EP0588622B2 - Bleichmittel - Google Patents

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Publication number
EP0588622B2
EP0588622B2 EP93307279A EP93307279A EP0588622B2 EP 0588622 B2 EP0588622 B2 EP 0588622B2 EP 93307279 A EP93307279 A EP 93307279A EP 93307279 A EP93307279 A EP 93307279A EP 0588622 B2 EP0588622 B2 EP 0588622B2
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EP
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Prior art keywords
peroxyacid
bleach
acid
sodium
norbornane
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EP93307279A
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English (en)
French (fr)
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EP0588622B1 (de
EP0588622A1 (de
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Anthony Henry Clements
John Richard Nicholson
Colin Watt Kerr
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds

Definitions

  • the present invention relates to the use of an organic peroxyacid for the bleaching of stains.
  • hydrophobic stains are frequently encountered and are often regarded as difficult to remove, e.g. collar and cuff stains, sweat and sebum.
  • a hydrophobic peroxyacid bleach is therefore highly desirable in order to counteract these types of stains.
  • One particular problem with hydrophobic peroxyacids is the dye damage they can cause on coloured fabrics, especially nylon, acetate and tri-acetate fabrics.
  • EP-A-267165 discloses peroxy acids which incorporate sulphone groups which are relatively polar and add hydrophilic character to the compounds which incorporate them. This document states (page 3 lines 3 to 5) that some sulphone peroxycarboxylic acids exhibit a low level of damage to dyes in coloured articles. Separately in this document (page 23 lines 50 and 51) it is stated that "the tendency to cause dye damage will vary but will usually be reduced by the presence of one or more sulphone groups". A variety of peroxycarboxylic acids are disclosed in this prior document, including some norbornyl compounds.
  • FR-A-2336393 and corresponding US-A-4134850 disclose bleaching using a peroxy acid in which a cyclohexane ring is substituted with one or more percarboxy groups and possibly one or more carboxy groups.
  • this invention provides use, as colour-care bleach in bleach or detergent compositions for the cleaning of fabrics, of an organic peroxyacid wherein the peroxyacid is a bi- or tri-cycloaliphatic compound which contains at least eight carbon atoms and is sufficiently hydrophobic that it has a log 10 P of 0.3 to 4.5 or of a precursor of a said peroxyacid convertible in situ into said peroxyacid.
  • the peroxyacid is a bi- or tri-cycloaliphatic compound which contains at least eight carbon atoms and is sufficiently hydrophobic that it has a log 10 P of 0.3 to 4.5 or of a precursor of a said peroxyacid convertible in situ into said peroxyacid.
  • the organic peroxyacid will not contain any sulphone group.
  • the smallest cross-sectional area may be measured by using molecular graphics that are drawn with the Chem-X system developed and distributed by Chemical Design Ltd, Oxford, England: The molecular dimensions in three orthogonal dimensions are measured, and the smallest cross-sectional area is the product of multiplying the two smallest values.
  • the cross-sectional areas of some molecules as measured by this method are shown in Table I of Example I.
  • the peroxyacids of the invention will have hydrophobocity expressed as log 10 P of from 0.3-4.5, wherein P represents the octanol-water partition coefficient. This can conveniently be a calculated value determined by using the Med Chem Programme from Pomona College Medicinal Chemistry Project, Seaver Chem. Lab., Claremont, California.
  • the upper limit of hydrophobicity is constrained by the need for solubility of the peroxyacid, and is set at a log 10 P of 4.5.
  • the lower limit is set at 0.3, preferably 1.0, and more preferably 1.5.
  • peroxyacids are dependent on the electrophilic reactivity, which is indicated by its pKa (the dissociation constant).
  • the peroxyacid of the invention has a pKa of from 7-9.
  • the pKa can be determined using the following method. Sodium hydroxide (0.001N or 0.01 molar) was added to 150 ml of peroxyacid solution (10 -4 to 10 -3 molar) and the pH plotted until a final pH of 10 was reached, The pKa value was calculated according to the method described in 'H.T.S. Britton "Hydrogen Ions" Vol. 1. Chapman and Hall, p. 217-218.
  • Preferred organic peroxyacids include bi- or tricycloaliphatic groups such as norbornyl and adamantyl groups in which there is at least one pair of rings which share more than two carbon atoms.
  • Such preferred peroxyacid compounds can be represented by the general formula: wherein:
  • a preferred ensemble within the group of bicycloaliphatic peroxyacid compounds is represented by the general formula: bicyclo [a.b.c] alkyl peroxyacid wherein:
  • bicyclo [2.2.1] heptane peroxyacid compounds having 1 to 3 CO 3 H groups substituted on the basic ring structure which is:
  • the side groups thereon may be independently chosen from -H, -CO 3 H, -CH 3 and -CH 2 CO 3 H, with the proviso that at least one -CO 3 group is present
  • the -CO 3 H peroxyacid groups may be attached to any of the positions in the molecule.
  • the following compounds in cis or trans, endo or exo, (+) or (-) form are particularly suitable for use in the present invention: 2-methylnorbornane-2-peroxyacid, norbornane-2-peroxyacid, 3-methylnorbornane-2-peroxyacid, 2-norbornane-peroxyaceticacid, norbornane-2,3-diperoxyacid, norbornane-1-peroxyacid and norbornane-2-peroxyacid.
  • a useful class within the group of tri-cycloaliphatic peroxyacids is that of adamantoic peroxyacids whose basic structure is: This is substituted with 1 to 3 -CO 3 H sidegroups, and other sidegroups are selected from -H, -OR, -Cl, -Br, -F, -NO 2 , -R, and -CONR 2 , R being selected from C 1 -C 4 alkyl or alkylene groups.
  • a preferred example of this class of adamantoic-peroxyacids is adamantoic-1-peroxyacid.
  • Peroxyacids of the invention cover a wide range of peroxyacid compounds having configurations of the side groups in the endo, exo, trans, cis, (+) and (-) forms and mixtures thereof in one molecule and use thereof in a composition.
  • the peroxyacids may be presented in the acid or salt form and they may be generated from a precursor in situ in a wash liquor.
  • suitable precursors are esters or amides of norbornane acids.
  • the peroxyacid according to the invention can be present in amounts of from 0.05-70%, preferably from 0.5-60%, more preferably from 0.7-55% and most preferably from 1-50% by weight of the composition.
  • peroxyacids as herein before described are colour-caring, i.e. colour-safe, or colour friendly.
  • a measure for this colour-safety is the rate of dye-damage.
  • dye damage is determined by way of the following method.
  • the difference in reflectance of coloured cloths before and after washing with a bleach, optionally with a detergent base, is determined. This is also determined without using bleach, optionally with a detergent base, as the control.
  • the difference in reflectances, measured at a wavelength of 640 nm using a Beckman Grating Spectrophotometer, is an indication of the dye damage that is caused by the bleach.
  • the stain bleaching performance was measured by determining the difference (Delta R460) in %reflectance of cloths at 460 nm before and after washing.
  • the dye damage caused by the peroxyacids according to the present invention can be less than 20%, more preferably less than 15%, most preferably less than 10%.
  • the bleaching composition will also contain a surfactant material.
  • the surface-active material may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof.
  • suitable actives are commercially available and are fully described in literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
  • Typical synthetic anionic surface-actives are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from 8 to 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher aryl radicals.
  • suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (C 8 -C 18 ) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (C 9 -C 20 ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 -C 15 ) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those esters of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and ammonium salts of sulphuric acid esters of higher (C 9 -C 18 ) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and ammonium salts of
  • the preferred anionic detergent compounds are sodium (C 10 -C 15 ) alkylbenzene sulphonates, sodium (C 16 -C 18 ) alkyl sulphates and sodium (C 16 -C 18 ) alkyl ether sulphates.
  • nonionic surface-active compounds which may be used, preferably together with the anionic surface-active compounds, include in particular the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C 6 -C 22 ) phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; the condensation products of aliphatic (C 8 -C 18 ) primary or secondary linear or branched alcohols with ethyleneoxide, generally 2-30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine.
  • alkylene oxides usually ethylene oxide
  • alkyl (C 6 -C 22 ) phenols generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule
  • condensation products of aliphatic (C 8 -C 18 ) primary or secondary linear or branched alcohols with ethyleneoxide generally 2-30 EO
  • nonionic surface-actives include alkyl polyglycosides, sugar esters, long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides.
  • Amounts of amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives.
  • soaps may also be incorporated in the compositions of the invention, preferably at a level of less than 25% by weight. They are particularly useful at low levels in binary (soap/anionic) or ternary mixtures together with nonionic or mixed synthetic anionic and nonionic compounds.
  • Soaps which are used are preferably the sodium, or, less desirably, potassium salts of saturated or unsaturated C 10 -C 24 fatty acids or mixtures thereof.
  • the amount of such soaps can be varied between 0.5% and 25% by weight, with lower amounts of 0.5% to 5% being generally sufficient for lather control. Amounts of soap between 2% and 20%, especially between 5% and 10%, are used to give a beneficial effect on detergency. This is particularly valuable in compositions used in hard water when the soap acts as a supplementary builder.
  • the surfactant is present in an amount of from 0.4 to 80.0%, preferably from 0.8 to 75%, more preferably from 1.0 to 70% by weight of the composition.
  • composition of the invention may also further and preferably contain:
  • the peroxyacids of the present invention may be used in combination with a peroxygen bleach or a precursor-peroxygen system. Combinations like these will result in the hydrophilic bleach bleaching the hydrophilic stains and the hydrophobic bleach the hydrophobic stains without substantially affecting the colours. Further, there is no need for washing twice to remove all stains.
  • the peroxygen compounds are normally compounds which are capable of yielding hydrogen peroxide in aqueous solution.
  • Hydrogen peroxide sources are well known in the art. They include the alkali metal peroxides, organic peroxides such as urea peroxide, and inorganic persalts, such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Mixtures of two or more such compounds may also be suitable.
  • Particularly preferred are sodium perborate tetrahydrate and, especially, sodium perborate monohydrate.
  • Sodium perborate monohydrate is preferred because of its higher active oxygen content.
  • Sodium percarbonate may also be preferred for environmental reasons.
  • Alkylhydroxy peroxides are another class of peroxygen compounds. Examples of these materials include cumene hydroperoxide and t-butyl hydroperoxide.
  • Organic peroxyacids may also be suitable for use herein as hydrophilic bleach.
  • All these peroxygen compounds may be utilized alone or in conjunction with a peroxyacid bleach precursor.
  • Peroxyacid bleach precursors are known and amply described in literature, such as in the GB Patents 836,988; 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 US Patents 1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.
  • peroxyacid bleach precursors Another useful class of peroxyacid bleach precursors is that of the quaternary ammonium substituted peroxyacid precursors as disclosed in US Patents 4,751,015 and 4,397,757, in EP-A-284292 and EP-A-331,229.
  • peroxyacid bleach precursors of this class are: 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphophenyl carbonate chloride - (SPCC); N-octyl,N,N-dimethyl-N10-carbophenoxy decyl ammonium chloride -(ODC); 3-(N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate; and N,N,N-trimethyl ammonium toluyloxy benzene sulphonate.
  • SPCC 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphophenyl carbonate chloride -
  • ODC N-octyl,N,N-dimethyl-N10-carbophenoxy decyl ammonium chloride -(ODC)
  • ODC N-octyl,N,N-dimethyl-N10-carboph
  • peroxyacid bleach precursors can be used in the present invention, though some may be more preferred than others.
  • the preferred classes are the esters, including acyl phenol sulphonates and acyl alkyl phenol sulphonates; acyl-amides; and the quaternary ammonium substituted peroxyacid precursors.
  • Highly preferred peroxyacid bleach precursors or activators include sodium-4-benzoyloxy benzene sulphonate (SBOBS); N,N,N',N'-tetraacetyl ethylene diamine (TAED); sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-benzoyloxy benzoate; SPCC trimethyl ammonium toluyloxy benzene sulphonate; penta acetyl glucose (PAG) and benzoyl tetracetyl glucose.
  • SBOBS sodium-4-benzoyloxy benzene sulphonate
  • TAED N,N,N',N'-tetraacetyl ethylene diamine
  • TAED sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate
  • sodium-4-methyl-3-benzoyloxy benzoate sodium-4-methyl-3-benzoyloxy benzoate
  • compositions may also additionally include a bleach catalyst such as the manganese-complexes and copper-ions as disclosed in EP-A-458,397/EP-A-458,938 and/or an organic bleach catalyst of the sulfonimine type as described in EP-A-446,982 and EP-A-453,002.
  • a bleach catalyst such as the manganese-complexes and copper-ions as disclosed in EP-A-458,397/EP-A-458,938 and/or an organic bleach catalyst of the sulfonimine type as described in EP-A-446,982 and EP-A-453,002.
  • proteolytic enzymes which are suitable for use in the present invention are normally solid, catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.
  • proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available and can be used in the composition of the present invention.
  • suitable proteolytic enzymes are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis, such as the commercially available subtilisins Maxatase®, as supplied by Gist-Brocades, N.V, Delft, Holland, and Alcalase®, as supplied by Novo Industri A/S, Copenhagen, Denmark.
  • protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available, e.g. from Novo Industri A/S under the registered trade names Esperase® and Savinase®.
  • Esperase® Novo Industri A/S under the registered trade names Esperase® and Savinase®.
  • the preparation of these and analogous enzymes is described in British Patent Specification 1,243,784.
  • proteases are pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, papain, bromelin, carboxypeptidases A and B, aminopeptidase and aspergillopeptidases A and B.
  • the amount of proteolytic enzymes normally used in the composition of the invention may range from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, depending upon their activity. They are generally incorporated in the form of granules, prills or "marumes" in an amount such that the final washing product has proteolytic activity of from about 2-20 Anson units per kilogram of final product.
  • enzymes such as cellulases, lipases, cellulases and amylases, may also be used in addition to proteolytic enzymes as desired.
  • Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
  • Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its water-soluble salts; the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid; and polyacetal carboxylates as disclosed in US patents 4,144,226 and 4,146,495.
  • alkali metal polyphosphates such as sodium tripolyphosphate
  • the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid and polyacetal carboxylates as disclosed in US patents 4,144,226 and 4,146,495.
  • precipitating builder materials examples include sodium orthophosphate, sodium carbonate and long-chain fatty acid soaps.
  • Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, such as Zeolite 4 A, zeolite B or P, zeolite X, and also zeolite MAP (maximum aluminium P) as described in EP-A-384,070 (Unilever).
  • zeolites are the best known representatives, such as Zeolite 4 A, zeolite B or P, zeolite X, and also zeolite MAP (maximum aluminium P) as described in EP-A-384,070 (Unilever).
  • compositions may contain any one of the organic or inorganic builder materials, such as sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl malonate, carboxymethyfoxy succinate and the water-insoluble crystalline or amorphous aluminosilicate builder materials, or mixtures thereof.
  • organic or inorganic builder materials such as sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl malonate, carboxymethyfoxy succinate and the water-insoluble crystalline or amorphous aluminosilicate builder materials, or mixtures thereof.
  • These builder materials may be present at a level of, for example, from 5 to 80% by weight, preferably from 10 to 60% by weight.
  • additives examples include lather boosters, such as alkanolamides, particularly the monoethanol amides derived from palmkernel fatty acids and coconut fatty acids, lather depressants, such as alkyl phosphates and silicones, anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers, stabilizers, such as the various organic phosphonates known under the Trade name "Dequest” and ethylene diamine tetraacetic acid, fabric softening agents, inorganic salts, such as sodium sulphate, and, usually present in very small amounts, fluorescent agents, perfumes, enzymes, such as proteases, cellulases, lipases and amylases, germicides, dye transfer inhibitors such as PVP and PVA and colourants.
  • lather boosters such as alkanolamides, particularly the monoethanol amides derived from palmkernel fatty acids and coconut fatty acids
  • lather depressants such as al
  • the peroxyacids can be used in a process of washing fabrics.
  • fabrics used herein includes fibres, textiles and fabrics of both animal and vegetable origins, synthetics and mixtures thereof, such as cottons, mercerised cotton, cellulosics, wool and other protein fibres, bast fibres, viscose, polyester, acrylic, nylon, tri-acetate and di-acetate.
  • the invention is of especial importance to coloured cotton, nylon and acetate fabrics.
  • the peroxyacids can be prepared in a number of ways, e.g. as described in the J. Chem. Soc. 1968, 1317, Tetrahedron 198, 36 , 1023 and in the J. Chem. Soc. Perkin Trans. II, 1986, 781 and in Tetrahedron 1985, 41 , 4237.
  • Dicyclopentadiene is heated with an ⁇ , ⁇ -unsaturated acid to 160°C in the presence of iron filings for several hours, and extracted into alkali.
  • ⁇ , ⁇ -unsaturated acid may for example be chosen Acrylic acid, Crotonic acid, Methacrylic acid, Fumaric acid, Maleic acid, Mesaconic acid and Itaconic acid. Acidification and extraction into chloroform allowed isolation of the substituted norborn-5-ene-2-carboxylic acid.
  • the unsaturation may be readily removed by hydrogenation over palladium-on-charcoal in absolute ethanol, giving the saturated acid.
  • the conversion of the acid to peroxyacid may be carried out using methanesulphonic acid as solvent in an ice bath.
  • High strength (85%) hydrogen peroxide (five fold excess per acid group) was added dropwise with temperature monitoring and the mixture was stirred at room temperature for several hours. Work-up yielded the peroxyacid, in most cases as a colourless oil, although norbornane-2-percarboxylic acid was a white solid.
  • the peroxyacid is preferably used in a detergent composition and may be presented in any product form such as powders, granules, pastes and liquids.
  • the peroxyacid can also be incorporated in detergent additive products.
  • Such additive products are intended to supplement or boost the performance of conventional detergent compositions and may contain any of the components of such compositions, although they will not comprise all of the components present in a fully formulated detergent composition.
  • the peroxyacid can be suitably incorporated in a product that can be used for direct application purposes.
  • the cross-sectional area can be calculated by determining the dimensions of the peroxyacid with molecular graphics that are drawn with the Chem-X system developed and distributed by Chemical Design Ltd Oxford, England. The area is obtained by multiplying the two smallest dimensions in perpendicular directions.
  • This example shows the excellent anti-dye-damaging results that are obtained with the peroxyacids according to the invention.
  • the dye damaging effects of n-pernonanoic acid and 2-norbornane peracetic acid were determined.
  • a detergent base (4 g/l) and Dequest 2041 (1 ml of 5.4% solution) were added to 450 ml of 18°FH water in a tergotometer thermostatted at 40°C.
  • Peroxyacid was added to give a concentration of 9.2x10 -4 mole/l.
  • the pH adjusted to the appropriate value (6 to 10).
  • Eight (5x5 cm) pieces of blue disperse dyed nylon (ca. 3 g) were added and washed at 100 rpm for 30 minutes. The cloths were rinsed thoroughly and dried. Reflectance measurements were performed on the cloths before and after washing and the % dye damage was determined.
  • n-pernonanoic acid with a smallest cross-sectional area of 22.0A 2 , a log P of 3.47 and pKa of 8.1, was compared with 2-norbornane peroxyacetic acid, a compound according to the present invention.
  • This example shows the superior anti-dye-damaging effect of 2-norbornane-peracetic acid in the pH range of 6-10.
  • Peradamantoic acid is the best performer. NBC is third best at a pH of 6 and second best at a pH of 9. At pH 9 there are only relatively small differences between the base control and perbenzoic and norbornane 2-peroxyacids. Peradamantoic acid comes through very strongly as being the best performer, with almost complete removal of the stain, both at pH 6 and 9.
  • the method as in example V was used in determining the tea stain bleaching effect of sterically hindered hydrophobic peroxyacids, the differences being that 3 replicates were used, the reflectance was measured before and after washing, tests were done over a pH range of from 6 to 10 and 4 g/l NSPA base powder was used.
  • This example shows that the bleaches according to the invention do not only show good dye damage performance, but good stain-bleaching performance as well.

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Claims (7)

  1. Verwendung einer organischen Peroxysäure als Farbpflegebleichmittel in Bleich- oder Waschmitteln zur Reinigung von Textilien, wobei die Peroxysäure eine bi- oder tricycloaliphatische Verbindung ist, die mindestens acht Kohlenstoffatome enthält, und ausreichend hydrophob ist, so daß sie einen Log10 P von 0,3 bis 4,5 aufweist, oder einer Vorstufe der Peroxysäure, die in situ in diese Peroxysäure umwandelbar ist.
  2. Verwendung einer Peroxysäure nach Anspruch 1, wobei die Peroxysäure ausgewählt ist aus der Gruppe, wiedergegeben durch die Grundformeln:
    Figure 00180001
       worin:
    W eine C1-C4-Alkylengruppe, eine direkte Bindung darstellt oder nicht vorliegt,
    jeder Rest X, Y eine C2-C4-Alkylengruppe darstellt und
    Z eine C1-C4-Alkylengruppe darstellt,
       wobei jeder Rest W, X, Y und Z gegebenenfalls (jedoch vorzugsweise nicht) olefinische Ungesättigtheit einschließt, wenn mindestens zwei Kohlenstoffatome enthalten sind; und
    Figure 00190001
    worin:
    P, Q, R, S, T, U = C1-C2-Alkylen oder eine direkte Bindung wiedergeben oder nicht vorliegen, mit der Maßgabe, daß nicht mehr als 2 Gruppen entweder direkte Bindungen wiedergeben oder nicht vorliegen,
    wobei das Bleichmittel mit 1 bis 3 Seitengruppen -CO3H oder RCO3H und anderen Seitengruppen, ausgewählt aus -H, -OR, - Cl, -Br, -F, -NO2, -R und -CONR2, worin R eine C1-C4-Alkyloder Alkylengruppe darstellt, substituiert ist.
  3. Verwendung einer Peroxysäure nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, daß die Peroxysäure ausgewählt ist aus Peradamantansäure, Norbornan-2-peroxysäure und Norbornan-1-peroxysäure.
  4. Verwendung einer Peroxysäure nach einem der vorstehenden Ansprüche, wobei die Peroxysäure einen pKa-Wert von 7 bis 9 aufweist.
  5. Verwendung einer Peroxysäure nach einem der vorstehenden Ansprüche, wobei die Peroxysäure keine Sulfongruppe enthält.
  6. Verwendung einer Peroxysäure nach einem der vorstehenden Ansprüche, wobei die Bleich- oder Waschmittelzusammensetzung weiterhin ein hydrophiles Bleichmittel oder eine Bleichmittelvorstufe davon umfaßt.
  7. Verwendung einer Peroxysäure nach einem der vorstehenden Ansprüche, wobei die Bleich- oder Waschmittelzusammensetzung umfaßt:
    0,4 bis 80 Gewichtsprozent von einem oder mehreren Tensiden
    5 bis 80 Gewichtsprozent Waschmittelbuilder und
    0,5 bis 60 Gewichtsprozent von mindestens einer der in einem der Ansprüche 1 bis 5 definierten Peroxysäuren.
EP93307279A 1992-09-16 1993-09-15 Bleichmittel Expired - Lifetime EP0588622B2 (de)

Priority Applications (1)

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EP93307279A EP0588622B2 (de) 1992-09-16 1993-09-15 Bleichmittel

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EP92308431 1992-09-16
EP92308431 1992-09-16
EP93307279A EP0588622B2 (de) 1992-09-16 1993-09-15 Bleichmittel

Publications (3)

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EP0588622A1 EP0588622A1 (de) 1994-03-23
EP0588622B1 EP0588622B1 (de) 1999-02-17
EP0588622B2 true EP0588622B2 (de) 2002-12-04

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4134850A (en) † 1975-12-23 1979-01-16 Interox Chemicals Limited Bleaching composition
EP0120591B1 (de) † 1983-02-23 1987-09-23 The Procter & Gamble Company Detergens-Ingredienzien und ihre Verwendung in Reinigungszusammensetzungen und Waschverfahren
EP0325289A1 (de) † 1988-01-20 1989-07-26 AUSIMONT S.p.A. Bleicher, die imidoaromatische Percarbonsäure enthalten
US4917811A (en) † 1988-09-20 1990-04-17 Lever Brothers Company Bleach compositions and process for making same
WO1990007501A1 (en) † 1988-12-24 1990-07-12 Interox Chemicals Limited Peroxycarboxylic acids
EP0435379A2 (de) † 1989-12-22 1991-07-03 Akzo Nobel N.V. Suspension, Beschichtung, Agglomerierung und Verwendung von Imidoperoxicarboxylsäuren

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3266352D1 (en) * 1981-06-22 1985-10-24 Procter & Gamble Mixed peroxyacid bleaches having improved bleaching power
EP0106584B2 (de) * 1982-09-30 1990-08-08 The Procter & Gamble Company Bleichmittelzusammensetzungen
ES2002615T3 (es) * 1986-11-03 1994-12-01 Monsanto Co Acidos sulfonaperoxicarboxilicos.
GB9012876D0 (en) * 1990-06-08 1990-08-01 Interox Chemicals Ltd Peroxycompounds
US5405413A (en) * 1993-06-24 1995-04-11 The Procter & Gamble Co. Bleaching compounds comprising acyl valerolactam bleach activators

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4134850A (en) † 1975-12-23 1979-01-16 Interox Chemicals Limited Bleaching composition
EP0120591B1 (de) † 1983-02-23 1987-09-23 The Procter & Gamble Company Detergens-Ingredienzien und ihre Verwendung in Reinigungszusammensetzungen und Waschverfahren
EP0325289A1 (de) † 1988-01-20 1989-07-26 AUSIMONT S.p.A. Bleicher, die imidoaromatische Percarbonsäure enthalten
US4917811A (en) † 1988-09-20 1990-04-17 Lever Brothers Company Bleach compositions and process for making same
WO1990007501A1 (en) † 1988-12-24 1990-07-12 Interox Chemicals Limited Peroxycarboxylic acids
EP0435379A2 (de) † 1989-12-22 1991-07-03 Akzo Nobel N.V. Suspension, Beschichtung, Agglomerierung und Verwendung von Imidoperoxicarboxylsäuren

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Development of a test to predict colour fading of cotton fabrics after multi-cycle laundering with a bleach-containing domestic detergent", Duncan Phillips et al., ISDC vol. 112, 1996, pp. 287-293 †

Also Published As

Publication number Publication date
EP0588622B1 (de) 1999-02-17
EP0588622A1 (de) 1994-03-23

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