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EP0550077A1 - Granular laundry bleaching composition - Google Patents

Granular laundry bleaching composition Download PDF

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Publication number
EP0550077A1
EP0550077A1 EP92200005A EP92200005A EP0550077A1 EP 0550077 A1 EP0550077 A1 EP 0550077A1 EP 92200005 A EP92200005 A EP 92200005A EP 92200005 A EP92200005 A EP 92200005A EP 0550077 A1 EP0550077 A1 EP 0550077A1
Authority
EP
European Patent Office
Prior art keywords
percarbonate
compositions
sodium
bleaching composition
weight
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.)
Ceased
Application number
EP92200005A
Other languages
German (de)
French (fr)
Inventor
Marina Trani
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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 Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP92200005A priority Critical patent/EP0550077A1/en
Priority to KR1019940702293A priority patent/KR940703911A/en
Priority to JP5511910A priority patent/JPH07502770A/en
Priority to CA002126847A priority patent/CA2126847A1/en
Priority to RU94035995/04A priority patent/RU94035995A/en
Priority to PCT/US1992/011222 priority patent/WO1993012843A1/en
Priority to BR9207019A priority patent/BR9207019A/en
Priority to AU34224/93A priority patent/AU666918B2/en
Priority to MX9207671A priority patent/MX9207671A/en
Priority to MA23046A priority patent/MA22754A1/en
Priority to CN93101189A priority patent/CN1075749A/en
Publication of EP0550077A1 publication Critical patent/EP0550077A1/en
Ceased 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
    • C11D3/395—Bleaching agents
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the present invention relates to bleaching compositions for laundry.
  • Granular laundry bleaching compositions are described which comprise percarbonate as the bleaching specie, said compositions being stable upon storage.
  • the inorganic perhydrate bleach most widely used in the context of laundry bleaching is sodium perborate in the form of either the monohydrate or tetrahydrate.
  • concerns about the impact of boron salts on the environment have led to an increasing interest in other perhydrate salts, of which sodium percarbonate is the most readily available.
  • Percarbonate salts particularly sodium percarbonate
  • detergent compositions containing sodium percarbonate are known in the art.
  • Percarbonate salts, particularly sodium percarbonate are attractive perhydrates for use in detergent compositions because they dissolve readily in water, are weight efficient and, after giving up their available oxygen, provide a useful source of carbonate ions for detergency purposes.
  • percarbonate salts have been restricted hitherto by the relative instability of the bleach both as is and in use .
  • Sodium percarbonate loses its available oxygen at a significant rate in the presence of ions of heavy metals such as iron, copper and manganese and also in the presence of moisture, these effects being accelerated at temperatures in excess of about 30°C.
  • Moisture and heavy metal ions are unavoidable components of conventional granular laundry treatment compositions. Also percarbonate decomposition due to moisture becomes more of an issue during storage as laundry treatment products are often stored in humid environments when the product picks up moisture. This has resulted in marginally acceptable percarbonate bleach stability under Northern European summer conditions, where the average maximum temperature over the hottest months is from 21°C to 25°C, and unacceptable stability under temperatures higher than this. Such conditions are found in the Middle East and Southern Asia and also in Southern Europe where average maximum temperatures are in the 27°C to 33°C range for the hottest summer month.
  • composition comprising an alkali metal salt of percarbonate together with a crystalline layered silicate or mixtures thereof.
  • Granular bleaching compositions comprising percarbonate have been described for instance in FR 2,385,837, US 4,428,914 and GB 1,553,505.
  • Crystalline layered silicate and their methods of preparation have been described for instance in EP-A-164 514, DE-A-34 17 649 and DE-A-37 42 043 and their application to the field of laundry treatment has been described in applicant's copending British applications GB 90 21 761.3, GB 90 18157.9 and GB 91 08639.7.
  • compositions according to the present invention also allow adequate control of the pH in the bleaching liquor, giving appropriate balance between bleaching performance and fabric safety.
  • compositions according to the present invention are granular bleaching compositions comprising more than 20% and up to 80% by weight of the total composition of an alkali metal salt of percarbonate bleach and from 5% to 80% by weight of the total composition of a crystalline layered silicate of formula NaMSi x O 2x+1 .yH2O wherein M is sodium or hydrogen, x is a number of from 1.9 to 4 and y is a number of from 0 to 20, or mixtures thereof.
  • Preferred compositions herein further comprise an anhydrous acidifying agent, preferably citric acid.
  • the compositions according to the present invention comprise an alkali metal salt of percarbonate, preferably sodium percarbonate.
  • Sodium percarbonate is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1, 1-diphosphonic acid (HEDP) or an amino-phosphonate, that is incorporated during the manufacturing process.
  • EDTA 1-hydroxyethylidene 1, 1-diphosphonic acid
  • HEDP 1-diphosphonic acid
  • the percarbonate can be incorporated into detergent compositions without additional protection.
  • the percarbonate Whilst heavy metals present in the sodium carbonate used to manufacture the percarbonate can be controlled by the inclusion of sequestrants in the reaction mixture, it is preferred that the percarbonate be protected from heavy metals present as impurities in other ingredients of the product. It has been found that the total level of Iron, Copper and Manganese ions in the product should not exceed 25 ppm and preferably should be less than 20 ppm in order to avoid an unacceptably adverse effect on percarbonate stability.
  • compositions according to the present invention comprise more than 20% by weight of the total composition of percarbonate, up to 80% by weight of the total composition, preferably from 40% to 50%.
  • the second essential component of the invention is a crystalline layered silicate.
  • the crystalline layered silicates suitable for use herein are of the granular formula NaMSi x O 2x+1 .yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, or mixtures thereof.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-164 514 and methods for their preparation are disclosed in DE-A-34 17 649 and DE-A-37 42 043.
  • x in the general formula above has a value of 2, 3 or 4 and is preferably 2.
  • M is sodium and y is 0 and preferred examples of this formula comprise the ⁇ , ⁇ , ⁇ and ⁇ forms of Na2Si2O5
  • These materials are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6.
  • the most preferred material is ⁇ - Na2Si2O5 , NaSKS-6.
  • Crystalline layered silicates are incorporated either as dry mixed solids, or as solid components of agglomerates with other components.
  • compositions according to the present invention comprise from 5% to 80% by weight of the total composition of said crystalline layered silicates or mixtures thereof, preferably from 15% to 25%.
  • compositions according to the present invention further comprise an anhydrous acidifying agent or mixtures thereof.
  • the purpose of said acidifying agent is to control the alkalinity generated by the percarbonate in the bleaching liquor. Said agent need to be incorporated in the product in an anhydrous form, and to have a good stability in oxidizing environment.
  • Suitable anhydrous acidifying agents for use herein are carboxylic acids such as citric acid, succinic acid, adipic acid, glutaric acid, 3 chetoglutaric acid, citramalic acid, tartaric acid and maleic acid.
  • Other suitable acidifying agents include sodium bicarbonate, sodium sesquicarbonate and silicic acid. Highly preferred for use herein is citric acid.
  • citric acid is commercially available in anhydrous form, it additionally acts as a builder and a chelant, and it is biodegradable.
  • the compositions according to the present invention comprise from up to 15% by weight of the total composition of anhydrous citric acid, preferably from 2% to 8%, most preferably about 5%.
  • compositions in accordance with the invention can also comprise optional ingredients such as optical brighteners, anti dusting agents such as olefines and waxes, enzymes, chelants, dispersants, surfactants, soil release agents, photoactivated bleaches such as Zn phthalocyanine sulphonate, dyes, pigments and perfumes are examples of such optional ingredients and can be added in varying amounts as desired.
  • optional ingredients such as optical brighteners, anti dusting agents such as olefines and waxes, enzymes, chelants, dispersants, surfactants, soil release agents, photoactivated bleaches such as Zn phthalocyanine sulphonate, dyes, pigments and perfumes are examples of such optional ingredients and can be added in varying amounts as desired.
  • Optional but highly preferred ingredients are peroxy carboxylic acids bleach or precursors thereof, commonly referred to as bleach activators, which are preferably added in a prilled or agglomerated form.
  • bleach activators peroxy carboxylic acids bleach or precursors thereof, commonly referred to as bleach activators, which are preferably added in a prilled or agglomerated form.
  • suitable compounds of this type are disclosed in British Patent GB 1 586 769 and GB 2 143 231 and a method for their formation into a prilled form is described in European Published Patent Application EP-A-62 523.
  • TAED tetracetyl ethylene diamine
  • NOBS n-nonanoyloxybenzenesulphonate
  • ATC acetyl triethyl citrate
  • compositions according to the present invention naturally comprise inorganic filler salts such as alkali metal carbonates bicarbonates and sulphates.
  • inorganic filler salts such as alkali metal carbonates bicarbonates and sulphates.
  • Such fillers for instance sodium bicarbonate, may also act as acidifying agent as described herein above. Accordingly, sodium percarbonate is a preferred filler material for use herein.
  • compositions according to the present invention can be made by a variety of methods well known in the art, including dry-mixing, spray drying, agglomeration and granulation and combinations thereof.
  • compositions according to the present invention can be prepared with different bulk densities, from conventional granular products to so-called “concentrated” products (i.e. with a bulk density above 600g/l).
  • compositions 1 2 3 4 5 6 Sodium percarbonate 40.0 35.0 54.0 55.0 46.0 47.0 TAED 8.7 7.6 11.7 - 9.5 - Silicate layered SKS-6 25.0 30.0 20.0 10.0 18.0 20.0 Anhydrous citric acid 10.0 12.0 12.0 5.0 5.0 5.0 Sodium sulphate 15.3 14.3 1.0 20.0 0.5 15.0 Sodium bicarbonate - - - 5.0 18.0 - NOBS - - - - - 10.3 minors up to 100%
  • compositions were made by mixing the listed ingredients in the listed proportions.
  • the self heating rates of the products were monitored as follows.
  • the product is made and put in a bottle.
  • the bottle is then put in an oven which is heated up to 70°c.
  • a probe in the product allows to monitor the temperature of the product.
  • the bottle is covered and the system is isolated in an adiabatic/thermo bell which maintains the temperature of the oven constant at 70°c as above. This places the product in adiabatic conditions and from thereon, the temperature of the product is monitored.
  • the temperature increase thus measured is due to the self-heating of the product (runaway reaction).
  • SHR1 is the average temperature increase measured during the first two hours of adiabatic conditions
  • SHR2 is the average temperature increase measured during the three following hours
  • SHR3 is the average temperature increase measured beyond 5 hours.
  • the table below lists the results obtained for various compositions, with and without crystalline layered silicate. In some cases the runaway reaction was out of control and experiments had to be interrupted for safety reasons. Such experiments are marked "ooc" (out of control).
  • compositions 7-12 show good thermal stability, and no temperature increase is reported after 5 hours storage and beyond. In the absence of crystalline layered silicate i.e. in compositions 7a-12a, self-heating rates measured were so high that experiments had to be stopped for safety purposes.

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  • Chemical & Material Sciences (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)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

A granular bleaching composition is disclosed which comprises an alkali metal salt of percarbonate and a crystalline layered silicate or mixtures thereof. Preferred compositions further comprise an anhydrous acidifiant agent. The compositions provide effective bleaching and are as stable as perborate based bleaching compositions.

Description

    Technical field
  • The present invention relates to bleaching compositions for laundry. Granular laundry bleaching compositions are described which comprise percarbonate as the bleaching specie, said compositions being stable upon storage.
    • Background of the invention
  • The inorganic perhydrate bleach most widely used in the context of laundry bleaching is sodium perborate in the form of either the monohydrate or tetrahydrate. However, concerns about the impact of boron salts on the environment have led to an increasing interest in other perhydrate salts, of which sodium percarbonate is the most readily available.
  • Detergent compositions containing sodium percarbonate are known in the art. Percarbonate salts, particularly sodium percarbonate, are attractive perhydrates for use in detergent compositions because they dissolve readily in water, are weight efficient and, after giving up their available oxygen, provide a useful source of carbonate ions for detergency purposes.
  • However, the inclusion of percarbonate salts in detergent compositions has been restricted hitherto by the relative instability of the bleach both as is and in use. Sodium percarbonate loses its available oxygen at a significant rate in the presence of ions of heavy metals such as iron, copper and manganese and also in the presence of moisture, these effects being accelerated at temperatures in excess of about 30°C.
  • Moisture and heavy metal ions are unavoidable components of conventional granular laundry treatment compositions. Also percarbonate decomposition due to moisture becomes more of an issue during storage as laundry treatment products are often stored in humid environments when the product picks up moisture. This has resulted in marginally acceptable percarbonate bleach stability under Northern European summer conditions, where the average maximum temperature over the hottest months is from 21°C to 25°C, and unacceptable stability under temperatures higher than this. Such conditions are found in the Middle East and Southern Asia and also in Southern Europe where average maximum temperatures are in the 27°C to 33°C range for the hottest summer month.
  • There has therefore been much activity by workers in the field to increase percarbonate stability so as to make it a viable component of detergent formulations. This activity has tended to concentrate on the protection of the percarbonate by coating the crystalline product or by inclusion of stabilising agents during its manufacture, or both. Thus, while it has proved possible to incorporate percarbonate salts in conventional detergent compositions so as to have acceptable percarbonate stability over periods reflecting normal product shelf life, the percarbonate salts have proved complex and expensive to manufacture. This has restricted their broadscale utilisation, as evidenced by the relatively small number of commercially available products containing percarbonate.
  • It is therefore an object of the present invention to provide a granular laundry bleaching composition incorporating an alkali metal percarbonate bleach, said bleach displaying improved stability.
  • It is a further object of the present invention to provide a granular laundry bleaching composition incorporating an alkali metal percarbonate bleach displaying improved stability, in which the percarbonate bleach does not require complex protection techniques.
  • It has now been found that these objects could be met by formulating a composition comprising an alkali metal salt of percarbonate together with a crystalline layered silicate or mixtures thereof.
  • Granular bleaching compositions comprising percarbonate have been described for instance in FR 2,385,837, US 4,428,914 and GB 1,553,505. Crystalline layered silicate and their methods of preparation have been described for instance in EP-A-164 514, DE-A-34 17 649 and DE-A-37 42 043 and their application to the field of laundry treatment has been described in applicant's copending British applications GB 90 21 761.3, GB 90 18157.9 and GB 91 08639.7.
  • The compositions according to the present invention also allow adequate control of the pH in the bleaching liquor, giving appropriate balance between bleaching performance and fabric safety.
    • Summary of the invention
  • Compositions according to the present invention are granular bleaching compositions comprising more than 20% and up to 80% by weight of the total composition of an alkali metal salt of percarbonate bleach and from 5% to 80% by weight of the total composition of a crystalline layered silicate of formula NaMSixO2x+1.yH₂O wherein M is sodium or hydrogen, x is a number of from 1.9 to 4 and y is a number of from 0 to 20, or mixtures thereof. Preferred compositions herein further comprise an anhydrous acidifying agent, preferably citric acid.
    • Detailed description of the invention
  • As a first essential component, the compositions according to the present invention comprise an alkali metal salt of percarbonate, preferably sodium percarbonate. Sodium percarbonate is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1, 1-diphosphonic acid (HEDP) or an amino-phosphonate, that is incorporated during the manufacturing process. For the purposes of the present invention, the percarbonate can be incorporated into detergent compositions without additional protection.
  • Whilst heavy metals present in the sodium carbonate used to manufacture the percarbonate can be controlled by the inclusion of sequestrants in the reaction mixture, it is preferred that the percarbonate be protected from heavy metals present as impurities in other ingredients of the product. It has been found that the total level of Iron, Copper and Manganese ions in the product should not exceed 25 ppm and preferably should be less than 20 ppm in order to avoid an unacceptably adverse effect on percarbonate stability.
  • The compositions according to the present invention comprise more than 20% by weight of the total composition of percarbonate, up to 80% by weight of the total composition, preferably from 40% to 50%.
  • The second essential component of the invention is a crystalline layered silicate. The crystalline layered silicates suitable for use herein are of the granular formula



            NaMSixO2x+1.yH₂O



    wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, or mixtures thereof. Crystalline layered sodium silicates of this type are disclosed in EP-A-164 514 and methods for their preparation are disclosed in DE-A-34 17 649 and DE-A-37 42 043. For the purposes of the present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the α, β, γ and δ forms of Na₂Si₂O₅ These materials are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is δ - Na₂Si₂O₅, NaSKS-6. Crystalline layered silicates are incorporated either as dry mixed solids, or as solid components of agglomerates with other components.
  • The compositions according to the present invention comprise from 5% to 80% by weight of the total composition of said crystalline layered silicates or mixtures thereof, preferably from 15% to 25%.
  • As an optional but highly preferred component, the compositions according to the present invention further comprise an anhydrous acidifying agent or mixtures thereof. The purpose of said acidifying agent is to control the alkalinity generated by the percarbonate in the bleaching liquor. Said agent need to be incorporated in the product in an anhydrous form, and to have a good stability in oxidizing environment. Suitable anhydrous acidifying agents for use herein are carboxylic acids such as citric acid, succinic acid, adipic acid, glutaric acid, 3 chetoglutaric acid, citramalic acid, tartaric acid and maleic acid. Other suitable acidifying agents include sodium bicarbonate, sodium sesquicarbonate and silicic acid. Highly preferred for use herein is citric acid. Indeed, citric acid is commercially available in anhydrous form, it additionally acts as a builder and a chelant, and it is biodegradable. The compositions according to the present invention comprise from up to 15% by weight of the total composition of anhydrous citric acid, preferably from 2% to 8%, most preferably about 5%.
  • Compositions in accordance with the invention can also comprise optional ingredients such as optical brighteners, anti dusting agents such as olefines and waxes, enzymes, chelants, dispersants, surfactants, soil release agents, photoactivated bleaches such as Zn phthalocyanine sulphonate, dyes, pigments and perfumes are examples of such optional ingredients and can be added in varying amounts as desired.
  • Optional but highly preferred ingredients are peroxy carboxylic acids bleach or precursors thereof, commonly referred to as bleach activators, which are preferably added in a prilled or agglomerated form. Examples of suitable compounds of this type are disclosed in British Patent GB 1 586 769 and GB 2 143 231 and a method for their formation into a prilled form is described in European Published Patent Application EP-A-62 523. Preferred examples of such compounds are tetracetyl ethylene diamine (TAED), sodium 3, 5, 5 trimethyl hexanoylorybenzene sulphonate, diperoxy dodecanoic acid as described for instance in US 4 818 425 and nonylamide of peroxyadipic acid as described for instance in US 4 259 201 and n-nonanoyloxybenzenesulphonate (NOBS), and acetyl triethyl citrate (ATC) such as described in European Patent application 91870207.7.
  • The compositions according to the present invention naturally comprise inorganic filler salts such as alkali metal carbonates bicarbonates and sulphates. Such fillers, for instance sodium bicarbonate, may also act as acidifying agent as described herein above. Accordingly, sodium percarbonate is a preferred filler material for use herein.
  • The compositions according to the present invention can be made by a variety of methods well known in the art, including dry-mixing, spray drying, agglomeration and granulation and combinations thereof.
  • The compositions according to the present invention can be prepared with different bulk densities, from conventional granular products to so-called "concentrated" products (i.e. with a bulk density above 600g/l).
    • Examples 1) Part A
  • The following examples will illustrate the present invention. The following granular compositions are made by dry-mixing the listed ingredients in the listed proportions.:
    Compositions 1 2 3 4 5 6
    Sodium percarbonate 40.0 35.0 54.0 55.0 46.0 47.0
    TAED 8.7 7.6 11.7 - 9.5 -
    Silicate layered SKS-6 25.0 30.0 20.0 10.0 18.0 20.0
    Anhydrous citric acid 10.0 12.0 12.0 5.0 5.0 5.0
    Sodium sulphate 15.3 14.3 1.0 20.0 0.5 15.0
    Sodium bicarbonate - - - 5.0 18.0 -
    NOBS - - - - - 10.3
    minors up to 100%
    • 2) Part B
  • The following compositions were made by mixing the listed ingredients in the listed proportions. The self heating rates of the products were monitored as follows. The product is made and put in a bottle. The bottle is then put in an oven which is heated up to 70°c. A probe in the product allows to monitor the temperature of the product. As soon as the product reaches 70°c, the bottle is covered and the system is isolated in an adiabatic/thermo bell which maintains the temperature of the oven constant at 70°c as above. This places the product in adiabatic conditions and from thereon, the temperature of the product is monitored. The temperature increase thus measured is due to the self-heating of the product (runaway reaction). The results below list three self heating rates, all in °c/hour: SHR1 is the average temperature increase measured during the first two hours of adiabatic conditions; SHR2 is the average temperature increase measured during the three following hours, and SHR3 is the average temperature increase measured beyond 5 hours. The table below lists the results obtained for various compositions, with and without crystalline layered silicate. In some cases the runaway reaction was out of control and experiments had to be interrupted for safety reasons. Such experiments are marked "ooc" (out of control).
    Compositions 7 7a 8 8a 9 9a
    Sodium percarbonate 47.0 47.0 47.0 47.0 47.0 47.0
    TAED 10.2 10.2 10.2 10.2 10.2 10.2
    Silicate SKS-6 20.0 -- 20.0 -- 20.0 --
    Citric acid 10.0 10.0 8.0 8.0 8.0 8.0
    Sodium Sulphate 11.7 31.7 13.7 33.7 9.2 29.2
    Sodium bicarbonate --- --- --- --- 4.5 4.5
    SHR1* 2.3 4.5 2.2 4.0 2.5 3.9
    SHR2** 0.6 8.9 0.6 8.0 0.5 7.7
    SHR3*** 0 ooc 0 ooc 0 ooc
    Compositions 10 10a 11 11a 12 12a
    Sodium percarbonate 47.0 47.0 47.0 47.0 47.0 47.0
    TAED 10.2 10.2 10.2 10.2 10.2 10.2
    Silicate SKS-6 18.0 -- 20.0 -- 42.8 ---
    Citric acid 7.0 7.0 5.0 5.0 --- ---
    Sodium Sulphate 16.7 34.7 16.7 36.7 --- 42.8
    Sodium bicarbonate --- --- --- --- --- ---
    SHR1* 2.7 4.1 2.2 4.1 2.2 4.0
    SHR2** 0.6 8.3 0.4 8.2 0.3 10.8
    SHR3*** 0 ooc 0 ooc 0 ooc
    • Comments:
  • Compositions 7-12 show good thermal stability, and no temperature increase is reported after 5 hours storage and beyond. In the absence of crystalline layered silicate i.e. in compositions 7a-12a, self-heating rates measured were so high that experiments had to be stopped for safety purposes.

Claims (7)

  1. A granular bleaching composition comprising more than 20% and up to 80% by weight of the total composition of an alkali metal salt of percarbonate bleach and from 5% to 80% by weight of the total composition of a crystalline layered silicate of formula NaMSixO2x+1.yH₂O wherein M is sodium or hydrogen, x is a number of from 1.9 to 4 and y is a number of from 0 to 20, or mixtures thereof.
  2. A granular bleaching composition according to claim 1 which comprises from 40% to 50% by weight of the total composition of a percarbonate bleach.
  3. A granular bleaching composition according to any of the preceding claims, characterized in that it comprises from 15% to 25% by weight of the total composition of said crystalline layered silicate or mixtures thereof.
  4. A granular bleaching composition according to any of the preceding claims, characterized in that the crystalline layered silicate is of the formula NaMSixO2x+1.yH₂O, wherein x is 2, M is sodium and y is 0.
  5. A granular bleaching composition according to any of the preceding claims, characterized in that it further comprises an anhydrous acififying agent.
  6. A granular bleaching composition according to claim 5 wherein said anhydrous acidifying agent is anhydrous citric acid.
  7. A granular bleaching composition according to claim 6 which comprises up to 15%, preferably from 2% to 12%, most preferably 5% by weight of the total composition of anhydrous citric acid.
EP92200005A 1992-01-03 1992-01-03 Granular laundry bleaching composition Ceased EP0550077A1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
EP92200005A EP0550077A1 (en) 1992-01-03 1992-01-03 Granular laundry bleaching composition
KR1019940702293A KR940703911A (en) 1992-01-03 1992-12-24 Granular percarbonate laundry bleach containing layered silicate stabilizer
JP5511910A JPH07502770A (en) 1992-01-03 1992-12-24 Granular percarbonate laundry bleach containing layered silicate stabilizers
CA002126847A CA2126847A1 (en) 1992-01-03 1992-12-24 Granular percarbonate laundry bleach containing layered silicate stabilizer
RU94035995/04A RU94035995A (en) 1992-01-03 1992-12-24 Granulated bleach composition
PCT/US1992/011222 WO1993012843A1 (en) 1992-01-03 1992-12-24 Granular percarbonate laundry bleach containing layered silicate stabilizer
BR9207019A BR9207019A (en) 1992-01-03 1992-12-24 Bleach for washing granular percarbonate containing layered silicate stabilizer
AU34224/93A AU666918B2 (en) 1992-01-03 1992-12-24 Granular percarbonate laundry bleach containing layered silicate stabilizer
MX9207671A MX9207671A (en) 1992-01-03 1992-12-30 GRANULATED BLEACHING COMPOSITION FOR LAUNDRY.
MA23046A MA22754A1 (en) 1992-01-03 1992-12-30 GRANULAR BLEACHING COMPOSITION FOR LAUNDRY.
CN93101189A CN1075749A (en) 1992-01-03 1993-01-02 Granular laundry bleaching composition

Applications Claiming Priority (1)

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EP92200005A EP0550077A1 (en) 1992-01-03 1992-01-03 Granular laundry bleaching composition

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EP0550077A1 true EP0550077A1 (en) 1993-07-07

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EP (1) EP0550077A1 (en)
JP (1) JPH07502770A (en)
KR (1) KR940703911A (en)
CN (1) CN1075749A (en)
AU (1) AU666918B2 (en)
BR (1) BR9207019A (en)
CA (1) CA2126847A1 (en)
MA (1) MA22754A1 (en)
MX (1) MX9207671A (en)
RU (1) RU94035995A (en)
WO (1) WO1993012843A1 (en)

Cited By (15)

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Publication number Priority date Publication date Assignee Title
EP0639639A1 (en) * 1993-08-17 1995-02-22 The Procter & Gamble Company Detergent compositions comprising percarbonate bleaching agents
WO1995025065A1 (en) * 1994-03-14 1995-09-21 Henkel Kommanditgesellschaft Auf Aktien Long-shelf-life fixed hydrogen peroxide-containing multi-substance mixtures in solid form, process for their production and their use
WO1996001887A1 (en) * 1994-07-07 1996-01-25 Henkel Kommanditgesellschaft Auf Aktien Powdered bleaching and washing agent
WO1996014267A1 (en) * 1994-11-02 1996-05-17 Henkel Kommanditgesellschaft Auf Aktien Direct synthesis of crystalline disilicates from sodium silicate solution
EP0737738A2 (en) 1995-04-12 1996-10-16 Cleantabs A/S Bleach tablets
EP0750661A1 (en) * 1994-03-14 1997-01-02 The Procter & Gamble Company Granular bleaching compositions
DE19525197A1 (en) * 1995-07-11 1997-01-16 Hoechst Ag Granular detergent builder
WO1997009269A1 (en) * 1995-09-04 1997-03-13 Henkel Kommanditgesellschaft Auf Aktien Solid multicomponent mixtures containing stable-in-storage hydrogen peroxide, method of preparing them and their use
EP0695800A3 (en) * 1994-08-04 1997-10-15 Hoechst Ag Washing composition
EP0745664B1 (en) * 1994-02-25 1998-05-13 Eka Chemicals AB Bleaching agent
US5854198A (en) * 1996-03-15 1998-12-29 Lever Brothers Company, Division Of Conopco, Inc. Particulate aluminosilicate-built detergent compositions comprising cogranules of zeolite map and alkali metal silicate
GB2353800A (en) * 1999-09-02 2001-03-07 Procter & Gamble Antibacterial detergent compositions
WO2009017748A1 (en) * 2007-07-30 2009-02-05 Milliken & Company Solid cleaning composition and method of use
WO2009122125A1 (en) * 2008-04-01 2009-10-08 Reckitt Benckiser Inc. Laundry treatment compositions
FR3072390A1 (en) * 2017-10-18 2019-04-19 Quadrimex Chemical Sas EXTENDED COMPOSITION COMPRISING A MIXTURE OF TWO PRODUCTS FOR THE DESTRUCTION OF ORGANOPHOSPHORUS AND / OR ORGANOSOUFRES POLLUTANTS

Families Citing this family (1)

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JPH09511533A (en) * 1994-09-19 1997-11-18 ザ、プロクター、エンド、ギャンブル、カンパニー Granular bleaching composition

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EP0337219A2 (en) * 1988-04-15 1989-10-18 Hoechst Aktiengesellschaft Storage stabilized detergent with increased bleaching effect
EP0416366A2 (en) * 1989-09-08 1991-03-13 Hoechst Aktiengesellschaft Dishwashing composition comprising layered silicates

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EP0416366A2 (en) * 1989-09-08 1991-03-13 Hoechst Aktiengesellschaft Dishwashing composition comprising layered silicates

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0639639A1 (en) * 1993-08-17 1995-02-22 The Procter & Gamble Company Detergent compositions comprising percarbonate bleaching agents
US5846922A (en) * 1994-02-25 1998-12-08 Eka Chemicals Ab Bleaching agent
EP0745664B1 (en) * 1994-02-25 1998-05-13 Eka Chemicals AB Bleaching agent
WO1995025065A1 (en) * 1994-03-14 1995-09-21 Henkel Kommanditgesellschaft Auf Aktien Long-shelf-life fixed hydrogen peroxide-containing multi-substance mixtures in solid form, process for their production and their use
EP0750661A4 (en) * 1994-03-14 1998-10-07 Procter & Gamble PELLET BLEACHING COMPOSITIONS
EP0750661A1 (en) * 1994-03-14 1997-01-02 The Procter & Gamble Company Granular bleaching compositions
WO1996001887A1 (en) * 1994-07-07 1996-01-25 Henkel Kommanditgesellschaft Auf Aktien Powdered bleaching and washing agent
EP0695800A3 (en) * 1994-08-04 1997-10-15 Hoechst Ag Washing composition
WO1996014267A1 (en) * 1994-11-02 1996-05-17 Henkel Kommanditgesellschaft Auf Aktien Direct synthesis of crystalline disilicates from sodium silicate solution
EP0737738A3 (en) * 1995-04-12 1998-04-01 Cleantabs A/S Bleach tablets
EP0737738A2 (en) 1995-04-12 1996-10-16 Cleantabs A/S Bleach tablets
DE19525197A1 (en) * 1995-07-11 1997-01-16 Hoechst Ag Granular detergent builder
WO1997009269A1 (en) * 1995-09-04 1997-03-13 Henkel Kommanditgesellschaft Auf Aktien Solid multicomponent mixtures containing stable-in-storage hydrogen peroxide, method of preparing them and their use
US5854198A (en) * 1996-03-15 1998-12-29 Lever Brothers Company, Division Of Conopco, Inc. Particulate aluminosilicate-built detergent compositions comprising cogranules of zeolite map and alkali metal silicate
GB2353800A (en) * 1999-09-02 2001-03-07 Procter & Gamble Antibacterial detergent compositions
WO2009017748A1 (en) * 2007-07-30 2009-02-05 Milliken & Company Solid cleaning composition and method of use
WO2009122125A1 (en) * 2008-04-01 2009-10-08 Reckitt Benckiser Inc. Laundry treatment compositions
FR3072390A1 (en) * 2017-10-18 2019-04-19 Quadrimex Chemical Sas EXTENDED COMPOSITION COMPRISING A MIXTURE OF TWO PRODUCTS FOR THE DESTRUCTION OF ORGANOPHOSPHORUS AND / OR ORGANOSOUFRES POLLUTANTS
FR3072391A1 (en) * 2017-10-18 2019-04-19 Quadrimex Chemical EXTENDED COMPOSITION COMPRISING A MIXTURE OF TWO PRODUCTS FOR THE DESTRUCTION OF ORGANOPHOSPHORUS AND / OR ORGANOSOUFRES POLLUTANTS

Also Published As

Publication number Publication date
AU666918B2 (en) 1996-02-29
AU3422493A (en) 1993-07-28
JPH07502770A (en) 1995-03-23
CN1075749A (en) 1993-09-01
BR9207019A (en) 1995-12-05
MX9207671A (en) 1994-05-31
MA22754A1 (en) 1993-07-01
CA2126847A1 (en) 1993-07-08
KR940703911A (en) 1994-12-12
WO1993012843A1 (en) 1993-07-08
RU94035995A (en) 1996-06-20

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