EP0892846B1 - Renfor ateur de pouvoir de blanchiment pour compositions d'agents de blanchiment et de detergents textiles - Google Patents

Renfor ateur de pouvoir de blanchiment pour compositions d'agents de blanchiment et de detergents textiles Download PDF

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Publication number
EP0892846B1
EP0892846B1 EP97914305A EP97914305A EP0892846B1 EP 0892846 B1 EP0892846 B1 EP 0892846B1 EP 97914305 A EP97914305 A EP 97914305A EP 97914305 A EP97914305 A EP 97914305A EP 0892846 B1 EP0892846 B1 EP 0892846B1
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Prior art keywords
bleach
weight
radical
acids
bis
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EP97914305A
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German (de)
English (en)
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EP0892846A1 (fr
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Thomas Wehlage
Dieter Boeckh
Werner Bertleff
Alfred Oftring
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BASF SE
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BASF SE
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Priority claimed from DE1996111992 external-priority patent/DE19611992A1/de
Priority claimed from DE1996125908 external-priority patent/DE19625908A1/de
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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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • 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

Definitions

  • the invention relates to the use of amines as bleach boosters for laundry detergent compositions and bleaches containing them and Laundry detergent compositions.
  • bleaching effect of used as a bleach Peroxy compounds, peracids and combinations of peroxy compounds with peracid-releasing activators by adding bleach boosters or bleach catalysts can be reinforced.
  • a metal-free Bleaching catalysts are, for example, iminium salts, sulfonimines and N-sulfonyloxaziridines used.
  • EP-B1-0 313 146 describes the use of secondary amines of the formula (C 6-20 hydrocarbyl) (C 1-20 hydrocarbyl) NH generally described in amounts of 1-10% by weight as additional plasticizers in detergent compositions containing a bleach and a bleach activator.
  • EP-A3-0 236 270 describes aliphatic secondary amines in amounts of 1 - 10% by weight as foam-generating agents or surface-active compounds in combination with a special bleach and bleach activators generally described in speckles.
  • JP-A-07197097 describes bleaching compositions which a peroxide of the oxygen type, a bleach activator based on acyloxianilide derivatives and one or more amines, amine salts or quaternary ammonium salts contained in an amount of at least 1 wt .-%.
  • the amines can be the hydrophilic secondary amines diethanolamine, ethanolmethylamine, Be diisopropanolamine or N-methylaniline.
  • the compositions are used for bleaching dyed textiles, fading the coloring should be avoided.
  • JP 06248295 contains bleaching compositions with good storage stability described, which have a high bleaching power and decolorization avoid textiles.
  • the compositions contain peroxides and a Salt from a bleach activator from an aromatic peracid precursor anion and a quaternary ammonium ion in an amount of at least 0.7% by weight, which is derived from the hydrophilic secondary amines diethanolamine, Can derive diisopropanolamine or dimethylamine.
  • EP-A-0 173 398 describes detergent compositions which can clean and soften textiles in a washing liquid.
  • essential fabric softening ingredient can be a mixture of long chain secondary amine with cellulase can be used.
  • usable are dilaurylamine, distearylamine and tallow methylamine in one Amount of 0.5 to 15 wt .-%, preferably 1 to 10 wt .-%, particularly preferably 2 to 5 wt .-% described.
  • the detergent compositions can contain bleaches and bleach activators.
  • DD 129 565 describes detergent compositions, the graying inhibitors contain.
  • Ricinoleic acid ethanolamide can be used as a graying inhibitor in an amount of 5 parts by weight in combination with sodium borate perhydrate be used. Also suitable are dodecylethanolamine, Hexadecylethanolamine and oleic acid ethanolamide in an amount of 1 to 5 parts by weight described.
  • WO 86/07603 contains detergents for low washing temperatures described as an aliphatic amine compound as a washing power reinforcing additive contain.
  • the amidoamines listed can be secondary amines be, in the detergents described only tertiary amines in Amounts of more than 1% by weight are used, optionally in addition to bleaching agents and bleach activators.
  • cyclic secondary amines are used as quenchers for Singlet oxygen described. They are in a bleach next to one active halogen-containing compound in an amount of 0.5 to 40 % By weight, preferably 2.0 to 30% by weight.
  • a bleach detergent composition can 0.1 to 30 wt .-% of the cyclic hindered contain secondary amine, the proportion in the example formulations is at least 5 parts by weight.
  • aromatic secondary amines are radical scavengers for free radicals in liquid hydrogen peroxide compositions described that do not contain an activator.
  • WO 95/33035 describes detergent compositions which Contain oleoyl sarcosinate and a surface active amine.
  • a surface active Amines are preferably primary or tertiary amines. Secondary amines with two long chain alkyl residues are disclosed. The Amines are preferably primary or tertiary amines. Secondary amines with two long chain alkyl radicals are disclosed.
  • compositions are found to be particularly effective in removing greasy or oily soiling.
  • EP-A1-0 026 528 describes detergent compositions which also act as a plasticizer. They can contain a cationic secondary amine. Examples include coconut methylamine in an amount of 2% by weight and Laurylbenzylamine specified.
  • the object of the present invention is to provide a bleaching booster To provide bleach or laundry detergent compositions.
  • Another object of the present invention is to provide a bleach booster to provide, which is effective at a low temperature.
  • Another object of the present invention is to provide a bleach booster To provide that for bleaching hydrophobic and / or hydrophilic stains suitable for textiles.
  • Another object of the present invention is to use a bleach or Textile detergent composition with a bleach and a bleach booster to provide which has an improved bleaching effect.
  • Another object of the present invention is to provide a bleach or fabric detergent composition which exhibits an improved bleaching effect at a low temperature. Another object is to provide a bleach or fabric detergent composition that improves the removal of hydrophobic and / or hydrophilic soils from textiles. Another object is to provide a bleach or textile detergent composition which contains a bleaching system and at least one enzyme, the bleaching system not or only slightly impairing the enzyme action.
  • the amines enhance the bleaching action of bleaching compositions or textile detergent formulations.
  • they intensify the bleaching effect of bleaching or textile detergent compositions containing peroxy compounds or peracids, particularly in the case of hydrophobic / lipophilic soiling on textiles, and also in the case of hydrophilic, lipophobic soiling.
  • the bleaching or textile detergent compositions containing the claimed amines are preferably used for bleaching hydrophobic soils on textiles.
  • the bleach-strengthening effect of the amines enables the use of the bleaching or textile detergent compositions at low temperatures, in particular in the range up to a maximum of 40 ° C., at which bleaching agent compositions are often insufficiently effective.
  • the bleach-strengthening effect of the amines used according to the invention can be increased still further by adding suitable bleach activators and, if appropriate, additional bleach-stabilizing additives.
  • amines according to the invention in the bleaching or textile detergent compositions causes the effect of likewise enzymes present, for example proteases not or only very little is affected.
  • enzymes for example proteases not or only very little is affected.
  • Known bleach systems usually lead to one significant impairment of the effectiveness of enzymes.
  • R 1 NH - [(CR 3 R 4 ) m -NH] n -R 2 where n has an integer value from 0 to 20 and m has an integer value from 2 to 4, the radicals R 3 and R 4 are independently C 1-30 , preferably C 1
  • the secondary amine can be mono- or bis- ⁇ -branched.
  • a bis- ⁇ -branched secondary amine can have the general formula (II) R 4 R 3 HC-HN-CHR 1 R 2 have, where the radicals R 1 , R 2 , R 3 and R 4 independently of one another have the meaning given above.
  • hydrocarbyl used in the description and claims is used describes hydrocarbon-based residues with the specified Number of carbon atoms, however, that can be pure hydrocarbon residues can also have substituents. Examples of expression Residues included “hydrocarbyl residues" are given below.
  • the R 1 radical can be a C 6-14 alkyl radical and the R 2 radical can be a C 1-30 alkyl radical, preferably R 2 is a C 1-20 alkyl radical, particularly preferably a C 1-10 alkyl radical, where the alkyl radicals can be straight-chain or branched.
  • the radical R 1 can be a C 6-14 alkenyl radical and the radical R 2- can be a C 2-30 alkenyl radical, preferably R 2 is a C 2-20 -, particularly preferably a C 2-10 alkenyl radical, the alkenyl radicals can be straight-chain or branched.
  • the R 2 radical can also be a C 5-18 cycloalkyl radical which can have branches, it being possible for a ring structure to be formed from five to eight carbon atoms.
  • the radical R 2 can be a C 7-18 aralkyl radical in which an aromatic radical is connected to the amine nitrogen atom via an alkyl group.
  • the radical R 2 can also be a C 7-18 heteroalkyl radical or a C 6-18 aryl radical or a C 3-18 heteroaryl radical, an aromatic radical being bonded directly to the amine nitrogen atom in the case of the latter compounds
  • the radicals R 1 and R 2 can also carry one or more, preferably none or one, substituents, such as hydroxyl groups, C 1-4 alkoxy radicals, amino groups, C 1-4 alkylamino radicals, (di-C 1-4 alkyl) amino radicals , Chlorine atoms, bromine atoms, nitro groups, cyano groups, C 1-4 thioalkyl radicals, C 1-4 sulfoalkyl radicals, carboxyl groups, sulfo groups, carboxy-C 1-4 alkyl radicals, carboxyamide radicals or phenyl, tolyl or benzyl radicals.
  • substituents such as hydroxyl groups, C 1-4 alkoxy radicals, amino groups, C 1-4 alkylamino radicals, (di-C 1-4 alkyl) amino radicals , Chlorine atoms, bromine atoms, nitro groups, cyano groups, C 1-4 thioalkyl radicals, C 1-4
  • the carbon chains of the radicals R 1 and R 2 can be interrupted by oxygen atoms, amino groups, C 1-4 alkylamino radicals, carbamide radicals, oxocarbonyl radicals or carbonyl radicals.
  • the radicals R 1 and R 2 can furthermore together form a cyclic radical, so that together with the amine nitrogen atom they form a cyclic structure.
  • the ring of the cyclic radical is preferably formed from 3 to 13, preferably 5 to 9, in particular 6 to 8 carbon atoms, which in turn can be substituted as described above.
  • Preferred cyclic amines are azacyclohexane, azacycloheptane, azacyclooctane, azacyclononane, azacyclodecane, azacycloundecane and azacyclododecane, which are optionally substituted by C 1-8 -alkyl radicals.
  • Other heteroatoms, such as oxygen or nitrogen atoms, can also be present in the ring structure.
  • aromatic, cycloaliphatic or heterocyclic radicals can also like the aliphatic radicals can be substituted by the aforementioned radicals.
  • the radicals R 1 and R 2 are hydrophobic radicals.
  • the R 2 radical is preferably a branched C 1-30 alkyl radical, preferably a C 1-20 alkyl radical, particularly preferably a C 1-10 alkyl radical, C 2-30 alkenyl radical, preferably a C 2-20 alkenyl radical , particularly preferably a C 2-10 alkenyl radical, a C 5-18 cycloalkyl radical, a C 7-18 aralkyl radical or a C 7-18 heteroaralkyl radical or a C 6-18 aryl radical or a C 3-18 -, preferably a C 6-18 heteroaryl radical.
  • the secondary amines are preferably substituted asymmetrically.
  • the radicals R 1 and R 2 are then different from one another, it being possible for each of the radicals R 1 and R 2 to have one of the structures described above.
  • the R 2 radical is preferably an optionally branched C 1-6 alkyl radical, a C 2-6 alkenyl radical, a C 5-8 cycloalkyl radical, a C 7-9 aralkyl radical or C 7-9 heteroaralkyl radical or a C. 6-10 aryl or C 3-6 heteroaryl.
  • the radical R 1 is preferably a C 6-14 hydrocarbyl radical or hydroxycarbyl radical, which preferably has no or one branch, and the radical R 2 or hydrocarbyl radical is a C 1-5 hydrocarbyl radical, preferably a methyl radical, and n has the value zero.
  • the radical R 1 can in particular have 7 to 11 carbon atoms.
  • radicals R 1 and R 2 can be further substituted in accordance with one embodiment of the invention, as described above.
  • Examples of preferred amines are N-hexyl-N-methylamine, N-heptyl-N-methylamine, N-octyl-N-methylamine, N-nonyl-N-methylamine, N-decyl-N-methylamine, N-dodecyl-N-methylamine, N-tridecyl-N-methylamine, N-tetradecyl-N-methylamine, N-benzyl-N-methylamine, N-phenylethyl-N-methylamine, N-phenylpropyl-N-methylamine, which each have linear or branched hydrocarbon radicals can, as well as the corresponding N-alkyl-N-ethylamine, N-alkyl-N-hydroxyethylamine, N-alkyl-N-propylamine, N-alkyl-N-hydroxypropylamine, N-alkyl-N-isopropylamine, N-alkyl-N-butylamines and N
  • the radicals R 1 and R 2 on the secondary nitrogen atom can give a cyclic structure.
  • the secondary amines are compounds of the general formula (III) where p and q independently have an integer value from 0 to 4, preferably 0, 1 or 2,
  • X is a C 1-8 , preferably C 1-4 alkylene radical which can be interrupted by O, S, -OC (O) -, NR or -NR-C (O) -, where R is a C 1- 8 -, preferably a C 1-4 alkyl radical, or X is a C 2-8 , preferably C 2-4 alkenylene radical,
  • Y is a C 1-8 , preferably C 1-4 alkylene radical which can be interrupted by O, S, -OC (O) -, -NR-C (O) -, or Y is a C 2-8 , preferably C 2-4 alkenylene, O, S, -OC (O) -, NR or -NR-C (III)
  • X and Y can together form a CC double bond, provided that p + q has a value of at least 2.
  • One or more hydrogen atoms bonded to carbon can be replaced by C 1-10 , preferably C 1-4 , in particular C 1 hydrocarbyl radicals.
  • the bridgehead carbon atoms in particular can carry these hydrocarbyl radicals.
  • one or more points rings through two hydrogen atoms on adjacent ring carbon atoms a C-C bond must be replaced, so that at this point a C-C double bond is trained.
  • X and Y are independently C 1-8 alkylene radicals, each having a C atom of X and Y via a CC single bond or via a C 1-8 -, preferably C 1-4 -, in particular C 1 -alkylene radical or a C 2-8 -, preferably C 2-4 -alkenylene radical are connected.
  • X and Y together can form an aromatic ring, preferably one form aromatic 6-ring if p + q has a value of at least 2.
  • p, q, X, Y are chosen such that each ring present in the molecule has at least 5 ring atoms.
  • the secondary amines have of the formula (III) in the ring structure 5 to 20, preferably 6 to 14, particularly preferably 7 to 12 carbon atoms.
  • one or more, preferably 1 to 5, in particular 1 to 3, hydrogen atoms bonded to carbon in the general formula (III) are replaced by C 1-10 , preferably C 1-4 , in particular C 1 hydrocarbyl radicals .
  • These hydrogen atoms can also be replaced by C 1-10 , preferably C 1-4 , in particular C 1 alkyl radicals, which can be straight-chain or branched, by C 1-10 , preferably C 1-4 , in particular C 1 Alkoxy radicals, C 6-12 , preferably C 6-8 aryl radicals or C 6-12 , preferably C 6-8 aralkyl radicals.
  • Particularly preferred substituents are methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl and tert-butyl residues, especially methyl residues.
  • At least one ring is in the general formula (III) unsaturated.
  • the total number is Ring carbon atoms according to an embodiment of the invention 5 to 20, preferably 6 to 14, particularly preferably 7 to 12 carbon atoms.
  • the amines are of the formula (III) benzo-fused amines with 5 to 20, preferably 6 to 14, particularly preferably 7 to 12 ring carbon atoms.
  • the secondary amines of the formula (III) are cyclic, bicyclic or oligocyclic amines.
  • p + q has the value 0 to 4, preferably 0 to 2
  • X and Y have a total of 3 to 12, preferably 3 to 6 carbon atoms.
  • p and q have the value 0 and each of the radicals X and Y is independently a C 2-6 , preferably C 2-4 alkylene radical.
  • the sum of the carbon atoms of the radicals X and Y is preferably 4 to 6.
  • At least one of the radicals X and Y can be an alkenylene radical, that is to say have a double bond.
  • p + q has the value 2 to 6, preferably 2, 3 or 4, and the radicals X and Y together form one aromatic radical, preferably a benzene nucleus.
  • p + q has the value 2 to 7, preferably 2, 3 or 4, and X and Y together form a C-C double bond.
  • p has the value 0 and q has the value Value 1 on.
  • p has the value 1 and q has the value Value 1 on.
  • p has the value 0 and q has the value 1
  • the radical X is an oxygen or sulfur atom
  • the radical Y is a C 2-6 -, preferably C 2-4 -, in particular C 2-3 -Alkylene or -alkenylene radical which can be interrupted by O, S, -OC (O) -, -NR-C (O) -, with the above meaning for R.
  • the secondary amines have the general formula (IV).
  • X are independently C 1-8 , preferably C 3-4 alkylene, C 2-8 , preferably C 3-4 alkenylene or form an aromatic ring, especially an aromatic C 6 ring (benzene ring).
  • Y is a C 1-8 -, preferably C 1-4 -, in particular C 1-2 -alkylene radical, C 2-8 -, preferably C 2-4 -, in particular C 2 -alkenylene radical, O, S or a CC- single bond.
  • X and Y can be interrupted as described for formula (III).
  • both radicals X form aromatic C 6 nuclei and Y is an oxygen atom, sulfur atom or a methylene radical.
  • One or more hydrogen atoms bonded to carbon can pass through Substituents can be replaced, as described above for the compounds of Formula (III) are listed.
  • bicyclic secondary amines are azabicyclo [2.2.1] heptanes, Azabicyclo [2.2.2] octanes, azabicyclo [3.2.1] octanes, azabicyclo [3.3.0] octanes, Azabicyclo [3.2.2] nonanes, azabicyclo [3.3.1] nonanes, azabicyclo [4.2.1] nonanes, Azabicyclo [4.2.2] decane, Azabicyclo [4.3.1] decane, where the nitrogen atom at every position of the bridges, but not in the Bridgehead position can be present.
  • the secondary amino group is located thus in the ring structure. 1,3,3-Trimethyl-6-azabicyclo [3.2.1] octane are preferred and 3-azabicyclo [3.2.2] nonane.
  • the total number is Carbon atoms in the cyclic, bicyclic or oligocyclic secondary Amine 5 to 40, preferably 6 to 30, in particular 7 to 20 carbon atoms.
  • Amines can be even more effective than bleach boosters than the acyclic amines.
  • the preparation of the secondary amines used according to the invention is known. You can, for example, by reductive amination of aldehydes or by amination of nitriles. Cyclic amines can moreover by reducing the corresponding lactams and bicyclic Amines can be produced by Diels-Alder reactions.
  • the preferably cyclic, bicyclic or oligocyclic secondary amine can be used as a free amine in detergent and cleaning agent formulations become. It can also be present as an ammonium salt, the Anion, for example, a tosylate, sulfate, chloride, bromide or an anion an inorganic or organic acid.
  • the anion should be stable to oxidation.
  • suitable inorganic acids for the formation of the anion are sulfuric acid, phosphoric acid, polyphosphoric acid, boric acid and hydrochloric acid.
  • suitable anions are silicate and aluminosilicate anions.
  • suitable organic acids are carboxylic acids, such as C 1-25 monocarboxylic acids, C 2-25 dicarboxylic acids, C 6-25 tricarboxylic acids, butanetetracarboxylic acid, polycarboxylic acids, such as polyacrylic acid, polymaleic acid, copolymers and terpolymers of acrylic acid and maleic acid with other monomers, Sulfonic acids, such as C 1-25 alkyl, aralkyl and aryl sulfonic acids, phosphonic acids, such as C 1-25 alkyl, aralkyl and arylphosphonic acids, and C 1-25 aminophosphonic acids with 1 to 4 tertiary amino groups and 1 to 6 phosphonic acid groups ,
  • An example of a salt of secondary amine and a polycarboxylic acid is the salt of the amine with the acrylic acid / maleic acid copolymer Sokalan® CP 45 from BASF AG, the cations Na + and H + usually contained in the polycarboxylate being
  • the secondary amine is preferably used in the form of a salt. Salts with such anions are particularly preferably used here are usually contained in detergents or bleaches.
  • the secondary amines used according to the invention are used as bleach boosters or bleach catalysts in bleach or laundry detergent compositions used according to an embodiment of the invention based on active oxygen. It can be inorganic and / or organic peracids (percarboxylic acids) and / or peroxy compounds act in combination with the invention, in particular secondary, amine especially for lipophilic and / or lipophobic soiling and a stronger bleaching effect at low temperatures show than without the combination with the amines.
  • alkali perborates or alkali carbonate perhydrates examples are alkali perborates or alkali carbonate perhydrates, in particular the sodium salts.
  • peracetic acid which preferably in commercial textile washing or commercial Cleaning is used.
  • Bleach or textile detergent compositions which can be used advantageously contain C 1-12 -percarboxylic acids, C 8-16 -dipercarboxylic acids, imidopercaproic acids or aryldipercaproic acids.
  • Preferred examples of usable acids are peracetic acid, linear or branched octanoic, nonanoic, decanoic or dodecane monoperacids, decanoic and dodecanediperic acid, mono- and diperphthalic acids, isophthalic acids and terephthalic acids, phthalimidopercaproic acid (PAP) and terephthaloyldiamidopercaproic acid (PAP).
  • Polymeric peracids can also be used, for example those which contain basic acrylic acid units in which a peroxy function is present.
  • the percarboxylic acids can be used as free acids or as salts of the acids, preferably alkali or alkaline earth metal salts can be used.
  • the bleach or fabric detergent compositions are preferred especially for bleaching textiles, especially soiled textiles preferably with hydrophobic or lipophilic stains such as Chlorophyll from green parts of plants (spinach, grass, leaves) or carotene Vegetable plants (carrots, tomatoes, peppers) used. According to one Embodiment they are preferred for bleaching lipophobic / hydrophilic Soiling, like tea used.
  • the bleaching power amplification according to the invention by using the inventive especially secondary, amines are particularly effective at Use in activated bleach or fabric detergent compositions.
  • the secondary amine is used in combination with a Bleach activator and an active oxygen-releasing peroxy compound used.
  • the bleaching effect achieved here exceeds that of an amine-free one activated bleach composition, especially for lipophilic stains such as chlorophyll or carotene and / or lipophobic soiling like tea.
  • the secondary amines used according to the invention can be used together with other suitable bleaching catalysts become.
  • Examples are quaternized imines and sulfonimines, as for example in US 5 360 568, US 5 360 569 and EP-A-0 453 003 are described, as are manganese complexes, such as, for example are described in WO-A 94/21777.
  • Other usable metal-containing Bleaching catalysts are in EP-A-0 458 397, EP-A-0 458 398, EP-A-0 549 272.
  • Another class of substances that can be used are the acyloxybenzenesulfonic acids and their alkali metal and alkaline earth metal salts, it being possible to use C 1-14 -acyl radicals.
  • Acetyl, propionyl, octanoyl, nonanoyl and benzoyl residues are preferred, in particular acetyl residues and nonanoyl residues.
  • Particularly suitable bleach activators of this class of substances are acetyloxybenzenesulfonic acid, benzoyloxybenzenesulfonic acid and nonanoyloxybenzenesulfonic acid (NOBS) or isononanoyloxybenzenesulfonic acid (isoNOBS). They are preferably used in the form of their sodium salts.
  • O-acyl oxime esters such as O-acetylacetone oxime, O-benzoylacetone oxime, Bis (propylimino) carbonate, bis (cyclohexylimino) carbonate.
  • Acylated oximes which can be used according to the invention are, for example, in EP-A-0 028 432.
  • Oxime esters which can be used according to the invention are, for example in EP-A-0 267 046.
  • N-Acylcaprolactams such as N-acetylcaprolactam
  • N-benzoyl caprolactam N-octanoyl caprolactam
  • carbonyl biscaprolactam N-Acylcaprolactams
  • 2-alkyl- or 2-aryl- (4H) -3,1-benzoxazin-4-ones such as they are described, for example, in EP-B1-0 332 294 and EP-B 0 502 013 are.
  • 2-phenyl- (4H) -3,1-benzoxazin-4-one and 2-methyl- (4H) -3,1-benzoxazin-4-one are usable.
  • cationic nitriles such as those in EP 303 520 and EP 458 396 A1 can be used.
  • Cation nitriles are the methosulfates or tosylates of trimethylammonium acetonitrile, N, N-dimethyl-N-octylammonium acetonitrile, 2- (trimethylammonium) propionitrile, 2- (trimethylammonium) -2-methyl-propionitrile.
  • the methosulfates of N-methylpiperazinium-N, N'-diacetonitrile are suitable and N-methylmorpholinium acetonitrile (MMA).
  • the bleach activators which can be used according to the invention are preferably included Room temperature in a solid physical state because of intensive contact of the amine with the bleach activator before use for achieving the optimal bleaching effect can be disadvantageous.
  • suitable crystalline bleach activators are tetraacetylethylenediamine (TAED), NOBS, isoNOBS, carbonyl biscaprolactam (CBC), benzoyl caprolactam, bis (2-propylimino) carbonate, Bis (cyclohexylimino) carbonate, O-benzoylacetone oxime and 2-phenyl- (4H) -3,1-benzoxazin-4-one, anthranil, phenylanthranil N-methylmorpholinium acetonitrile, N-octanoylcaprolactam (OCL) and N-methylpiperazine-N, N'-diacetonitrile as well as liquid or poorly crystallizing bleach activators in a form made up as a solid product.
  • the Bleach or textile detergent compositions for example in Detergents and cleaning agents can be used, additionally one or more bleach stabilizers.
  • These are additives that Traces of heavy metals can adsorb, bind or complex.
  • Examples for additives which can be used according to the invention and have a bleach-stabilizing effect are polyanionic compounds such as polyphosphates, polycarboxylates, Polyhydroxypolycarboxylates, soluble silicates as complete or partial neutralized alkali or alkaline earth salts, especially as neutral Na or Mg salts, which are relatively weak bleach stabilizers.
  • Bleach stabilizers that can be used are, for example, complexing agents, such as ethylenediaminetetraacetate (EDTA), nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA), ⁇ -alaninediacetic acid (ADA), ethylenediamine-N, N'-disuccinate (EDDS) and phosphonates such as ethylenediaminetetramethylenephosphonate, Diethylene triamine pentamethylene phosphonate or hydroxyethylidene-1,1-diphosphonic acid in the form of the acids or as partial or complete neutralized alkali metal salts.
  • complexing agents such as ethylenediaminetetraacetate (EDTA), nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA), ⁇ -alaninediacetic acid (ADA), ethylenediamine-N, N'-disuccinate (EDDS) and phosphonates such as
  • the detergents according to the invention preferably contain at least one Bleach stabilizer, particularly preferably at least one of the strong ones mentioned above Bleach stabilizers.
  • the bleaching or Textile detergent compositions according to one embodiment of the invention almost all common components of washing, bleaching and cleaning agents contain. In this way you can, for example, build funds that are especially suitable for textile treatment at low temperatures, and also those which in several temperature ranges up to the traditional range of Cottons are suitable.
  • the main components of textile detergents, bleaches and cleaning agents are, in addition to Bleaching agent composition consisting of bleaching agent, according to the invention, in particular secondary, amine and optionally bleach activator, builders (Builder), i.e. inorganic builders and / or organic cobuilders, and surfactants, especially anionic and / or nonionic surfactants.
  • builders i.e. inorganic builders and / or organic cobuilders
  • surfactants especially anionic and / or nonionic surfactants.
  • auxiliary substances and accompanying substances such as adjusting agents, complexing agents, Phosphonates, dyes, corrosion inhibitors, graying inhibitors and / or Soil release polymers, color transfer inhibitors, bleach catalysts, Peroxide stabilizers, electrolytes, optical brighteners, enzymes, perfume oils, Foam regulators and activating substances are present in these agents when this is appropriate.
  • inorganic builder substances such as aluminosilicates, silicates, carbonates and phosphates.
  • Suitable inorganic builders are, for example, aluminosilicates with ion-exchanging Properties, like zeolites.
  • zeolites Different types are suitable, in particular zeolite A, X, B, P, MAP and HS in their Na form or in forms in which Na partly against other cations, such as Li, K, Ca, Mg or ammonium are exchanged.
  • Suitable zeolites are, for example, in EP-A038 591, EP-A 021 491, EP-A 087 035, US 4 604 224, GB-A2 013 259, EP-A 522 726, EP-A 384 070 and WO 94/24 251.
  • Suitable inorganic builders are, for example, amorphous or crystalline silicates like amorphous disilicates, crystalline disilicates like that Layered silicate SKS-6 (manufacturer Hoechst).
  • the silicates can be in the form of their Alkali, alkaline earth or ammonium salts are used. Preferably Na, Li and Mg silicates are used.
  • Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, such as C 9 to C 11 alcohol sulfates, C 12 to C 13 alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.
  • Suitable anionic surfactants are sulfated ethoxylated C 8 to C 22 alcohols (alkyl ether sulfates) or their soluble salts.
  • Compounds of this type are prepared, for example, by first alkoxylating a C 8 to C 22 , preferably a C 10 to C 18 alcohol, such as a fatty alcohol, and then sulfating the alkoxylation product.
  • Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 3 to 20, mol of ethylene oxide being used per mol of fatty alcohol.
  • the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide.
  • alkoxylated C 8 are suitable also - to C 22 alcohols, the ethylene oxide and propylene oxide or ethylene oxide and butylene oxide.
  • the alkoxylated C 8 to C 22 alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution.
  • alkane sulfonates such as C 8 to C 24 , preferably C 10 to C 18 alkane sulfonates, and soaps, such as the salts of C 8 to C 24 carboxylic acids.
  • anionic surfactants are C 9 to C 20 linear alkylbenzenesulfonates (LAS).
  • N-acyl sarcosinates with aliphatic saturated or unsaturated C 8 to C 25 acyl radicals, preferably C 10 to C 20 acyl radicals, for example N-oleoylsarcosinate.
  • the anionic surfactants are preferably added to the detergent in the form of salts added.
  • Suitable cations in these salts are alkali metal ions such as Sodium, potassium and lithium and ammonium ions, such as hydroxyethylammonium, Di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium ions.
  • Suitable nonionic surfactants are, for example, alkoxylated C 8 to C 22 alcohols, such as fatty alcohol alkoxylates or oxalcohol alkoxylates.
  • the alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as the surfactant.
  • block polymers of ethylene oxide, propylene oxide and / or butylene oxide or addition products are considered, which contain the alkylene oxides mentioned in a statistical distribution. 2 to 50, preferably 3 to 20, mol of at least one alkylene oxide are used per mole of alcohol.
  • Ethylene oxide is preferably used as the alkylene oxide.
  • the alcohols preferably have 10 to 18 carbon atoms.
  • nonionic surfactants are alkylphenol ethoxylates with C 6 - to C 14 -alkyl chains and 5 to 30 mol ethylene oxide units.
  • Nonionic surfactants are alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. This Compounds usually contain 1 to 20, preferably 1.1 to 5, glucoside units.
  • N-alkyl glucamides of the general structure IV or V wherein R 6 is C 6 to C 22 alkyl, R 7 H or C 1 to C 4 alkyl and R 8 is a polyhydroxyalkyl radical having 5 to 12 carbon atoms and at least 3 hydroxy groups.
  • R 6 is preferably C 10 to C 18 alkyl
  • R 7 is methyl
  • R 8 is a C 5 or C 6 radical.
  • such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C 10 -C 18 carboxylic acids.
  • the detergents according to the invention preferably contain C 10 -C 16 alcohols ethoxylated with 3-12 mol ethylene oxide, particularly preferably ethoxylated fatty alcohols as nonionic surfactants.
  • Suitable unsaturated C 4 -C 8 dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred.
  • Group (i) includes monoethylenically unsaturated C 3 -C 8 monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. From group (i), preference is given to using acrylic acid and methacrylic acid.
  • Group (ii) includes monoethylenically unsaturated C 2 -C 22 olefins, vinyl alkyl ethers with C 1 -C 8 alkyl groups, styrene, vinyl esters of C 1 -C 8 carboxylic acids, (meth) acrylamide and vinyl pyrrolidone. From group (ii), preference is given to using C 2 -C 6 olefins, vinyl alkyl ethers having C 1 -C 4 alkyl groups, vinyl acetate and vinyl propionate.
  • Group (iii) comprises (meth) acrylic esters of C 1 to C 8 alcohols, (meth) acrylonitrile, (meth) acrylamides of C 1 -C 8 amines, N-vinylformamide and vinylimidazole.
  • polymers of group (ii) contain vinyl esters in copolymerized form, can also partially or completely to vinyl alcohol structural units are hydrolyzed.
  • Suitable copolymers and terpolymers are, for example known from US 3 887 806 and DE-A 43 13 909.
  • Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates see US 5,227,446, DE-A-44 15 623, DE-A-43 13 909, are also suitable as organic cobuilders.
  • Suitable unsaturated carboxylic acids include maleic acid, Fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid, and mixtures of acrylic acid and maleic acid, which in Amounts of 40 to 95% by weight, based on the component to be grafted, be grafted on.
  • Suitable modifying monomers are those above mentioned monomers of groups (ii) and (iii).
  • Grafted mined or mined from this group are preferred reduced starches and grafted polyethylene oxides are used, with 20 to 80 % By weight of monomers, based on the graft component, in the Graft polymerization can be used.
  • a graft is preferably used Mixture of maleic acid and acrylic acid in a weight ratio of 90:10 to 10:90 inserted.
  • Polyglyoxylic acids suitable as organic cobuilders are, for example, in EP-B-001 004, US 5,399,286, DE-A-41 06 355 and EP-A-656 914.
  • the end groups of the polyglyoxylic acids can have different structures.
  • Polyamidocarboxylic acids suitable as organic cobuilders and modified Polyamidocarboxylic acids are for example from EP-A-454 126, EP-B-511 037, WO 94/01486 and EP-A-581 452.
  • Polyaspartic acid or cocondensates of aspartic acid with further amino acids, C 4 -C 25 mono- or dicarboxylic acids and / or C 4 -C 25 mono- or diamines are also preferably used as organic cobuilders.
  • Polyaspartic acids modified with C 6 -C 22 mono- or dicarboxylic acids or modified with C 6 -C 22 mono- or diamines are particularly preferably used.
  • Suitable condensation products of citric acid as organic cobuilders Hydroxycarboxylic acids or polyhydroxy compounds are for example from WO 93/22362 and WO 92/16493 are known.
  • Such carboxyl groups containing condensates usually have molecular weights of up to 10,000, preferably up to 5,000.
  • polyesters are known, for example from US 3,557,039, GB-A 1 154 730, EP-A-185 427, EP-A-241 984, EP-A-241 985, EP-A-272 033 and US 5,142,020.
  • soil release polymers are amphiphilic graft or Copolymers of vinyl and / or acrylic esters on polyalkylene oxides (see US 4,746,456, US 4,846,995, DE-A-37 11 299, US 4,904,408, US 4,846,994 and US 4,849,126) or modified celluloses, such as methyl cellulose, Hydroxypropyl cellulose or carboxymethyl cellulose.
  • color transfer inhibitors are homopolymers and copolymers of vinyl pyrrolidone, vinyl imidazole, vinyl oxazolidone and of 4-vinylpyridine-N-oxide with molecular weights from 15,000 to 100,000 and crosslinked fine-particle polymers based on these monomers.
  • the use of such polymers mentioned here is known, see DE-B-22 32 353, DE-A-28 14 287, DE-A-28 14 329 and DE-A-43 16 023.
  • the at least one secondary amine-containing bleaching agent compositions in enzyme-containing Detergents and cleaning agents used.
  • the enzymes show in many cases a bleaching agent supporting and their effect enhancing effect that when using the invention Bleaching compositions is particularly pronounced.
  • suitable Enzymes are, for example, proteases, amylases, lipases and cellulases, especially proteases. Several enzymes can be combined be used.
  • the bleaching agent compositions according to the invention impair which contain at least one secondary amine, the effect in particular primary washing action, the enzymes not or only very slightly.
  • Known bleaching compositions on the other hand, often show one enzyme-damaging effect, which increases the effectiveness or activity of Enzymes is reduced. In the bleaching compositions according to the invention this enzyme damage can be avoided and a high Enzyme activity can be achieved. This is especially true when using cyclic, bicyclic or oligocyclic secondary amines the case.
  • the bleaching compositions which can be used according to the invention are household also in the field of commercial textile washing and cleaning used.
  • peracetic acid is used as a bleaching agent in this application used, which is added to the wash liquor as an aqueous solution.
  • the secondary amine used according to the invention can be used either separately as a single component in the washing or cleaning process added or mixed together with other feedstocks in advance and then added together.
  • the claimed amines are preferably in Textile detergent compositions used that have at least one bleach and at least one bleach activator, preferably solid at room temperature and optionally a bleach stabilizer and optionally others Bleach catalysts included.
  • the amines to be used according to the invention are preferably in powder or granular detergents used. It can be classic heavy-duty detergents or concentrated or compacted detergents act.
  • Inorganic builders preferably used in detergents Sodium carbonate, sodium hydrogen carbonate, zeolite A and P as well as amorphous and crystalline sodium silicates.
  • Organic cobuilders preferably used in detergents Acrylic acid / maleic acid copolymers, acrylic acid / maleic acid / vinyl ester terpolymers and citric acid.
  • Inorganic bleaching agents preferably used in detergents are sodium perborate and sodium carbonate perhydrate.
  • Inorganic surfactants preferably used in detergents Fatty alcohol sulfates, linear alkyl benzene sulfonates (LAS) and soaps, the proportion of LAS is preferably below 8% by weight, particularly preferably below 4% by weight.
  • Nonionic surfactants preferably used in detergents are C 11 - to C 17 -oxoalcohol ethoxylates with 3-13 ethylene oxide units, C 10 - to C 16 -fatty alcohol ethoxylates with 3-13 ethylene oxide units and additionally ethoxylated with 1-4 propylene oxide or butylene oxide units Fat or oxo alcohols.
  • the claimed amines are preferred in Textile detergent compositions used that have at least one enzyme contain.
  • Enzymes preferably used in detergents are protease, lipase and cellulase, particularly preferred is protease.
  • suitable Proteases are, for example, Savinase, Desazym and Esperase (manufacturer Novo Nordisk).
  • a suitable lipase is, for example, Lipolase (manufacturer Novo Nordisk).
  • a suitable cellulase is, for example, Celluzym (manufacturer Novo Nordisk).
  • Graying inhibitors and soil release polymers preferably used in detergents are graft polymers of vinyl acetate on polyethylene oxide of molecular weight 2,500-8,000 in a weight ratio of 1.2: 1 to 3.0: 1, Polyethylene terephthalate / oxyethylene terephthalate with a molecular weight of 3,000 to 25,000 from polyethylene oxides with a molecular weight of 750 to 5,000 with terephthalic acid and Ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate from 8: 1 to 1: 1 and block polycondensates according to DE-A-44 03 866.
  • Color transfer inhibitors preferably used in detergents are soluble Vinyl pyrrolidone and vinyl imidazole copolymers with molecular weights above 25,000 as well finely divided crosslinked polymers based on vinylimidazole.
  • the powdered or granular detergents according to the invention can contain up to Contain 60% by weight of inorganic adjusting agents. Usually this is done Sodium sulfate used.
  • the detergents according to the invention are preferably but low in adjusting agents and contain only up to 20% by weight, particularly preferred only up to 8% by weight of adjusting agents.
  • the detergents according to the invention can have different bulk densities Range from 300 to 1,200, in particular 500 to 950 g / l. modern Compact detergents usually have high bulk densities and show one Granular structure.
  • the bleaching compositions for textile washing also means considered as additives to peroxide-containing or peroxide-free detergents be applied.
  • They essentially contain the Bleach composition, consisting of bleach, secondary amine and optionally bleach activator, and optionally further auxiliaries and additives, in particular stabilizers, pH regulators, thickeners and Surfactants.
  • the textile detergent composition is essentially free of phosphate.
  • this is the invention Textile detergent essentially free of linear alkylbenzenesulfonates and preferably based on fatty alcohol sulfonates.
  • the textile detergent composition according to the invention contains at least one polycarboxylate, preferably in an amount of 0.1 to 7.5% by weight.
  • the invention also relates to the use of a bleach or textile detergent composition for removing hydrophobic and / or hydrophilic stains on textiles.
  • washing operations were carried out in a Launder-O-meter, type Atlas Standard under the following conditions: washing conditions device Launder-O-meter cycles 1 duration 30 min temperatures 22 ° C, 38 ° C and 60 ° C water hardness 3.0 mmol / l Test fabric 2.5 g test fabric with chlorophyll soiling (WFK: CFTAS-4) additionally 4 ⁇ 2.5 g cotton balast fabric amount of liquor 250 ml liquor ratio 1:20 laundry detergent III and IV from Table 1 using the activator specified in Table 3 or the percarboxylic acid specified in Table 4 and using the amines specified in Table 3 and 4 instead of N-methyl-N-octylamine detergent concentration 4.5 g / l
  • the bleaching effect of the detergent composition was determined by measuring the color strength of the test fabrics. This measurement was carried out photometrically. The reflectance values measured at the individual test tissues at 18 wavelengths in the range from 400 to 700 nm at a distance of 20 nm were converted according to the method described in A. Kud, Seifen, ⁇ le, Fette, Wachsen 119 , pp. 590-594 (1993) the respective color strengths of the test soils before and after washing are determined and the absolute bleaching effect A abs is calculated in%.
  • the amount of the secondary amine used was as follows Examples 0.5% by weight. There were also comparative tests carried out without the use of a secondary amine and without use a bleach activator and a secondary amine, and using amines not according to the invention (experiments with nonylamine and N-octyl-N, N-dimethylamine).
  • the examples show that the use of secondary according to the invention Amines as bleach boosters to bleach compositions or Detergent and detergent compositions performs an essential show improved bleaching effect.
  • the bleaching compositions according to the invention are in a wide variety of technical applications can be used, especially those in which a low Temperature, preferably a maximum of 40 ° C, a bleaching effect can be achieved should.
  • Successful bleaching is especially important when bleaching is difficult
  • Soiling such as lipophilic compounds, for example chlorophyll stains (Chlorophyll) or carotene spots, attainable as well for lipophobic soiling, such as tea.
  • Soiling such as lipophilic compounds, for example chlorophyll stains (Chlorophyll) or carotene spots, attainable as well for lipophobic soiling, such as tea.
  • the secondary amines according to the invention as bleach boosters the effectiveness of many bleaching compositions increase significantly.

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Claims (18)

  1. Mise en oeuvre des composés à faible masse moléculaire polymères ou oligomères comportant des groupes amine secondaires -NHR1, composés de formule générale (I) R1NH-[(CR3R4)m-NH]n-R2 dans laquelle n représente un nombre entier compris entre 0 et 20, et m représente un nombre entier compris entre 2 et 4, les restes R3 et R4 représentent, indépendamment l'un de l'autre, un reste hydrocarbyle en C1 à C30, de préférence en C1 à C15, et le reste R1 représente un reste hydrocarbyle en C6 à C14, et le reste R2 représente, indépendamment de R1, un reste hydrocarbyle en C1 à C30, ou bien R1 et R2 forment, éventuellement conjointement, un reste cyclique,
    ou de leurs sels, en tant que renforçateur de pouvoir de blanchiment pour compositions d'agents de blanchiment et de détergents textiles.
  2. Mise en oeuvre selon la revendication 1, dans laquelle l'amine secondaire est présente sous forme de sel d'ammonium, et l'anion est le tosylate, le sulfate, le chlorure, le bromure, l'anion d'un acide inorganique ou organique.
  3. Mise en oeuvre des composés de formule générale (III)
    Figure 00710001
    dans laquelle p et q représentent, indépendamment l'un de l'autre, un nombre entier compris entre 0 et 4, de préférence 0, 1 ou 2,
    X représente un reste alkyle en C1 à C8 qui est éventuellement interrompu par un atome de O, de S, un reste -O-C(O)-, N-R ou -NR-C(O)-, lesquels R représente un reste alkyle en C1 à C8, ou
    X représente un reste alcényle en C2 à C8,
    Y représente un reste alkyle en C1 à C8 qui est éventuellement interrompu par un atome de O, de S, un reste -O-C(O)-, N-R ou -NR-C(O)-, ou
    Y représente un reste alcényle en C2 à C8, un atome de O, de
    S, un reste -O-C(O)- -NR-C(O)-, formule dans laquelle R représente un reste alkyle en C1 à C8, ou
    Y représente une liaison C-C simple,
    ou X et Y forment conjointement une liaison C-C double, à condition que p+q vaille au moins 2,
    ou un atome de carbone de X et un atome de carbone de Y sont liés par une liaison C-C simple ou bien par un reste alcène en C1 à C8 ou alcényle en C2 à C8, à condition que X et Y représentent des restes alkyle en C1 à C8,
    ou X et Y forment conjointement un cycle aromatique, à condition que p+q vaille au moins 2,
    un ou plusieurs atomes d'hydrogène liés à des atomes de carbone pouvant être remplacés par un reste hydrocarbyle, alcoxy en C1 à C10, aryle en C6 à C12 ou aralkyle en C6 à C12,
    ou des composés de formule générale (IV)
    Figure 00720001
    dans laquelle les X représentent, indépendamment l'un de l'autre, un reste alkyle en C1 à C8, alcényle en C2 à C8 ou un cycle aromatique, et
    Y représente un reste alkyle en C1 à C8, alcényle en C2 à C8, un atome de O, de S ou une liaison C-C simple,
    ou de leurs sels, en tant que renforçateur de pouvoir de blanchiment pour des compositions d'agents de blanchiment et de détergents textiles.
  4. Mise en oeuvre selon la revendication 1 ou 2, où, dans la formule (I), n vaut 0, le reste R1 représente un reste hydrocarbyle en C6 à C14 et le reste R2 représente un reste hydrocarbyle en C1 à C5.
  5. Mise en oeuvre selon l'une quelconque des revendications précédentes, lors de laquelle la composition de détergents textiles contient au moins un agent de blanchiment et au moins un activateur de blanchiment et éventuellement un stabilisant de blanchiment et éventuellement d'autres catalyseurs de blanchiment.
  6. Mise en oeuvre selon l'une quelconque des revendications précédentes, lors de laquelle la composition de détergents textiles contient au moins une enzyme.
  7. Mise en oeuvre selon l'une quelconque des revendications précédentes, pour le blanchiment de salissures hydrophobes sur des textiles.
  8. Mise en oeuvre selon l'une quelconque des revendications précédentes, lors de laquelle la température de blanchiment ou de lavage est de 40°C au maximum.
  9. Composition d'agents de blanchiment ou de détergents textiles contenant
    (a) des agents de blanchiment sous forme de composé peroxy et/ou d'acide percarboxylique, à raison de 0,5% à 40% en poids,
    (b) des activateurs de blanchiment à raison de 0 à 20% en poids, et
    (c) les amines secondaires telles que définies dans la revendication 4, à raison de 0,1% à 1,0% en poids.
  10. Composition d'agents de blanchiment ou de détergents textiles contenant
    (a) des agents de blanchiment sous forme de composé peroxy et/ou d'acide percarboxylique, à raison de 0,5% à 40% en poids,
    (b) au moins un activateur de blanchiment choisi dans le groupe formé par la tétraacétyléthylènediamine (TAED), le NOBS, l'isoNOBS, le carbonylbiscaprolactame, le benzoylcaprolactame, le bis(2-propylimino)carbonate, le bis(cyclohexylimino)carbonate, le O-benzoylacétonoxime et le 2-phényl-(4H)-3,1-benzoxazin-4-one, l'anthranile, le phénylanthranile, le N-méthylmorpholinium-acétonitrile, le N-méthylpipérazin-N,N'-diacétonitrile et le N-octanoylcaprolactame (OCL), à raison de 0,1% à 20% en poids, et
    (c) les amines secondaires telles que définies dans la revendication 3 ou 4, à raison de plus de 0,1% à moins de 1,0% en poids.
  11. Composition d'agents de blanchiment ou de détergents textiles contenant
    (a) des agents de blanchiment sous forme de composé peroxy et/ou d'acide percarboxylique, à raison de 0,5% à 40% en poids,
    (b) des activateurs de blanchiment à raison de 0 à 20% en poids, et
    (c) des amines secondaires de formule générale R1R2NH ou les sels d'ammonium correspondants, où le reste R1 représente un reste alkyle ou phénylalkyle présentant 7 à 12 atomes de C, et le reste R2 représente un groupe alkyle en C1 à C4.
  12. Composition d'agents de blanchiment ou de détergents textiles contenant
    (a) au moins un agent de blanchiment choisi dans le groupe formé par les perborates de sodium, les perhydrate de carbonate de sodium, les acides percarboxyliques en C1 à C12, les acides dipercarboxyliques en C8 à C16, les acides imidopercaproïques et les acides aryldipercaproïques, à raison de 0,5% à 40% en poids,
    (b) des activateurs de blanchiment à raison de 0 à 20% en poids, et
    (c) les amines secondaires telles que définies dans la revendication 3 ou 4, à raison de plus de 0,1% à moins de 1,0% en poids.
  13. Composition d'agents de blanchiment ou de détergents textiles contenant
    (a) des agents de blanchiment sous forme de composé peroxy et/ou d'acide percarboxylique, à raison de 0,5% à 40% en poids,
    (b) les activateurs de blanchiment à raison de 0 à 20% en poids, et
    (c) les amines secondaires telles que définies dans l'une quelconque des revendications 1 à 4, à raison de 0,1% à moins de 0,5% en poids.
  14. Composition d'agents de blanchiment ou de détergents textiles contenant
    (a) des agents de blanchiment sous forme de composé peroxy et/ou d'acide percarboxylique, à raison de 0,5% à 40% en poids,
    (b) au moins un activateur de blanchiment choisi dans le groupe formé par la tétraacétyléthylènediamine (TAED), le NOBS, l'isoNOBS, le carbonylbiscaprolactame, le benzoylcaprolactame, le bis(2-propylimino)carbonate, le bis(cyclohexylimino)carbonate, le O-benzoylacétonoxime et le 2-phényl-(4H)-3,1-benzoxazin-4-one, l'anthranile, le phénylanthranile, le N-méthylmorpholinium-acétonitrile, le N-méthylpipérazin-N,N'-diacétonitrile et le N-octanoylcaprolactame (OCL), à raison de 0,1% à 20% en poids, et
    (c) les amines secondaires telles que définies dans l'une quelconque des revendications 1 à 4, à raison de plus de 0,1% à moins de 0,5% en poids.
  15. Composition d'agents de blanchiment ou de détergents textiles contenant
    (a) au moins un agent de blanchiment choisi dans le groupe formé par le perborate de sodium, le perhydrate de carbonates de sodium, les acides percarboxyliques en C1 à C12, les acides dipercarboxyliques en C8 à C16, les acides imidopercaproïques et les acides aryldipercaproïques, à raison de 0,5% à 40% en poids,
    (b) des activateurs de blanchiment à raison de 0 à 20% en poids, et
    (c) les amines secondaires telles que définies dans l'une quelconque des revendications 2, 3 ou 4, à raison de plus de 0,1% à moins de 0,5% en poids.
  16. Composition d'agents de blanchiment ou de détergents textiles contenant
    (a) des agents de blanchiment sous forme de composé peroxy et/ou d'acide percarboxylique, à raison de 0,5% à 40% en poids,
    (b) des activateurs de blanchiment à raison de 0 à 20% en poids, et
    (c) les amines secondaires telles que définies dans la revendication 3, à raison de 0,01% à 5% en poids.
  17. Composition d'agents de blanchiment ou de détergents textiles selon d'une quelconque des revendications 8 à 16, contenant de plus une enzyme.
  18. Mise en oeuvre de la composition d'agents de blanchiment ou de détergents textiles selon l'une quelconque des revendications 9 à 17, pour l'élimination des salissures hydrophobes et/ou hydrophiles sur des textiles.
EP97914305A 1996-03-26 1997-03-25 Renfor ateur de pouvoir de blanchiment pour compositions d'agents de blanchiment et de detergents textiles Expired - Lifetime EP0892846B1 (fr)

Applications Claiming Priority (5)

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DE1996111992 DE19611992A1 (de) 1996-03-26 1996-03-26 Bleichkraftverstärker für Bleichmittel- und Textilwaschmittelzusammensetzungen
DE19611992 1996-03-26
DE19625908 1996-06-27
DE1996125908 DE19625908A1 (de) 1996-06-27 1996-06-27 Bleichkraftverstärker für Bleichmittel- und Textilwaschmittelzusammensetzungen
PCT/EP1997/001513 WO1997035950A1 (fr) 1996-03-26 1997-03-25 Renforçateur de pouvoir de blanchiment pour compositions d'agents de blanchiment et de detergents textiles

Publications (2)

Publication Number Publication Date
EP0892846A1 EP0892846A1 (fr) 1999-01-27
EP0892846B1 true EP0892846B1 (fr) 2002-10-23

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EP97914305A Expired - Lifetime EP0892846B1 (fr) 1996-03-26 1997-03-25 Renfor ateur de pouvoir de blanchiment pour compositions d'agents de blanchiment et de detergents textiles

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Country Link
US (2) US6130198A (fr)
EP (1) EP0892846B1 (fr)
JP (1) JP2000507294A (fr)
AT (1) ATE226624T1 (fr)
BR (1) BR9708383A (fr)
DE (1) DE59708566D1 (fr)
ES (1) ES2187764T3 (fr)
WO (1) WO1997035950A1 (fr)

Families Citing this family (8)

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Publication number Priority date Publication date Assignee Title
DE10020767B4 (de) * 2000-04-27 2008-12-04 Rudolf Weber Textilwaschmittel mit Niedrigtemperaturbleiche
US7008545B2 (en) * 2002-08-22 2006-03-07 Hercules Incorporated Synergistic biocidal mixtures
US20060231505A1 (en) * 2002-08-22 2006-10-19 Mayer Michael J Synergistic biocidal mixtures
US7504372B2 (en) * 2004-09-08 2009-03-17 Clariant Produkte (Deutschland) Gmbh Mixtures of bleaching agents
GB0502056D0 (en) * 2005-02-01 2005-03-09 Unilever Plc Modified sodium carbonate carrier meterial
US20080087390A1 (en) * 2006-10-11 2008-04-17 Fort James Corporation Multi-step pulp bleaching
GB0911428D0 (en) * 2009-07-02 2009-08-12 Reckitt Benckiser Nv Composition
CA2809858C (fr) * 2010-09-20 2019-11-12 Sirna Therapeutics, Inc. Nouveaux lipides cationiques de faible poids moleculaire pour l'administration d'oligonucleotides

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE129656C (fr) *
US3751222A (en) * 1971-12-13 1973-08-07 Colgate Palmolive Co A process of cleaning cloth
DE2301235C3 (de) * 1973-01-11 1982-01-28 Hoechst Ag, 6000 Frankfurt Oxidations-, Bleich- und Waschmittel
EP0026529B2 (fr) * 1979-09-29 1992-08-19 THE PROCTER & GAMBLE COMPANY Compositions détergentes
GB8421801D0 (en) * 1984-08-29 1984-10-03 Unilever Plc Detergent composition
WO1986007603A1 (fr) * 1985-06-22 1986-12-31 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage pour basses temperatures de lavage
IT1187723B (it) * 1985-08-01 1987-12-23 Montefluos Spa Composizione granulare contenente perborato attivato
US4762636A (en) * 1986-02-28 1988-08-09 Ciba-Geigy Corporation Process for the preparation of granules containing an active substance and to the use thereof as speckles for treating substrates
EP0315204A3 (fr) * 1987-11-04 1990-07-04 Lion Corporation Composition de blanchiment
EP0349153A3 (fr) * 1988-06-28 1990-03-14 The Clorox Company Système stabilisant les compositions liquides d'eau oxygénée et compositions stabilisées de cette manière
JPH06248295A (ja) * 1993-02-26 1994-09-06 Lion Corp 漂白性組成物
JPH07197097A (ja) * 1993-12-28 1995-08-01 Lion Corp 漂白剤組成物および漂白洗剤組成物
WO1995033035A1 (fr) * 1994-06-01 1995-12-07 The Procter & Gamble Company Compositions de detergents contenant un sarcosinate d'oleoyle
WO1996004244A1 (fr) * 1994-08-05 1996-02-15 Warwick International Group Limited Activateurs de blanchiment

Also Published As

Publication number Publication date
ES2187764T3 (es) 2003-06-16
BR9708383A (pt) 1999-08-03
JP2000507294A (ja) 2000-06-13
ATE226624T1 (de) 2002-11-15
US6413929B1 (en) 2002-07-02
EP0892846A1 (fr) 1999-01-27
DE59708566D1 (de) 2002-12-05
US6130198A (en) 2000-10-10
WO1997035950A1 (fr) 1997-10-02

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