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EP0350096A2 - Compositions détergentes de blanchiment - Google Patents

Compositions détergentes de blanchiment Download PDF

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Publication number
EP0350096A2
EP0350096A2 EP19890201690 EP89201690A EP0350096A2 EP 0350096 A2 EP0350096 A2 EP 0350096A2 EP 19890201690 EP19890201690 EP 19890201690 EP 89201690 A EP89201690 A EP 89201690A EP 0350096 A2 EP0350096 A2 EP 0350096A2
Authority
EP
European Patent Office
Prior art keywords
bleach
detergent composition
sodium
composition according
bleach activator
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19890201690
Other languages
German (de)
English (en)
Other versions
EP0350096A3 (fr
Inventor
David William Thornthwaite
David William Roberts
Peter Stanford Sims
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0350096A2 publication Critical patent/EP0350096A2/fr
Publication of EP0350096A3 publication Critical patent/EP0350096A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3915—Sulfur-containing compounds

Definitions

  • This invention relates to the field of bleaching detergent compositions, and in particular to the so-­called low-temperature bleaching detergent compositions of the type wherein, during use, the bleach system functions by the generation of organic peroxyacids.
  • Such compositions essentially comprise a peroxide compound, e.g. a persalt, such as sodium perborate, and an organic compound (the so-called “bleach activator” or “bleach precursor”), which in solution can react at relatively low temperatures with the peroxide compound to form an organic peroxyacid, which, unlike the peroxide compound, is effective in bleaching at lower temperatures, e.g. ⁇ 60°C, such as are encountered in domestic washing and laundering operations.
  • compositions when used for fabric washing, also contain enzymes, especially proteolytic enzymes (proteases), which aid in the removal of proteolytic stains.
  • proteolytic enzymes proteolytic enzymes
  • peroxide compound is used here to indicate those percompounds which liberate active oxygen in solution, particularly the inorganic peroxide compounds, such as the alkali metal perborates, persilicates, percarbonates and perphosphates.
  • Bleaching detergent compositions containing such inorganic peroxide compounds and organic bleach activators therefor are known in the art.
  • Various substances have been proposed in the art as bleach activators or precursors. Generally, these are carboxylic acid derivatives, e.g.
  • esters such as those described in GB Patent Specifications 836,988 and 970,950
  • acyl amides such as those described in GB Patent Specifications 907,356; 855,735; 1,246,339 and US Patent Specification 4,128,49
  • acyl azoles such as those described in Canadian Patent Specification 844,481).
  • Other, more recent patent publications disclosing bleach activators are, for example, US Patent 4,283,301; US Patent 4,412,934 and EP-A-0120591.
  • Typical bleach activators within the concept of the aforedescribed patent publications are N,N,N′,N′-­tetraacetyl ethylene diamine (TAED), sodium acetoxy benzene sulphonate (SABS), sodium benzoyloxy benzene sulphonate (SBBS), sodium n- and iso-nonanoyloxy benzene sulphonate (SNOBS and iso-SNOBS).
  • diacyloxy benzene sulphonates as defined hereinafter, when added to aqueous liquors containing a source of alkaline hydrogen peroxide, provide a very effective bleaching of oxidizable stains on fabrics at temperatures of ⁇ 40°C.
  • These diacyloxy benzene sulphonate compounds can be used as bleach activator in alkaline detergent compositions containing a peroxide compound and an enzyme to form low-temperature bleaching detergent composition which are quite effective for removing a wide class of stains from fabrics in domestic and laundering operations at or below 40°C.
  • the bleach activator as used in the present invention is a 1,2-diacyloxy benzene-3,5-disulphonate having the formula: wherein R and R1 are each individually a linear or non-­linear alkyl group containing 1 to 10 carbon atoms, or a phenyl or substituted phenyl group containing 6 to 10 carbon atoms; and M is H, alkali metal, earth alkali metal, ammonium or substituted ammonium.
  • the invention provides an improved alkaline bleach detergent composition, especially for washing fabrics, comprising a surface-active material, a detergency builder, a proteolytic enzyme, a peroxide compound and a bleach activator, wherein the bleach activator is a 1,2-diacyloxy benzene-3,5-disulphonate having the formula : wherein R and R1 are each individually a linear or non-­linear alkyl group containing 1 to 10 carbon atoms, or a phenyl or substituted phenyl group containing 6 to 10 carbon atoms; and M is H, alkali metal, earth alkali metal, ammonium or substituted ammonium.
  • R and R1 may be equal or different groups. Preferably, R and R1 are equal. Preferred compounds are those wherein R and R1 are phenyl, p-tert-butyl phenyl, or linear or non-linear C6-C8 alkyl groups, and wherein M is alkali metal, particularly sodium.
  • bleach activators within this invention are illustrative of bleach activators within this invention : (disodium-1,2-dibenzoyloxy benzene-3,5 disulphonate) (disodium-1,2-di-tert.butyl benzoyloxy-3,5-disulphonate) (disodium-1,2-diheptanoyloxy benzene-3,5-disulphonate) (disodium-1,2-dinonanoyloxy benzene-3,5-disulphonate) (disodium-1,2-diacetoxy benzene-3,5-disulphonate)
  • the diacyloxy benzene disulphonates as defined herein are more weight-effective than the corresponding monoacyloxy benzene sulphonates, which means that, on an equal weight basis, they provide a much more effective bleaching, particularly at their optimal pH value.
  • Similar isomeric compounds, such as the 1,3-diacyloxy benzene-4,6-disulphonates and the 1,3 diacyloxy benzene-­4,5-disulphonates are either less effective or difficult to synthesize, and are outside the purview of the present invention.
  • Each of the bleach activators as defined here can be used as a single compound in the bleaching detergent compositions of the invention, though mixtures of two or more compounds, e.g. (I) + IV) or (I) + (IV) + (V) or (II) + (V), may also be used, as desired.
  • mixtures of two or more compounds e.g. (I) + IV) or (I) + (IV) + (V) or (II) + (V)
  • the use of such mixtures could be of benefit for the overal stain-­removing properties and is also within the purview of the present invention.
  • alkaline detergent compositions of the invention comprising the bleach activator described herein will have a 2-5 g/l solution pH within the range of 8.5-10.5, with pH values of about 8.5-9.0 being optimal and preferred.
  • Peroxide compounds are well known in the art. They include the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates 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 it has excellent storage stability while also dissolving very quickly in aqueous bleaching solutions.
  • the equivalent ratio of hydrogen peroxide (or a peroxide compound generating the equivalent amount of H2O2) to precursor will range from 0.5:1 to about 20:1, preferably 1:1 to 15:1, most preferably from 2:1 to 10:1.
  • a detergent formulation of the invention will normally also contain surface-active materials and detergency builders.
  • the bleach activator may be present at a level ranging from about 0.1% to 20% by weight, preferably from 0.5 to 10% by weight, particularly from 1% to 7.5% by weight, together with a peroxide bleaching compound, e.g. sodium perborate mono- or tetrahydrate, the amount of which is usually within the range of from about 2% to 40%, preferably from about 4% to 30%, particularly from about 10% to 25% by weight.
  • a peroxide bleaching compound e.g. sodium perborate mono- or tetrahydrate
  • the surface-active material may be naturally derived or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof. Many 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.
  • the total level of the surface-active material may range up to 50% by weight, preferably being from about 1% to 40% by weight of the composition, most preferably 4% to 25%.
  • Synthetic anionic surface-active materials are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 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 (C8-C18) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) 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 (C9-C18) 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 fatty acid amides of
  • nonionic surface-active compounds which may be used, preferably together with the anionic surface-active compounds, include in particular the reaction products of alkylene oxide, usually ethylene oxide, with alkyl (C6-C22) phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, generally 6-30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine.
  • alkylene oxide usually ethylene oxide
  • alkyl (C6-C22) phenols generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule
  • condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide generally 6-30 EO
  • nonionic surface-actives include alkyl polyglycosides, long chain tertiary amine oxides, long
  • 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 C10-C24 fatty acids or mixtures thereof.
  • the amount of such soaps can be varied between about 0.5% and about 25% by weight, with lower amounts of about 0.5% to about 5% being generally sufficient for lather control. Amounts of soap between about 2% and about 20%, especially between about 5% and about 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.
  • Detergency 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 akali 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
  • nitrilotriacetic acid and its water-­soluble salts the akali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid
  • polyacetal carboxylates as disclosed in US patents 4,144,226 and 4,146,49
  • precipitating builder materials examples include sodium orthophosphate, sodium carbonate and long chain fatty acid soaps.
  • compositions of the invention 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, carboxymethyloxy 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, carboxymethyloxy 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.
  • 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 made 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®.
  • the preparation of these and analogous enzymes is described in British Patent Specification 1,243,784.
  • Other commercial proteases are Kazusase® (obtainable from Showa-Denko of Japan), Optimase® (from Miles Kali-Chemie, Hannover, West-­Germany), and Superase® (obtainable from Pfizer of USA).
  • 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 on their activity. They are generally incorporated in the form of granules, prills, or "marumes" in an amount such that the final washing product has a proteolytic activity of from about 2-20 Anson units per kilogram of final product.
  • the detergent compositions of the invention can contain any of the conventional additives in the amounts in which such materials are normally employed in fabric washing detergent compositions.
  • these additives include lather boosters, such as alkanol amides, 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; peroxide stabilizers, such as ethylene diamine tetraacetic acid, ethylene diamine tetra(methylene phosphonic acid) and diethylene triamine penta(methylene phosphonic acids, inorganic salts, such as sodium sulphate, and, usually present in very small amounts, fluorescent agents, perfumes, germicides, colourants and other enzymes, such as cellulases, lipases and amylases.
  • lather boosters such as alkanol amides,
  • polymeric materials such as polyacrylic acid, polyethylene glycol and the copolymers (meth)acrylic acid and maleic acid, which may also be incorporated to function as auxiliary builders together with any of the principal detergency builders, such as the polyphosphates and especially aluminosilicates.
  • lipases are fungal lipases obtained from Humicola Lanuginosa or Thermomyces Lanuginosa, and bacterial lipases which react positively with the antibody of the lipase from Chromobacter Viscosum.
  • Fluorescent agents usable herein are, for example, those of the diamino stilbene/cyanuric chloride types), e.g. Blankophor® MBBH; those of the distyryl benzene types, e.g. Tinopal® CBS and Tinopal® BLS; and those of the triazole types, e.g. Blankophor® BHC and Tinopal® RBS.
  • Blankophor® BHC and Tinopal® BLS is preferred for cotton fabrics and Tinopal® RBS is preferred for nylon. Blankophor and Tinopal are registered Trade Marks.
  • the alkaline detergent compositions of the invention may be presented in any suitable state of aggregation, e.g. as solids or liquids. They are, however, preferably presented in free-flowing, particulate form, e.g. powdered or granular form, which can be produced by any of the known techniques commonly employed in the manufacture of such washing compositions, e.g. 1) by spray-drying an aqueous slurry comprising the surfactants and builders to form a detergent base powder, to which the heat-sensitive ingredients are added, such as, for example, the bleach activator, the enzyme(s), the peroxy compound, and optionally some other ingredients as conveniently desirable: 2) by dry-­mixing or 3) by dry mixing/wet-blending.
  • the bleach activator and enzymes are preferably added as granulated particles.
  • the alkaline detergent composition of the invention is presented in the form of a non-aqueous, liquid detergent composition.
  • a detergent base powder of the following nominal composition was prepared by spray-drying. Composition parts by weight Sodium alkyl benzene sulphonate 6.0 Fatty alcohol/7 ethoxylate 4.0 Alkaline sodium silicate (1:2) 6.0 Sodium triphosphate 36.0 Sodium carboxymethyl cellulose 0.3 Ethylene diamine tetraacetate (EDTA) 0.13 Fluorescent agent 0.3 Sodium sulphate 14.0
  • the bleach activator levels used in both series were pre­calculated to give 7 reflectance units ( ⁇ R460*) on standard tea-stained test cloth in the series I formulation under the wash conditions as stated below, except that the pH was kept at 9.5.
  • the sodium perborate level of series I was kept constant at 14% by weight, whereas this level was varied in series II to maintain a constant 1:1 equivalent ratio of perborate to activator in the compositions A-D.
  • the washes were all carried out isothermally at 40°C in water of 15.FH in the presence of 4 g/l product.
  • the wash pH was adjusted to pH 8.5 with sulphuric acid after adding all the wash components except the bleach activator.
  • Tea is a typical hydrophilic stain and RAGU® (a spaghetti sauce) is used as a typical hydrophobic stain.
  • a detergent base powder of the following nominal composition was prepared by spray-drying : Composition parts by weight Sodium alkyl benzene sulphonate 6.0 Fatty alcohol/7 ethoxylate 4.0 Fatty alcohol/3 ethoxylate 3.0 Alkaline sodium silicate (1:2) 6.0 Sodium tripolyphosphate 25.0 EDTA 0.1 Sodium carboxymethyl cellulose 0.5 Sodium polyacrylate polymer 1.0 Minors (perfume, fluorescers, etc.) 1.5 Sodium sulphate (+ moisture) -- to 80.0 --
  • composition (E) parts by weight Detergent base 80.0 80.0 Sodium perborate monohydrate 1.6 13.0 Bleach activator* 5.0 5.0 Dequest ® 2041 0.4 0.4 Savinase ® 4. OT granules 1.0 1.0 *The bleach activator used was compound (I). SBBS was used as comparison.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP89201690A 1988-07-04 1989-06-27 Compositions détergentes de blanchiment Withdrawn EP0350096A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB888815841A GB8815841D0 (en) 1988-07-04 1988-07-04 Bleaching detergent compositions
GB8815841 1988-07-04

Publications (2)

Publication Number Publication Date
EP0350096A2 true EP0350096A2 (fr) 1990-01-10
EP0350096A3 EP0350096A3 (fr) 1990-08-29

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ID=10639821

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EP89201690A Withdrawn EP0350096A3 (fr) 1988-07-04 1989-06-27 Compositions détergentes de blanchiment

Country Status (7)

Country Link
EP (1) EP0350096A3 (fr)
JP (1) JPH0267399A (fr)
AU (1) AU613209B2 (fr)
BR (1) BR8903270A (fr)
GB (1) GB8815841D0 (fr)
NO (1) NO892742L (fr)
ZA (1) ZA895080B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995029225A1 (fr) * 1994-04-22 1995-11-02 The Procter & Gamble Company Compositions de blanchiment comprenant une enzyme protease
US5932532A (en) * 1993-10-14 1999-08-03 Procter & Gamble Company Bleach compositions comprising protease enzyme

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009512772A (ja) * 2005-10-28 2009-03-26 ザ プロクター アンド ギャンブル カンパニー エステル化置換ベンゼンスルホネートを含有する組成物

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2817858A1 (de) * 1978-04-24 1979-10-25 Schuelke & Mayr Gmbh Lagerfaehige und mit wasser eine loesung mit hoher antimikrobieller wirkung ergebende mischung
EP0185522A2 (fr) * 1984-12-14 1986-06-25 The Clorox Company Diesters phényléniques mixtes comme precurseurs de peracides

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8629534D0 (en) * 1986-12-10 1987-01-21 Unilever Plc Enzymatic detergent & bleaching composition
EP0337274B1 (fr) * 1988-04-14 1994-11-30 Unilever N.V. Compositions détergentes pour tissus

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2817858A1 (de) * 1978-04-24 1979-10-25 Schuelke & Mayr Gmbh Lagerfaehige und mit wasser eine loesung mit hoher antimikrobieller wirkung ergebende mischung
EP0185522A2 (fr) * 1984-12-14 1986-06-25 The Clorox Company Diesters phényléniques mixtes comme precurseurs de peracides

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5932532A (en) * 1993-10-14 1999-08-03 Procter & Gamble Company Bleach compositions comprising protease enzyme
WO1995029225A1 (fr) * 1994-04-22 1995-11-02 The Procter & Gamble Company Compositions de blanchiment comprenant une enzyme protease
CN1083004C (zh) * 1994-04-22 2002-04-17 普罗格特-甘布尔公司 包括蛋白酶的漂白组合物

Also Published As

Publication number Publication date
AU3724589A (en) 1990-01-04
AU613209B2 (en) 1991-07-25
ZA895080B (en) 1991-03-27
EP0350096A3 (fr) 1990-08-29
NO892742L (no) 1990-01-05
JPH0267399A (ja) 1990-03-07
BR8903270A (pt) 1990-02-13
GB8815841D0 (en) 1988-08-10
NO892742D0 (no) 1989-07-03

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