EP0201958B1 - Pourable detergent and bleach compositions - Google Patents

Pourable detergent and bleach compositions Download PDF

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Publication number
EP0201958B1
EP0201958B1 EP86200689A EP86200689A EP0201958B1 EP 0201958 B1 EP0201958 B1 EP 0201958B1 EP 86200689 A EP86200689 A EP 86200689A EP 86200689 A EP86200689 A EP 86200689A EP 0201958 B1 EP0201958 B1 EP 0201958B1
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EP
European Patent Office
Prior art keywords
composition
acid
compositions
weight
peroxydicarboxylic
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Expired
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EP86200689A
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German (de)
French (fr)
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EP0201958A1 (en
Inventor
John Meijer
Aaldert Johannes De Jong
Joachim Willem Joseph Van Gendt
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Akzo NV
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Akzo NV
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Priority to AT86200689T priority Critical patent/ATE35425T1/en
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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
    • 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
    • C11D3/3947—Liquid compositions

Definitions

  • the invention relates to a pourable, aqueous detergent and bleach composition containing an anionic surfactant, a non-ionic surfactant and a suspended organic percompound.
  • a composition of the above type is disclosed in Netherlands Patent Specification No. 276 283.
  • a liquid composition of the type indicated above has great advantages as regards preparation and use. Its preparation does not require cost increasing shaping steps and its liquid form contributes to ease of handling and dispensing and does away with dusting problems.
  • the invention envisages eliminating this drawback.
  • the composition according to the invention is characterized in that the anionic surfactant is a linear alkyl benzene sulphonate, the nonionic surfactant an ethoxylated fatty alcohol and the organic percompound an aliphatic peroxydicarboxylic acid containing 8 to 13 carbon atoms, the pH of the composition being set to 3,5 to 4,1.
  • European Patent Application No. 0 160 342, published 06.11.85, disscloses liquid, aqueous bleaching compositions having a pH in the range of from 2 to 5 and containing an alkyl benzene sulphonate, an ethoxylated fatty alcohol, a suspended peroxy acid and an electrolyte; Examples IV and V in it disclose compositions having a pH of 4,5. Aside from the fact that the compositions according to the present invention are not disclosed in said European Patent Application, the present compositions display better storage stability as compared with compositions having a pH outside the claimed range but within the scope of said Application. This is demonstrated in the Examples below.
  • the present composition is storage stable, i.e. after 2 weeks' storage at 40°C it has entirely or practically entirely retained its active oxygen content.
  • the pourability of the present composition may be set in accordance with any particular need.
  • the viscosity of the composition measured with a Brookfield rotational viscometer (RV type; 20 rpm) at 20°C, is between 1 and 1200 mPa.s and preferably between 50 and 500 mPa.s.
  • the linear alkyl benzene sulphonate and the ethoxylated fatty alcohol to be contained in the present composition are substances that are also normally used in detergent compositions.
  • Preferred linear alkyl benzene sulphonates are those having 11 to 14 carbon atoms in the alkyl chain.
  • suitable ethoxylated fatty alcohols there are mentioned ethoxylated C 9 -C 18 alcohols having an average degree of ethoxylation from 3 to 15.
  • the amounts of the surfactants to be used may vary with the desired pourability.
  • the composition according to the invention preferably contains 2 to 20 % by weight of the linear alkyl benzene sulphonate and 5 to 30 % by weight of the ethoxylated fatty alcohol, calculated on the weight of the composition.
  • the bleaching agent to be used according to the invention is an aliphatic peroxydicarboxylic acid containing 8 to 13 carbon atoms.
  • the term peroxydicarboxylic acid as used here refers to both a monoperoxydicarboxylic acid and a diperoxydicarboxylic acid. Use also may be made of mixtures of these peracids or combinations of peracids of different chain lengths. It is preferred that the peroxydicarboxylic acid to be used should substantially consist of a diperoxydicarboxylic acid.
  • the diperoxydicarboxylic acids according to the invention may be mentioned 1,12-diperoxydodecanedioic acid and 1,13-diperoxytridecanedioic acid.
  • DPDA 1,12-diperoxydodecanedioic acid
  • the amount of peroxydicarboxylic acid to be used in the composition according to the invention is preferably such that the composition, calculated on the weight thereof, contains active oxygen in an amount ranging between 0,1 and 4 % by weight, preferably between 0,1 and 3 % by weight.
  • the average size is advantageously chosen between 1 and 100 micrometers.
  • the peroxydicarboxylic acids are compounds that are known in themselves and may be prepared by reacting a dicarboxylic acid with hydrogen peroxide under the influence of sulphuric acid.
  • sequestering agent in the composition for the purpose of complexing metal ions, the presence of which may cause decomposition of the peroxydicarboxylic acid.
  • these sequestering agents which must not be sensitive to the oxidative action of the peracid, may be mentioned dipicolinic acid, hydroxyethylidene diphosphonic acid, alkali metal pyrophosphate and phosphonic acid.
  • the amount of sequestering agent that may be used in the present composition is generally in the range of 0 to 1% by weight, preferably 0,01 to 1 % by weight, calculated on the.weight of the composition.
  • the pH of the composition is of great importance. It should be set to 3,5 to 4,1. At a pH higher than 4,1 the storage stability of the composition obtained will diminish; at a pH lower than 3,5 the composition obtained will be less suitable for washing and bleaching purposes because of a too low pH of the wash liquor upon dilution with water in, for instance, a washing machine. It has been found that the present composition, in spite of its displaying a slightly acidic reaction upon dilution with water, can be very effectively used in the treatment of dirty washing. This is surprising in that it had up to now been generally assumed that for this purpose neutral to alkaline conditions are required.
  • the present composition may still contain various commonly applied additives.
  • additives include dirt suspending agents, fluorescent and optical brighteners or whitening agents, perfumes and hydrotopic substances.
  • the choice thereof is, of course, dependent on the desired properties of the composition and on the compatibility with the other constituents.
  • some additives such as enzymes and particular oxidation sensitive brighteners or whitening agents cannot be incorporated as such in the present composition.
  • a suitable coating which may be in the form of, for instance, a solid detergent-active material which dissolves during the washing stage, after which its incorporation in the composition is no longer objectionable.
  • the present composition can be prepared in a simple manner by adding finely divided peroxydicarboxylic acid, with stirring, to an acidified (pH about 2) mixture in water of the anionic and the non-ionic surfactant and any other constituents, after which the pH of the resulting composition is set to the desired value with, say, sodium hydroxide.
  • composition A Three compositions according to the invention were tested for loss of active oxygen during storage.
  • the table below gives the constituents in percentages and the relevant properties of the compositions and the test results.
  • the table gives the test results of a comparative test conducted on a composition according to Example 4 of Netherlands Patent Specification No. 276 283 (Composition A).
  • compositions according to the invention display satisfactory storage stability at 40° C.
  • prior art composition A was subject to total decomposition, which was moreover attended with severe froth forming. It appears from the test results that also at 32° C composition A shows poor storage stability.
  • compositions corresponding to composition 3 a number of additives were incorporated after which the storage stability was determined in the same way as described above. Use was made of the following additives in the amounts given in brackets:
  • composition B was a liquid detergent concentrate containing about 37 % of water, about 40 % of surfactants and also enzymes and other substances, such as optical whitener; of this composition 120 ml were used.
  • composition C was a powdered detergent and bleach agent containing about 14% of surfactants, about 19 % of polyphosphate, about 15 % of sodium aluminium silicate, about 23 % of sodium sulphate, about 9 % of sodium perborate.
  • 4 H 2 0, about 4 % of tetraacetyl ethylene diamine and also enzymes and other additives; of this composition 131 g were used.
  • compositions according to the invention are compared with compositions having a pH outside the claimed range but within the scope of European Patent Application No. 0 160 342 as regards storage stability.
  • a composition was prepared containing
  • composition was divided into several portions which were each set to a different pH.
  • storage stability was determined by measuring the percentage of active oxygen remaining after storage at 40° C during 1, 3 and 4 weeks. The results are tabulated below.

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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)

Abstract

The present invention provides pourable, aqueous detergent and bleach compositions containing a linear alkyl benzene sulphonate, an ethoxylated fatty alcohol and a suspended peroxydicarboxylic acid, e.g. diperoxydodecanedioic acid, the pH of the compositions being set to 3,5 to 4,1.

Description

  • The invention relates to a pourable, aqueous detergent and bleach composition containing an anionic surfactant, a non-ionic surfactant and a suspended organic percompound.
  • A composition of the above type is disclosed in Netherlands Patent Specification No. 276 283. Over the detergent and bleach compositions which are in a form varying from powdered to granular as widely used in actual practice a liquid composition of the type indicated above has great advantages as regards preparation and use. Its preparation does not require cost increasing shaping steps and its liquid form contributes to ease of handling and dispensing and does away with dusting problems.
  • The above-mentioned Netherlands Patent Specification proposes as bleaching component suspended organic percompounds of the general formula R - 0 - 0 - Rl, where R and R1 represent organic radicals; moreover, the pH of the compositions described should be at least 7 and preference is given to alkaline reacting compositions. To these compositions, however, there is the disadvantage that they are not stable under storage conditions prevailing in actual practice, i.e. there occurs an unacceptable loss of active oxygen. Therefore, these compositions have not found acceptance in actual practice.
  • The invention envisages eliminating this drawback. The composition according to the invention is characterized in that the anionic surfactant is a linear alkyl benzene sulphonate, the nonionic surfactant an ethoxylated fatty alcohol and the organic percompound an aliphatic peroxydicarboxylic acid containing 8 to 13 carbon atoms, the pH of the composition being set to 3,5 to 4,1.
  • European Patent Application No. 0 160 342, published 06.11.85, disscloses liquid, aqueous bleaching compositions having a pH in the range of from 2 to 5 and containing an alkyl benzene sulphonate, an ethoxylated fatty alcohol, a suspended peroxy acid and an electrolyte; Examples IV and V in it disclose compositions having a pH of 4,5. Aside from the fact that the compositions according to the present invention are not disclosed in said European Patent Application, the present compositions display better storage stability as compared with compositions having a pH outside the claimed range but within the scope of said Application. This is demonstrated in the Examples below.
  • The present composition is storage stable, i.e. after 2 weeks' storage at 40°C it has entirely or practically entirely retained its active oxygen content. The pourability of the present composition may be set in accordance with any particular need. For practical purposes the viscosity of the composition, measured with a Brookfield rotational viscometer (RV type; 20 rpm) at 20°C, is between 1 and 1200 mPa.s and preferably between 50 and 500 mPa.s.
  • The linear alkyl benzene sulphonate and the ethoxylated fatty alcohol to be contained in the present composition are substances that are also normally used in detergent compositions. Preferred linear alkyl benzene sulphonates are those having 11 to 14 carbon atoms in the alkyl chain. As suitable ethoxylated fatty alcohols there are mentioned ethoxylated C9-C18 alcohols having an average degree of ethoxylation from 3 to 15. The amounts of the surfactants to be used may vary with the desired pourability. The composition according to the invention preferably contains 2 to 20 % by weight of the linear alkyl benzene sulphonate and 5 to 30 % by weight of the ethoxylated fatty alcohol, calculated on the weight of the composition.
  • The bleaching agent to be used according to the invention is an aliphatic peroxydicarboxylic acid containing 8 to 13 carbon atoms. The term peroxydicarboxylic acid as used here refers to both a monoperoxydicarboxylic acid and a diperoxydicarboxylic acid. Use also may be made of mixtures of these peracids or combinations of peracids of different chain lengths. It is preferred that the peroxydicarboxylic acid to be used should substantially consist of a diperoxydicarboxylic acid. As examples of the diperoxydicarboxylic acids according to the invention may be mentioned 1,12-diperoxydodecanedioic acid and 1,13-diperoxytridecanedioic acid. Particularly preferred is 1,12-diperoxydodecanedioic acid (referred to hereinafter as DPDA). The amount of peroxydicarboxylic acid to be used in the composition according to the invention is preferably such that the composition, calculated on the weight thereof, contains active oxygen in an amount ranging between 0,1 and 4 % by weight, preferably between 0,1 and 3 % by weight.
  • To prevent sedimentation of the suspended peroxydicarboxylic acid particles their average size is advantageously chosen between 1 and 100 micrometers.
  • The peroxydicarboxylic acids are compounds that are known in themselves and may be prepared by reacting a dicarboxylic acid with hydrogen peroxide under the influence of sulphuric acid.
  • Of importance is the quality of the water to be used in the present composition in order to obtain satisfactory storage stability. Favourable results may be obtained with bidistilled water or with deionized water.
  • It will be of advantage also to incorporate a sequestering agent in the composition for the purpose of complexing metal ions, the presence of which may cause decomposition of the peroxydicarboxylic acid. As examples of these sequestering agents, which must not be sensitive to the oxidative action of the peracid, may be mentioned dipicolinic acid, hydroxyethylidene diphosphonic acid, alkali metal pyrophosphate and phosphonic acid. The amount of sequestering agent that may be used in the present composition is generally in the range of 0 to 1% by weight, preferably 0,01 to 1 % by weight, calculated on the.weight of the composition.
  • The pH of the composition is of great importance. It should be set to 3,5 to 4,1. At a pH higher than 4,1 the storage stability of the composition obtained will diminish; at a pH lower than 3,5 the composition obtained will be less suitable for washing and bleaching purposes because of a too low pH of the wash liquor upon dilution with water in, for instance, a washing machine. It has been found that the present composition, in spite of its displaying a slightly acidic reaction upon dilution with water, can be very effectively used in the treatment of dirty washing. This is surprising in that it had up to now been generally assumed that for this purpose neutral to alkaline conditions are required.
  • The present composition may still contain various commonly applied additives. Examples of such additives include dirt suspending agents, fluorescent and optical brighteners or whitening agents, perfumes and hydrotopic substances. The choice thereof is, of course, dependent on the desired properties of the composition and on the compatibility with the other constituents. In this connection it should be noted that because of the oxidative action of the peroxydicarboxylic acid some additives, such as enzymes and particular oxidation sensitive brighteners or whitening agents cannot be incorporated as such in the present composition. However, such substances may previously be provided with a suitable coating, which may be in the form of, for instance, a solid detergent-active material which dissolves during the washing stage, after which its incorporation in the composition is no longer objectionable.
  • The present composition can be prepared in a simple manner by adding finely divided peroxydicarboxylic acid, with stirring, to an acidified (pH about 2) mixture in water of the anionic and the non-ionic surfactant and any other constituents, after which the pH of the resulting composition is set to the desired value with, say, sodium hydroxide.
  • The following examples serve to illustrate the invention. All percentages therein are by weight.
    • Example 1
  • Three compositions according to the invention were tested for loss of active oxygen during storage. The table below gives the constituents in percentages and the relevant properties of the compositions and the test results. In addition the table gives the test results of a comparative test conducted on a composition according to Example 4 of Netherlands Patent Specification No. 276 283 (Composition A).
    Figure imgb0001
  • The test results show that the compositions according to the invention display satisfactory storage stability at 40° C. At this temperature prior art composition A was subject to total decomposition, which was moreover attended with severe froth forming. It appears from the test results that also at 32° C composition A shows poor storage stability.
  • Into several compositions corresponding to composition 3 a number of additives were incorporated after which the storage stability was determined in the same way as described above. Use was made of the following additives in the amounts given in brackets:
    • -methylhydroxypropyl cellulose (1 %)
    • - optical brightener ATS-XE, a commercial product of Ciba Geigy (0,15%)
    • - perfumes Turbom, Lanea® and Kalifae, Commercial products of Naarden Chemie Int. Holland B. V. (0,3 %).
  • After 1 month's storage at 40°C all these compositions showed a loss of active oxygen of only a few per cent.
    • Example 2
  • Of the Composition 3 described in Example 1 an amount of 120 ml was tested under practical conditions for its capability of removing stains and dirty spots from domestic laundry. Comparative tests were carried out on recommended portions of two commercially available compositions, which are referred to hereinafter as composition B and composition C. Composition B was a liquid detergent concentrate containing about 37 % of water, about 40 % of surfactants and also enzymes and other substances, such as optical whitener; of this composition 120 ml were used. composition C was a powdered detergent and bleach agent containing about 14% of surfactants, about 19 % of polyphosphate, about 15 % of sodium aluminium silicate, about 23 % of sodium sulphate, about 9 % of sodium perborate. 4H20, about 4 % of tetraacetyl ethylene diamine and also enzymes and other additives; of this composition 131 g were used.
  • In each test in all 216 articles, including tea towels, sheets, pillow cases and underwear, were washed in an AEG-Turnamatm washer with tap water of 9° GH. The maximum washing temperature was 62° C, the total washing time, including heating up, was 59 minutes and the amount of water admitted 19 litres. Following the washing process the washing was rinsed with 5 x 17 litres of cold water and dried. Subsequently, the washing was rated by a panel by counting the number of clean fourth parts of the tea towels, sheets and pillow cases. Both sides were rated, so that the rating of a perfectly clean article was 8 points. The underwear was compared with totally clean underwear, the rating for totally clean underwear being 8 points and for less clean underwear between 0 and 8.
  • For each of the three compositions tested the ratings of 12 tests were averaged. For the composition according to the invention the rating was 6,8, for composition B it was 6,5 and for Composition C 6,9. These results show that the effectiveness of the composition according to the invention is excellent. Repeating the above tests at a maximum washing temperature of 40°C resulted in similar ratings.
    • Example 3
  • In this Example compositions according to the invention are compared with compositions having a pH outside the claimed range but within the scope of European Patent Application No. 0 160 342 as regards storage stability. A composition was prepared containing
  • 100 g of sodium dodecyl benzene sulphonate (85 %, the remainder substantially consisting of sodium sulphate and some sodium chloride),
  • 100 g of ethoxylated (7,5 EO) C12-C14 fatty alcohol, 5 g of Dequest 2010®,
  • 243 gof DPDA (aqueous paste with an active oxygen content of 5,1 %),
  • 557 g of water.
  • This composition was divided into several portions which were each set to a different pH. Of the resulting compositions the storage stability was determined by measuring the percentage of active oxygen remaining after storage at 40° C during 1, 3 and 4 weeks. The results are tabulated below.
    Figure imgb0002
  • The results in the table clearly demonstrate the good storage stability of the compositions according to the invention as compared with that of compositions having a pH outside the claimed range but within the scope of EP-A-0160 342.

Claims (3)

1. A pourable, aqueous detergent and bleach composition containing an anionic surfactant, a non-ionic surfactant and a suspended organic percompound, characterized in that the anionic surfactant is a linear alkyl benzene sulphonate, the non-ionic surfactant an ethoxylated fatty alcohol and the organic percompound an aliphatic peroxydicarboxylic acid containing 8 to 13 carbon atoms, the pH of the composition being set to 3,5 to 4.1.
2. A composition according to claim 1, characterized in that, calculated on the weight of the composition, the amount of linear alkyl benzene sulphonate is 2 to 20 % by weight and the amount of ethoxyiated fatty alcohol 5 to 30 % by weight, and the amount of peroxydicarboxylic acid is such that the composition contains 0,1 to 4 % by weight of active oxygen.
3. A composition according to claim 1 or 2, characterized in that the peroxydicarboxylic acid is 1,12- diperoxydodecanedioic acid.
EP86200689A 1985-05-07 1986-04-23 Pourable detergent and bleach compositions Expired EP0201958B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86200689T ATE35425T1 (en) 1985-05-07 1986-04-23 POURABLE CLEANING AND BLEACHING AGENTS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL8501296 1985-05-07
NL8501296 1985-05-07

Publications (2)

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EP0201958A1 EP0201958A1 (en) 1986-11-20
EP0201958B1 true EP0201958B1 (en) 1988-06-29

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Country Status (6)

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EP (1) EP0201958B1 (en)
JP (1) JPS61256000A (en)
AT (1) ATE35425T1 (en)
CA (1) CA1284448C (en)
DE (1) DE3660350D1 (en)
DK (1) DK164116C (en)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1294510C (en) * 1986-03-31 1992-01-21 Stanton Lane Boyer Stable liquid diperoxyacid bleach
US4770666A (en) * 1986-12-12 1988-09-13 The Procter & Gamble Company Laundry composition containing peroxyacid bleach and soil release agent
GB2245000B (en) * 1987-09-17 1992-06-03 Colgate Palmolive Co Liquid detergent composition
GB8806704D0 (en) * 1988-03-21 1988-04-20 Unilever Plc Stable liquid bleach compositions
US4828747A (en) * 1988-03-25 1989-05-09 Lever Brothers Company Suspending system for insoluble peroxy acid bleach
US4824592A (en) * 1988-03-25 1989-04-25 Lever Brothers Company Suspending system for insoluble peroxy acid bleach
US5358654A (en) * 1988-06-22 1994-10-25 Akzo Nobel N.V. Stable pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers
DE68905089T2 (en) * 1988-06-22 1993-07-22 Akzo Nv STABLE, POURABLE WATER-BASED BLEACH COMPOSITIONS CONTAINING SOLID ORGANIC PEROXYACIDS AND AT LEAST TWO POLYMERS.
US5126066A (en) * 1988-06-22 1992-06-30 Akzo N.V. Stable, pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers
EP0385522B1 (en) * 1989-02-27 2001-08-29 Unilever N.V. Liquid detergent composition
EP0412599B1 (en) * 1989-08-08 1995-12-13 Akzo Nobel N.V. Aqueous peroxide compositions with improved safety profile
EP0435379A3 (en) * 1989-12-22 1991-07-31 Akzo N.V. Suspension, coating, agglomeration and uses of imidoperoxycarboxylic acids
GB9003200D0 (en) * 1990-02-13 1990-04-11 Unilever Plc Aqueous liquid bleach composition
US5055218A (en) * 1990-04-13 1991-10-08 The Procter & Gamble Company Bleach granules containing an amidoperoxyacid
EP0511163B1 (en) * 1991-04-24 1995-07-26 Ciba-Geigy Ag Pourable aqueous dispersions of polycarboxylic acid corrosion inhibitors
US5453214A (en) * 1991-10-04 1995-09-26 Akzo Nobel N.V. Suspension and agglomeration of amidoperoxyacids
EP0592033A1 (en) * 1992-10-07 1994-04-13 The Procter & Gamble Company Process for making peroxyacid containing particles
US5409632A (en) * 1992-11-16 1995-04-25 The Procter & Gamble Company Cleaning and bleaching composition with amidoperoxyacid
WO1994024101A1 (en) * 1993-04-13 1994-10-27 Akzo Nobel N.V. Melt crystallization and suspension of amidoacids
US5932532A (en) * 1993-10-14 1999-08-03 Procter & Gamble Company Bleach compositions comprising protease enzyme
GB9425882D0 (en) * 1994-12-21 1995-02-22 Solvay Interox Ltd Thickened peracid compositions
GB9425881D0 (en) * 1994-12-21 1995-02-22 Solvay Interox Ltd Thickened peracid compositions
EP1001008A1 (en) * 1998-11-10 2000-05-17 The Procter & Gamble Company Liquid aqueous bleaching compositions comprising a sulphonated anionic surfactant
EP1122299B1 (en) * 1999-12-28 2005-07-06 Reckitt Benckiser N.V. Laundry composition
EP1113069A1 (en) * 1999-12-28 2001-07-04 Reckitt Benckiser N.V. Liquid peroxide bleaches comprising speckles in suspension

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2612587A1 (en) * 1975-03-27 1976-10-14 Procter & Gamble BLEACHING AGENT
US4170453A (en) * 1977-06-03 1979-10-09 The Procter & Gamble Company Peroxyacid bleach composition
DE2756583A1 (en) * 1977-12-19 1979-06-21 Henkel Kgaa BLEACHING AGENT SUITABLE FOR TEXTILE TREATMENT, CONTAINING PERCONNECTIONS AND OPTICAL BRIGHTENERS
EP0160342B2 (en) * 1984-05-01 1992-11-11 Unilever N.V. Liquid bleaching compositions
GB8411161D0 (en) * 1984-05-01 1984-06-06 Unilever Plc Multiple compartment pack
NL8402957A (en) * 1984-09-28 1986-04-16 Akzo Nv USE OF PEROXYCARBONIC ACID CONTAINING SUSPENSIONS AS A BLEACH COMPOSITION.

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DK164116C (en) 1992-10-12
DE3660350D1 (en) 1988-08-04
EP0201958A1 (en) 1986-11-20
JPS61256000A (en) 1986-11-13
DK208286A (en) 1986-11-08
ATE35425T1 (en) 1988-07-15
DK164116B (en) 1992-05-11
CA1284448C (en) 1991-05-28
DK208286D0 (en) 1986-05-06

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