WO2017186480A1 - Composition de blanchiment sans métal - Google Patents

Composition de blanchiment sans métal Download PDF

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Publication number
WO2017186480A1
WO2017186480A1 PCT/EP2017/058636 EP2017058636W WO2017186480A1 WO 2017186480 A1 WO2017186480 A1 WO 2017186480A1 EP 2017058636 W EP2017058636 W EP 2017058636W WO 2017186480 A1 WO2017186480 A1 WO 2017186480A1
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composition
constitute
bonded
total weight
hydrogen
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PCT/EP2017/058636
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English (en)
Inventor
Markus Frey
Hauke Rohwer
Bjoern Ludolph
Rachel Kohli Steck
Frank Huelskoetter
Stefano Scialla
Euan MAGENNIS
Adam HAYWARD
Adam MALEKPOUR
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Basf Se
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Publication of WO2017186480A1 publication Critical patent/WO2017186480A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
    • 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

Definitions

  • the present invention relates to the use of a composition comprising specific a-amino- aldehydes, H2O2, a precursor of H2O2 or a peracid and optionally an activator as a bleaching mixture for textile materials or dishes either manually or in an automatic washing machine or dish washer.
  • a composition comprising specific a-amino- aldehydes, H2O2, a precursor of H2O2 or a peracid and optionally an activator as a bleaching mixture for textile materials or dishes either manually or in an automatic washing machine or dish washer.
  • Further aspects of the invention are a process for bleaching of stains or of soiling on textile materials or dishes in the context of a wa process either manually or in an automatic washing machine or dish washer.
  • detergent formulations comprising such a composition.
  • Peroxide-containing bleaching agents have long been used in washing and cleaning processes. They have an excellent action at a liquor temperature of 90°C and above, but their performance noticeably decreases with lower temperatures.
  • Various transition metal ions added in the form of suitable salts, and coordination compounds containing such cations are known to activate H2O2. In that manner it is possible for the bleaching effect, which is unsatisfactory at lower temperatures, of H2O2 or precursors that release H2O2 and of other peroxo compounds, to be increased.
  • bleach activators are tetraacetylethylenediamine, pentaacetylglucose, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium un- decanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate, octanoyloxy- benzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, octanoyloxybenzene, nonanoyloxybenzene, decanoyl- oxybenzene, undecanoyloxybenzene and dodecano
  • composition comprising
  • H2O2 a precursor of H2O2, or a peracid
  • X- is an anion
  • Ri and R2 independently of each other are hydrogen or linear or branched Ci-C6alkyl; or Ri and R2 together with the carbon atom to which they are bonded constitute a 5 or 6 membered cycloalkyl group;
  • R3 and R 4 independently of each other are hydrogen, linear or branched Ci-Ci2alkyl
  • C2-Ci2alkyl which is interrupted by one or more O, C2-C 6 alkenyl or Cs-Cecycloalkyl;
  • R3 and R 4 together are -(CH2)2-0-(CH2)2- and constitute with the nitrogen atom to which they are bonded a 6 membered ring;
  • anion X- is Ch, Br, CI0 4 ", NO3 " , BF 4 - or PF6.
  • the compound is of formula (1 ).
  • the various C1-C6 alkyl groups are, for example, methyl, ethyl, propyl, butyl, pentyl or hexyl and their various isomers.
  • Component a) of the composition may be H2O2, a precursor of H2O2 or a peracid, which are present in an aqueous washing process.
  • inorganic peroxides are preferred.
  • H2O2 peroxides As precursors of H2O2 peroxides come into consideration. I. e. every compound which is capable of yielding hydrogen peroxide in aqueous solutions, for example, the organic and inorganic peroxides known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 10 to 95°C.
  • inorganic peroxides are used, for example persulfates, perborates, percarbonates and/or persilicates.
  • inorganic peroxides examples include sodium perborate tetrahydrate or sodium perborate monohydrate, sodium percarbonate, inorganic peroxyacid compounds, such as for example potassium monopersulphate (MPS). If organic or inorganic peroxyacids are used as the peroxygen compound, the amount thereof will normally be within the range of about 2-80 wt-%, preferably from 4-30 wt-%.
  • the organic peroxides are, for example, mono- or poly-peroxides, urea peroxides, a combination of a Ci-C4alkanol oxidase and Ci-C4alkanol (Such as methanol oxidase and etha- nol as described in WO95/07972), alkylhydroxy peroxides, such as cumene hydroperoxide and t-butyl hydroperoxide.
  • the peroxides may be in a variety of crystalline forms and have different water contents, and they may also be used together with other inorganic or organic compounds in order to improve their storage stability.
  • peroxo acids can also be used.
  • M signifies hydrogen or a cation
  • Rig signifies unsubstituted C-i-C-isalkyl; substituted C-i-C-isalkyl; unsubstituted aryl; substituted aryl; -(Ci-Cealkylene)-aryl, wherein the alkylene and/or the alkyl group may be substituted; and phthalimidoCi-Cealkylene, wherein the phthalimido and/or the alkylene group may be substituted.
  • Preferred mono organic peroxy acids and their salts are those of formula 19
  • M signifies hydrogen or an alkali metal
  • R'i9 signifies unsubstituted Ci-C4alkyl; phenyl;-Ci-C2alkylene-phenyl or
  • CH3COOOH and its alkali salts are especially preferred.
  • ⁇ -phthalimido peroxy hexanoic acid and its alkali salts are especially preferred.
  • diperoxyacids for example, 1 ,12-diperoxydodecanedioic acid (DPDA), 1 ,9-diperoxyazelaic acid, diperoxybrassilic acid, diperoxysebasic acid, diperoxyisophthalic acid, 2-decyldiperoxybutane-1 ,4-diotic acid and 4,4'-sulphonylbisperoxybenzoic acid.
  • DPDA 1,12-diperoxydodecanedioic acid
  • 1 ,9-diperoxyazelaic acid diperoxybrassilic acid
  • diperoxysebasic acid diperoxysebasic acid
  • diperoxyisophthalic acid diperoxyisophthalic acid
  • 2-decyldiperoxybutane-1 ,4-diotic acid 2,4'-sulphonylbisperoxybenzoic acid.
  • an additional bleach activator may be of advantage.
  • component a) comprises a precursor of H2 O2 and a bleach activator.
  • the weight ratio between the precursor of H2 O2 and the bleach activator can vary from 10 : 1 to 1 :1 .
  • bleach activator is frequently used as a synonym for peroxyacid bleach precursor. All the above mentioned peroxy compounds may be utilized alone or in conjunction with a peroxyacid bleach precursor.
  • the bleaching composition of the invention can be suitably formulated to contain from 0.25 to 60 wt-%, preferably from 0.5 to 30 wt-%, of the peroxy bleaching agent.
  • Such precursors are the corresponding carboxyacid or the corresponding carboxyanhydrid or the corresponding carbonylchlorid, or amides, or esters, which can form the peroxy acids on perhydrolysis. Such reactions are commonly known.
  • Peroxyacid bleach precursors are known and amply described in literature, such as in the British Patents 836988; 864,798; 907,356; 1 ,003,310 and 1 ,519,351 ; German Patent 3,337,921 ; EP-A-0185522; EP-A-0174132; EP-A-0120591 ; and U.S. Pat. Nos. 1 ,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.
  • Suitable bleach activators include the bleach activators, that carry O- and/or N-acyl groups and/or unsubstituted or substituted benzoyl groups.
  • R22 is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein R21 is linear or branched (C7-Ci5)alkyl, especially activators known under the names SNOBS, SLOBS and DOBA; acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran; and also acetylated sorbitol and mannitol and acylated sugar derivatives, especially pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone. It is also possible to use the combinations of conventional bleach activators known from German Patent Application
  • Nitrile compounds that form perimine acids with peroxides also come into consideration as bleach activators.
  • peroxyacid bleach precursors are that of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US Pat. Nos. 4,751 ,015 and 4,397,757, in EP-A0284292 and EP-A-331 ,229.
  • peroxyacid bleach precursors of this class are: 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphonphenyl carbonate chloride - (SPCC), N-octyl,N,N-dimehyl-N10 -carbophenoxy decyl ammonium chloride - (ODC), 3-(N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate and ⁇ , ⁇ , ⁇ -trimethyl ammonium toluyloxy benzene sulphonate.
  • SPCC 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphonphenyl carbonate chloride -
  • ODC N-octyl,N,N-dimehyl-N10 -carbophenoxy decyl ammonium chloride -
  • a further special class of bleach precursors is formed by the cationic nitriles as disclosed in EP-A-303,520, WO 96/40661 and in European Patent Specification No.'s 458,396, 790244 and 464,880.
  • These cationic nitriles also known as nitril quats have the formula
  • R30 is a Ci-C24alkyl; a Ci-C24alkenyl; an alkaryl having a Ci-C24alkyl; a substituted Ci- C24alkyl; a substituted Ci-C24alkenyl; a substituted aryl, R31 and R32 are each independently a Ci-C3alkyl; hydroxyalkyi having 1 to 3 carbon atoms,
  • R33 is is a Ci-C2oalkyl; a Ci-C2oalkenyl; a substituted Ci-C2oalkyl; a substituted
  • Ci-C2oalkenyl an alkaryl having a Ci-C2 4 alkyl and at least one other substituent, R34, R35, R36, R37 and R38 are each independently hydrogen, a Ci-Cioalkyl, a Ci-Cioalkenyl, a substituted Ci-Cioalkyl, a substituted Ci-Cioalkenyl, carboxyl, sulfonyl or cyano
  • R38, R39, R40 and R41 are each independently a Ci-C6alkyl,
  • n' is an integer from 1 to 3
  • n" is an integer from 1 to 16
  • X is an anion
  • nitril quats have the following formula
  • R42 and R43 form, together with the nitrogen atom to which they are bonded, a ring comprising 4 to 6 carbon atoms, this ring may also be substituted by d-d-alkyl,
  • Ci-C5-alkoxy, d-Cs-alkanoyl, phenyl, amino, ammonium, cyano, cyanamino or chlo- ro and 1 or 2 carbon atom(s) of this ring may also be substituted by a nitrogen atom, by a oxygen atom, by a N-R 47 -group and/or by a R44-N-R 47 -group, wherein R 47 is hydrogen, Ci-C5-alkyl, d-d-alkenyl, d-d-alkinyl, phenyl, d-Cg-aralkyl,
  • R44 is C1-C24-, preferably d-d-alkyl; C2-C24- alkenyl, preferably d-d-alkenyl, cyanomethyl or d-d-alkoxy-d-d-alkyl,
  • R45 and R46 are independently from each other hydrogen; d-d-alkyl; d-d-alkenyl;
  • phenyl or d-d-alkylphenyl preferably hydrogen, methyl or phenyl, whereby preferably the moiety R45 signifies hydrogen, if R46 is not hydrogen, and
  • X- is an anion
  • nitril quats of formula ( ⁇ ) are Suitable examples of nitril quats of formula ( ⁇ ).
  • A is a saturated ring formed by a plurality of atoms in addition to the Ni atom, the saturated ring atoms to include at least one carbon atom and at least one heteroatom in addition to the Ni atom, the said one heteroatom selected from the group consisting of O, S and N atoms, the substituent R47 bound to the Ni atom of the Formula ( ⁇ ) structure is (a) a C-i-Cs- alkyl or alkoxylated alkyl where the alkoxy is C2-4, (b) a C4-C24cycloalkyl, (c) a C 7 -C24alkaryl, (d) a repeating or nonrepeating alkoxy or alkoxylated alcohol, where the alkoxy unit is C2-4, or (e) -CR5oR5i-C ⁇ N where R50 and R51 are each H, a Ci-C24alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating alkoxyl or
  • the compounds of formula (1 ) or (2) are used together with a peroxide or peroxide precursor and a bleach activator which is selected from the group consisting of tetraacetylethylenediamine, pentaacetylglucose, sodium oc- tanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium deca- noyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate, sodium dodeca- noyloxybenzenesulfonate, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, deca- noyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, oc- tanoyloxybenzene, nonanoyloxybenzene, decanoyloxybenzene, undecanoyloxybenzo
  • bleach catalysts which are commonly known, for example transition metal complexes as disclosed in EP 1 194514, EP 1383857 or WO04/007657.
  • Further bleach catalysts are disclosed in: US2001044401 , EP0458397, WO9606154, EP1038946, EP0900264, EP0909809, EP1001009, WO9965905, WO0248301 , WO0060045, WO02077145, WO0185717, WO0164826, EP0923635, DE 19639603, DE102007017654, DE102007017657, DE102007017656, US20030060388, EP0918840B1 , EP1 174491 A2, EP0805794B1 , WO9707192A1 , US6235695B1 , EP0912690B1 , EP832969B1 , US6479450B1 , W09933947A1 , WO0032731A1 ,
  • Water soluble in the context of the present invention means a solubility in demineralised water at 25°C and atmospheric pressure of at least 0.5g in 10Og water.
  • component a) is present in an amount of from 2 parts to 90 parts by weight and component b) is present in an amount of from 0.02 parts to 20 parts by weight; the sum being 100 parts.
  • composition is used for the bleaching of stains or of soiling on textile materials in the context of a washing process or by the direct application of a stain remover at a pH between 7 and 1 1.
  • the temperature of the washing process is between 5° C and 95° C.
  • the temperature is between 10° C and 60° C, more preferably between 10° C and 40° C. In particular 30° C.
  • Another aspect of the invention is a composition
  • a composition comprising
  • X- is an anion
  • Ri and R2 independently of each other are hydrogen or linear or branched Ci-C6alkyl; or Ri and R2 together with the carbon atom to which they are bonded constitute a 5 or 6 membered cycloalkyl group;
  • R3 and R 4 independently of each other are hydrogen, linear or branched Ci-Ci2alkyl, C2-Ci 2 alkyl which is interrupted by one or more O, C2-C 6 alkenyl or Cs-Cecycloalkyl;
  • R3 and R 4 together are -(CH2)2-0-(CH2)2- and constitute with the nitrogen atom to which they are bonded a 6 membered ring.
  • an aspect of the invention is a process for the bleaching of stains or of soiling on tex- tile materials or dishes in the context of a washing process or by the direct application of a stain remover comprising
  • X- is an anion
  • Ri and R2 independently of each other are hydrogen or linear or branched Ci-C 6 alkyl; or Ri and R2 together with the carbon atom to which they are bonded constitute a 5 or 6 membered cycloalkyl group;
  • R3 and R4 independently of each other are hydrogen, linear or branched Ci-Ci2alkyl, C2-Ci2alkyl which is interrupted by one or more O, C2-C6alkenyl or Cs-Cscycloalkyl;
  • R3 and R 4 together are -(CH2)2-0-(CH2)2- and constitute with the nitrogen atom to which they are bonded a 6 membered ring.
  • a further aspect is a detergent, cleaning or bleaching composition
  • a detergent, cleaning or bleaching composition comprising
  • the composition may optionally also contain water, or a filler material, such as Na2S0 4 .
  • a filler material such as Na2S0 4 .
  • All wt-% are based on the total weight of the detergent, cleaning or bleaching composition.
  • the detergent, cleaning or bleaching compositions can be any kind of industrial or domestic cleaning or bleaching formulation.
  • the detergents may be in solid, liquid, gel-like or paste-like form.
  • the detergents may also be in the form of powders or (super-)compact powders or granules, in the form of single- or multi-layer tablets (tabs), in the form of washing agent bars, washing agent blocks, washing agent sheets, washing agent pastes or washing agent gels, or in the form of powders, pastes, gels or liquids used in capsules or in pouches (sachets).
  • the concentration of the H2O2 or its precursor, such as perborate or percarbonate may vary in the range from 0.05 g/L to 15 g/L, preferably 0.05 g/L to 8 g/L and more preferably from 0.05 g/L to 2 g/L.
  • the activator such as tetraacetylethylenediamine may vary from 0.01 g/L to 5 g/L, preferably from 0.015 g/L to 3 g/L, more preferably from 0.015 g/L to 1 g/L.
  • the compound of formula (1 ) or (2) may vary from 5 ⁇ /L to 1 mmol/L, preferably from 5 ⁇ /L to 0.5 mmol/L, more preferably from 20 ⁇ /L to 0.3 mmol/L.
  • the amount thereof is preferably from 0.5 to 50 wt-%, especially from 0.5 to 30 wt-%.
  • the amount thereof is preferably from 1 to 70 wt-%, especially from 1 to 50 wt-%. Special preference is given to an amount of from 5 to 50 wt-% and especially an amount of from 10 to 50 wt-%.
  • composition according to the invention can be, for example, a peroxide-containing heavy-duty detergent or a separate bleaching additive, or a stain remover that is to be applied directly.
  • a bleaching additive is used for removing coloured stains on textiles in a sep- arate liquor before the clothes are washed with a detergent.
  • a bleaching additive can also be used in a liquor together with a detergent.
  • Stain removers can be applied directly to the textile in question and are used especially for pretreatment in the event of heavy local soiling.
  • the stain remover can be applied in liquid form, by a spraying method or in the form of a solid substance, such as a powder especially as a granule.
  • the anionic surfactant A) can be, for example, a sulfate, sulfonate or carboxylate surfactant or a mixture thereof. Preference is given to alkylbenzenesulfonates, alkyl sulfates, alkyl ether sulfates, olefin sulfonates, fatty acid salts, alkyl and alkenyl ether carboxylates or to an a-sulfonic fatty acid salt or an ester thereof.
  • Preferred sulfonates are, for example, alkylbenzenesulfonates having from 10 to 20 carbon atoms in the alkyl radical, alkyl sulfates having from 8 to 18 carbon atoms in the alkyl radical, alkyl ether sulfates having from 8 to 18 carbon atoms in the alkyl radical, and fatty acid salts derived from palm oil or tallow and having from 8 to 18 carbon atoms in the alkyl moiety.
  • the average molar number of ethylene oxide units added to the alkyl ether sulfates is from 1 to 20, preferably from 1 to 10.
  • the cation in the anionic surfactants is preferably an alkaline metal cation, especially sodium or potassium, more especially sodium.
  • Preferred carboxylates are alkali metal sarcosinates of formula Ri9-CON(R2o)CH2COOMi wherein R1 9 is C9-Ci7alkyl or Cg-dzalkenyl, R2 0 is Ci-C4alkyl and Mi is an alkali metal, especially sodium.
  • the non-ionic surfactant B) may be, for example, a primary or secondary alcohol ethox- ylate, especially a C8-C20 aliphatic alcohol ethoxylated with an average of from 1 to 20 mol of ethylene oxide per alcohol group. Preference is given to primary and secondary C10-C15 aliphatic alcohols ethoxylated with an average of from 1 to 10 mol of ethylene oxide per alcohol group.
  • Non-ethoxylated non-ionic surfactants for example alkylpolyglycosides, glycerol monoethers and polyhydroxyamides (glucamide), may likewise be used.
  • the total amount of anionic and non-ionic surfactants is preferably from 3 to 50 wt-%, especially from 5 to 40 wt-% and more especially from 5 to 30 wt-%.
  • the lower limit of those surfactants to which even greater preference is given is 5 wt-%.
  • alkali metal phosphates especially tripolyphosphates, carbonates and hydrogen carbonates, especially their sodium salts, silicates, aluminum silicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylenepoly(alkylenephosphonates) and mixtures of such compounds.
  • Silicates that are especially suitable are sodium salts of crystalline layered silicates of the formula NaHSit02t+i.pH20 or Na2Sit02t+i .pH20 wherein t is a number from 1.9 to 4 and p is a number from 0 to 20.
  • aluminum silicates preference is given to those commercially available under the names zeolite A, B, X and HS, and also to mixtures comprising two or more of such components. Special preference is given to zeolite A.
  • polycarboxylates preference is given to polyhydroxycarboxylates, especially citrates, and acrylates, and also to copolymers thereof with maleic anhydride.
  • Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylene- diamine disuccinate either in racemic form or in the enantiomerically pure (S,S) form.
  • Biodegradable options are, for example, aminoacid acetates, such as Trilon M (BASF) and Dissolvine GL (AKZO), as well as asparaginic acid derivatives, such as Baypure CX (Lanx- ess).
  • aminoacid acetates such as Trilon M (BASF) and Dissolvine GL (AKZO)
  • AKZO Dissolvine GL
  • asparaginic acid derivatives such as Baypure CX (Lanx- ess).
  • Phosphonates or aminoalkylenepoly(alkylenephosphonates) that are especially suitable are alkali metal salts of 1-hydroxyethane-1 , 1-diphosphonic acid, nitrilot- ris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethy- lenetriaminepentamethylenephosphonic acid, and also salts thereof.
  • Also preferred poly- phosphonates have the following formula
  • Ri8 is CH2PO3H2 or a water soluble salt thereof and
  • d is an integer of the value 0, 1 , 2 or 3.
  • polyphosphonates wherein d is an integer of the value of 1
  • compositions may comprise, in addition to the combination according to the invention, one or more optical brighteners, for example from the classes bis-triazinylamino- stilbenedisulfonic acid, bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl or bis- benzofuranylbiphenyl, a bis-benzoxalyl derivative, bis-benzimidazolyl derivative or couma- rin derivative or a pyrazoline derivative.
  • optical brighteners for example from the classes bis-triazinylamino- stilbenedisulfonic acid, bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl or bis- benzofuranylbiphenyl, a bis-benzoxalyl derivative, bis-benzimidazolyl derivative or couma- rin derivative or a pyrazoline derivative.
  • optical brighteners for example from the classes bis-tria
  • Such additives are, for example, dirt-suspending agents, for example sodium carboxymethylcellulose; pH regulators, for example alkali metal or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and the granulating properties, for example sodium sulfate; perfumes; and also, if appropriate, antistatics and softening agents such as, for example, smectite; bleaching agents; pigments; and/or toning agents.
  • These constituents should especially be stable to any bleaching agent employed. If the detergent composition is used in an automatic dishwasher it is also common to use silver-corrosion inhibitors.
  • auxiliaries are added in a total amount of from 0.1 - 20 wt-%, preferably from 0.5 - 10 wt-%, especially from 0.5 - 5 wt-%, based on the total weight of the detergent formulation.
  • the detergent may optionally also comprise enzymes.
  • Enzymes can be added for the purpose of stain removal.
  • the enzymes usually improve the action on stains caused by protein or starch, such as, for example, blood, milk, grass or fruit juices.
  • Preferred enzymes are cellulases and proteases, especially proteases.
  • Cellulases are enzymes that react with cellulose and its derivatives and hydrolyse them to form glucose, cellobiose and cellooligosaccharides. Cellulases remove dirt and, in addition, have the effect of enhancing the soft handle of the fabric.
  • customary enzymes include, but are by no means limited to, the following: proteases as described in US-B-6 242 405, column 14, lines 21 to 32;
  • amylases as described in US-B-6 242 405, column 14, lines 47 to 56;
  • detergent proteases such as Alcalase ® , Esperase ® , Everlase ® ,
  • Savinase ® , Kannase ® and Durazym ® , are sold e.g. by NOVOZYMES A S.
  • detergent amylases such as Termamyl ® , Duramyl ® , Stainzyme ® , Natalase ® , Ban ® and Fungamyl ® , are sold e.g. by NOVOZYMES A S.
  • detergent cellulases such as Celluzyme ® , Carezyme ® and Endo- lase ® , are sold e.g. by NOVOZYMES A/S.
  • detergent lipases such as Lipolase ® , Lipolase Ultra ® and Lipo- prime ® , are sold e.g. by NOVOZYMES A/S.
  • Suitable mannanases such as Mannanaway ® , are sold by NOVOZYMES A/S.
  • proteases such as BLAP ® , Optimase ® , Opticlean ® , Maxacal ® , Maxapem ® , Esperase ® and/or Savinase ®
  • amylases such as Termamyl ® , Amylase-LT ® , Maxamyl ® and/or Duramyl ®
  • lipases such as Lipolase ® , Lipomax ® , Lumafast ® and/or Lipozym ® .
  • the enzymes which may be used can, as described e.g. in International Patent Applications WO 92/1 1347 and WO 94/23005, be ad- sorbed on carriers and/or embedded in encapsulating substances in order to safeguard them against premature inactivation. They are present in the cleaning formulations according to the invention preferably in amounts not exceeding 5 wt-%, especially in amounts of from 0.1 wt-% to 1 .2 wt-%.
  • Amylases The present invention preferably makes use of amylases having improved sta- bility in detergents, especially improved oxidative stability.
  • amylases are non-limitingly illustrated by the following: (a) An amylase according to WO 94/02597, Novo Nordisk A/S, published Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine (preferably threonine), of the methionine residue located in position 197 of the B.licheniformis alpha-amylase, known as TERMAMYL ® , or the homologous position variation of a similar parent amylase, such as B.
  • amyloliquefaciens B.subtilis, or B.stearothermophilus
  • Stability-enhanced amylases as described by Genencor International in a paper entitled "Oxidatively Resistant alpha-Amylases" presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. There- in it was noted that bleaches in automatic dishwashing detergents inactivate alpha- amylases but that improved oxidative stability amylases have been made by Genencor from B. licheniformis NCIB8061. Any other oxidative stability-enhanced amylase can be used.
  • Protease enzymes are usually present in preferred embodiments of the inven- tion at levels between 0.001 wt-% and 5 wt-%.
  • the proteolytic enzyme can be of animal, vegetable or microorganism (preferred) origin. More preferred is serine proteolytic enzyme of bacterial origin. Purified or nonpurified forms of enzyme may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants.
  • Suitable commercial proteolytic enzymes include Alcalase ® , Esperase ® , Durazyme ® , Savinase ® , Maxatase ® , Maxacal ® , and Maxapem ® 15 (protein engineered Maxacal). Purafect ® and subtilisin BPN and BPN' are also commercially available.
  • lipases comprise from about 0.001 wt-% to about 0.01 wt-% of the instant compositions and are optionally combined with from about 1 wt-% to about 5 wt-% of a surfactant having limesoap-dispersing properties, such as an alkyldimethylamine N-oxide or a sulfobetaine.
  • a surfactant having limesoap-dispersing properties such as an alkyldimethylamine N-oxide or a sulfobetaine.
  • Suitable lipases for use herein include those of bacterial, animal and fungal origin, including those from chemically or genetically modified mutants.
  • lipases When incorporating lipases into the instant compositions, their stability and effectiveness may in certain instances be enhanced by combining them with small amounts (e.g., less than 0.5 wt-% of the composition) of oily but non-hydrolyzing materials.
  • the enzymes when used, may be present in a total amount of from 0.01 to 5 wt-%, especially from 0.05 to 5 wt-% and more especially from 0.1 to 4 wt-%, based on the total weight of the detergent formulation.
  • the detergent formulation is a dishwashing detergent formulation, more preferably an automatic dishwashing detergent formulation, then it can optionally also comprise from about 0.001 wt-% to about 10 wt-%, preferably from about 0.005 wt-% to about 8 wt-%, most preferably from about 0.01 wt-% to about 6 wt-% of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes.
  • Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
  • the compositions may, in addition to comprising the catalysts described herein, also comprise photocatalysts the action of which is based on the generation of singlet oxygen.
  • Further preferred additives to the compositions according to the invention are dye-fixing agents and/or polymers which, during the washing of textiles, prevent staining caused by dyes in the washing liquor that have been released from the textiles under the washing conditions.
  • Such polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or pol- yvinylpyridine-N-oxides, which may have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range of from 5000 to 60 000, more especially from 10 000 to 50 000.
  • Such polymers are usually used in a total amount of from 0.01 to 5 wt-%, especially from 0.05 to 5 wt-%, more especially from 0.1 to 2 wt-%, based on the total weight of the detergent formulation.
  • Preferred polymers are those mentioned in WO-A-02/02865 (see especially page 1 , last paragraph and page 2, first paragraph) and those in WO-A-04/05688.
  • inventive detergent composition when used as hardsurface cleaner, especially when the composition is used in automatic dishwasher formulation then, it has been found out, that it is preferable to avoid the use of simple calcium-precipitating soaps as antifoams in the present compositions as they tend to deposit on the dishware. Indeed, phosphate esters are not entirely free of such problems and the formulator will generally choose to minimize the content of potentially depositing antifoams in the instant compositions.
  • foam suppressors are paraffin, paraffin/alcohol combinations, or bisfatty acid amides.
  • the dishwashing detergent formulations may also optionally contain one or more heavy metal chelating agents, such as hydroxyethyldiphosphonate (HEDP).
  • HEDP hydroxyethyldiphosphonate
  • chelating agents suitable for use herein can be selected from the group consisting of amino carboxylates, amino phos- phonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof.
  • Other suitable chelating agents for use herein are the commercial DEQUEST series, and che- lants from Nalco, Inc.
  • Aminocarboxylates useful as optional chelating agents include ethylenediaminetetrace- tates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.
  • Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates).
  • Further biodegradable sequestrants are, for example, aminoacid acetates, such as Trilon M (BASF) and Dissolvine GL (AKZO), as well as asparaginic acid derivatives, such as Bay pure CX.
  • the aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • a highly preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS").
  • these chelating agents or transition-metal selective sequestrants will generally comprise from about 0.001 wt-% to about 10 wt-%, more preferably from about 0.05 wt-% to about 1 wt-% of the dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations herein.
  • Preferred dishwashing detergent formulations may additionally contain a dispersant polymer.
  • a dispersant polymer is typically at levels in the range from 0 wt-% to about 25 wt-%, preferably from about 0.5 wt-% to about 20 wt-%, more preferably from about 1 wt-% to about 8 wt-% of the detergent composition.
  • Dispersant polymers are useful for improved filming performance of the present dishwasher detergent compositions, especially in higher pH embodiments, such as those in which wash pH exceeds about 9.5.
  • Particularly preferred are polymers, which inhibit the deposition of calcium carbonate or magnesium silicate on dishware.
  • Suitable polymers are preferably at least partially neutralized or alkali metal, ammonium or substituted ammonium (e.g., mono-, di- or triethanolammonium) salts of polycarboxylic acids.
  • the alkali metal, especially sodium salts are most preferred. While the molecular weight of the polymer can vary over a wide range, it preferably is from about 1 ,000 to about 500,000, more preferably is from about 1 ,000 to about 250,000.
  • Unsaturated monomeric acids that can be polymerized to form suitable dispersant polymers include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • monomeric segments containing no carboxylate radicals such as methyl vinyl ether, sty- rene, ethylene, etc. is suitable provided that such segments do not constitute more than about 50 wt-% of the dispersant polymer.
  • Copolymers of acrylamide and acrylate having a molecular weight of from about 3,000 to about 100,000, preferably from about 4,000 to about 20,000, and an acrylamide content of less than about 50 wt-%, preferably less than about 20 wt-% of the dispersant polymer can also be used. Most preferably, such dispersant polymer has a molecular weight of from about 4,000 to about 20,000 and an acrylamide content of from about 0 wt-% to about 15 wt-%, based on the total weight of the polymer. Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers.
  • Such copolymers contain as monomer units: a) from about 90 wt-% to about 10 wt-%, preferably from about 80 wt-% to about 20 wt-% acrylic acid or its salts and b) from about 10 wt-% to about 90 wt-%, preferably from about 20 wt-% to about 80 wt-% of a substituted acrylic monomer or its salt and have the general formula:
  • R a , Rb, or R c preferably R a or Rb, is a 1 to 4 carbon alkyl or hydroxyalkyl group; R a or Rb can be a hydrogen and R c can be a hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomer wherein R a is methyl, Rb is hydrogen, and R c is sodium.
  • a suitable low molecular weight polyacrylate dispersant polymer preferably has a molecular weight of less than about 15,000, preferably from about 500 to about 10,000, most prefera- bly from about 1 ,000 to about 5,000.
  • the most preferred polyacrylate copolymer for use herein has a molecular weight of about 3,500 and is the fully neutralized form of the polymer comprising about 70 wt-% acrylic acid and about 30 wt-% methacrylic acid.
  • dispersant polymers useful herein include the polyethylene glycols and polypropylene glycols having a molecular weight of from about 950 to about 30,000.
  • dispersant polymers useful herein include the cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate.
  • cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate.
  • Sodium cellulose sulfate is the most preferred polymer of this group.
  • Suitable dispersant polymers are the carboxylated polysaccharides, particularly starches, celluloses and alginates.
  • filler materials can also be present in the instant dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations. These include sucrose, sucrose esters, sodium sulfate, potassium sulfate, etc., in amounts up to about 70 wt-%, preferably from 0 wt-% to about 40 wt-% of the dishwashing detergent formulations, more preferably auto- matic dishwashing detergent formulations.
  • Preferred filler is sodium sulfate, especially in good grades having at most low levels of trace impurities.
  • Sodium sulfate used herein preferably has a purity sufficient to ensure it is non-reactive with bleach; it may also be treated with low levels of sequestrants, such as phosphonates or EDDS in magnesium-salt form. Note that preferences, in terms of purity sufficient to avoid decomposing bleach, applies also to pH-adjusting component ingredients, specifically including any silicates used herein.
  • Organic solvents that can be used in the cleaning formulations according to the invention, especially when the latter are in liquid or paste form, include alcohols having from 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol, diols having from 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol, and mixtures thereof, and the ethers derivable from the mentioned classes of compound.
  • Such water-miscible solvents are present in the cleaning formulations according to the invention preferably in amounts not exceeding 20 wt-%, especially in amounts of from 1 wt-% to 15 wt-%.
  • dishwashing detergent formulations more preferably automatic dishwashing deter- gent formulations herein will be buffered, i.e., they are relatively resistant to pH drop in the presence of acidic soils.
  • other compositions herein may have exceptionally low buffering capacity, or may be substantially unbuffered.
  • Techniques for controlling or varying pH at recommended usage levels more generally include the use of not only buffers, but also additional alkalis, acids, pH-jump systems, dual compartment containers, etc., and are well known to those skilled in the art.
  • Certain dishwashing detergent formulations comprise a pH-adjusting component selected from water-soluble alkaline inorganic salts and water-soluble organic or inorganic builders.
  • the pH-adjusting components are selected so that when the dishwashing detergent formulation, more preferably automatic dishwashing detergent formulation is dissolved in water at a concentration of 1 ,000-5,000 ppm, the pH remains in the range of above about 8, preferably from about 9.5 to about 1 1 .
  • the preferred nonphosphate pH-adjusting component can be selected from the group consisting of:
  • sodium silicate preferably hydrous sodium silicate having Si02:Na20 ratio of from about 1 :1 to about 2: 1 , and mixtures thereof with limited quantities of sodium metasilicate;
  • Preferred embodiments contain low levels of silicate (i.e. from about 3 wt-% to about 10 wt- % Si0 2 ).
  • Illustrative of highly preferred pH-adjusting component systems of this specialized type are binary mixtures of granular sodium citrate with anhydrous sodium carbonate, and three- component mixtures of granular sodium citrate trihydrate, citric acid monohydrate and anhydrous sodium carbonate.
  • the amount of the pH adjusting component in compositions used for automatic dishwashing is preferably from about 1 wt-% to about 50 wt-% of the composition.
  • the pH-adjusting component is present in the composition in an amount from about 5 wt-% to about 40 wt-%, preferably from about 10 wt-% to about 30 wt-%.
  • compositions herein having a pH between about 9.5 and about 1 1 of the initial wash solution particularly preferred automatic dishwashing detergent formulations embodiments comprise, by weight of the automatic dishwashing detergent formulations, from about 5 wt- % to about 40 wt-%, preferably from about 10 wt-% to about 30 wt-%, most preferably from about 15 wt-% to about 20 wt-%, of sodium citrate with from about 5 wt-% to about 30 wt- %, preferably from about 7 wt-% to 25 wt-%, most preferably from about 8 wt-% to about 20 wt-% sodium carbonate.
  • the essential pH-adjusting system can be complemented (i.e. for improved sequestration in hard water) by other optional detergency builder salts selected from nonphosphate de- tergency builders known in the art, which include the various water-soluble, alkali metal, ammonium or substituted ammonium borates, hydroxysulfonates, polyacetates, and poly- carboxylates. Preferred are the alkali metals, especially sodium, salts of such materials. Alternate water-soluble, non-phosphorus organic builders can be used for their sequestering properties.
  • polyacetate and polycarboxylate builders are the sodium, po- tassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid; nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, ox- ydisuccinic acid, carboxymethoxysuccinic acid, mellitic acid, and sodium benzene polycarboxylate salts.
  • Further biodegradable buildes are, for example, aminoacid acetates, such as Trilon M (BASF) and Dissolvine GL (AKZO), as well as asparaginic acid derivatives, such as Baypure CX.
  • the detergent formulations can take a variety of physical forms such as, for example, powder granules, tablets (tabs), gel and liquid. Examples thereof include, inter alia, conventional high-performance detergent powders, supercompact high-performance detergent pow- ders and tabs.
  • One important physical form is the so-called concentrated granular form, which is added to a washing machine.
  • compact or supercompact detergents are so-called compact or supercompact detergents.
  • Such detergents usually contain only small amounts of fillers or of substances, such as sodium sulfate or sodium chloride, required for detergent manufacture.
  • the total amount of such substances is usually from 0 to 10 wt-%, especially from 0 to 5 wt-%, more especially from 0 to 1 wt-%, based on the total weight of the detergent formulation.
  • Such (super)compact detergents usually have a bulk density of from 650 to 1000 g/l, especially from 700 to 1000 g/l and more especially from 750 to 1000 g/l.
  • the detergent formulations can also be in the form of tablets (tabs).
  • tabs The advantages of tabs reside in the ease of dispensing and convenience in handling. Tabs are the most compact form of solid detergent formulation and usually have a volumetric density of, for example, from 0.9 to 1.3 kg/litre. To achieve rapid dissolution, such tabs generally contain special dissolution aids: - carbonate/hydrogen carbonate/citric acid as effervescents;
  • - disintegrators such as cellulose, carboxymethyl cellulose or cross-linked poly(N-vinyl- pyrrolidone);
  • the tabs may also comprise combinations of such dissolution aids.
  • the detergent formulation may also be in the form of an aqueous liquid containing from 5 wt-% to 50 wt-%, preferably from 10 wt-% to 35 wt-%, of water or in the form of a nonaqueous liquid containing no more than 5 wt-%, preferably from 0 wt-% to 1 wt-% of water.
  • Non-aqueous liquid detergent formulations may comprise other solvents as carriers.
  • Low molecular weight primary or secondary alcohols for example methanol, ethanol, propanol and isopropanol, are suitable for that purpose.
  • the solubilising surfactant used is preferably a monohydroxy alcohol but polyols, such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1 ,3-propanediol, ethylene glycol, glycerol and 1 ,2- propanediol) can also be used.
  • Such carriers are usually used in a total amount of from 5 wt-% to 90 wt-%, preferably from 10 wt-% to 50 wt-%, based on the total weight of the detergent formulation.
  • the detergent formulations can also used in so-called "unit liquid dose" form.
  • an aspect of the invention is a granule comprising
  • the granules according to the invention comprise a water-soluble organic polymer as binder.
  • a water-soluble organic polymer as binder.
  • Such polymers may be used singly or in the form of mixtures of two or more polymers.
  • Water-soluble polymers that come into consideration are, for example, polyethylene glycols, copolymers of ethylene oxide with propylene oxide, gelatin, polyacrylates, polymeth- acrylates, polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates, polyvinylimidazoles, poly- vinylpyridine-N-oxides, copolymers of vinylpyrrolidone with long-chain a-olefins, copoly- mers of vinylpyrrolidone with vinylimidazole, poly(vinylpyrrolidone/dimethylaminoethyl methacrylates), copolymers of vinylpyrrolidone/dimethylaminopropyl methacrylamides, copolymers of vinylpyrrolidone/dimethylaminopropyl acrylamides, quaternised copolymers of vinylpyrrolidones and dimethylaminoethyl methacrylates, terpolymers
  • polyethylene glycols carboxymethyl cellulose
  • polyacrylamides polyvinyl alcohols
  • polyvinylpyrrolidones gelatin
  • hydro- lysed polyvinyl acetates copolymers of vinylpyrrolidone and vinyl acetate
  • poly- acrylates copolymers of ethyl acrylate with methacrylate and methacrylic acid, and polymathacrylates.
  • Encapsulating materials include especially water-soluble and water-dispersible polymers and waxes. Of those materials, preference is given to polyethylene glycols, polyamides, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates, copolymers of vinylpyrrolidone and vinyl acetate, and also polyacrylates, paraffins, fatty acids, copolymers of ethyl acrylate with methacrylate and methacrylic acid, and polymethacrylates.
  • additives (d) that come into consideration are, for example, wetting agents, dust removers, water-insoluble or water-soluble dyes or pigments, and also dissolution accelerators, optical brighteners and sequestering agents. Examples have already been given above.
  • Sodi- um /V-chloro-p-toluenesulfonamide trihydrate (98%; 25.92g, 0.090mol) is slowly added at 25°C to a solution of 1 -(2-methylprop-1-enyl)azepane (95%; 15.00g, 0.093mol) in dichloro- methane (300ml) and the resulting suspension stirred overnight.
  • the reaction mixture is filtered and the filtrate subsequently washed with 1 .1 % sodium hypochlorite (330g; 30g 12% sodium hypochlorite diluted with 300g ice), water (50ml), 1.1 % sodium hypochlorite (55g; 5g 12% sodium hypochlorite diluted with 50ml water) and water (2x100ml).
  • the organic phase is split off, dried over sodium sulfate, filtered and the solvent evaporated in vacuo.
  • the resulting dark brown oil (15.7g) is distilled to afford the title compound as colorless oil (1 1 .4g; assay ca. 98% by GLC), bp. 32°C / 0.035mbar;

Abstract

La présente invention concerne l'utilisation d'une composition comprenant des α-aminoaldéhydes spécifiques, H2O2, un précurseur de H2O2 ou un peracide et facultativement un activateur en tant que mélange de blanchiment pour des matériaux textiles ou de la vaisselle manuellement ou dans une machine à laver ou un lave-vaisselle automatique. D'autres aspects de l'invention concernent un procédé de blanchiment de taches ou de salissure sur des matières textiles ou de la vaisselle dans le contexte d'un processus de lavage, manuellement ou dans une machine à laver ou un lave-vaisselle automatique. D'autres aspects de l'invention concernent des formulations de détergent comprenant une telle composition.
PCT/EP2017/058636 2016-04-26 2017-04-11 Composition de blanchiment sans métal WO2017186480A1 (fr)

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