPI0614939A2 (en) phosphate-free dishwashing cleaning formulation, mixed powder or mixed granule for use in dishwashing cleaning formulations, and use of a combination of copolymers
JP2004238623A (en) Use of transition metal complex as bleach catalyst
EP0257861B1 (en) Fabric conditioning composition
EP0257860A2 (en) Method for conditioning fabrics
US4329245A (en) Bleaching detergent compositions
US7015185B2 (en) Ammonium nitriles and the use thereof as hydrophobic bleaching activators
EP0540090A2 (en) Liquid cleaning compositions
EP3898920A1 (en) Bleach activators containing two quarternary ammonium groups
JPH0791779B2 (en) Bleach enhancer, bleaching method and bleach
JPH0597803A (en) Peroxy acid
US5320775A (en) Bleach precursors with novel leaving groups
JP4996482B2 (en) Polymer hydrophobic amino nitrile quaternary ammonium compounds for bleaching activity
MXPA05006578A (en) Organic activator.
JP2008511701A (en) Diethylmethylammonium nitrile and detergents and detergents containing this ammonium nitrile
JPH02158700A (en) Detergent composition

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20210608

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20230701