EP0879876A1 - Process for preparation of granular detergent composition or component comprising a water-soluble cationic surfactant - Google Patents

Process for preparation of granular detergent composition or component comprising a water-soluble cationic surfactant Download PDF

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Publication number
EP0879876A1
EP0879876A1 EP97201517A EP97201517A EP0879876A1 EP 0879876 A1 EP0879876 A1 EP 0879876A1 EP 97201517 A EP97201517 A EP 97201517A EP 97201517 A EP97201517 A EP 97201517A EP 0879876 A1 EP0879876 A1 EP 0879876A1
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EP
European Patent Office
Prior art keywords
water
weight
cationic surfactant
detergent composition
soluble
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Withdrawn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
EP97201517A
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German (de)
French (fr)
Inventor
Christopher Andrew Morrison
Carole Patricia Denise Wilkinson
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
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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 EP97201517A priority Critical patent/EP0879876A1/en
Priority to PCT/IB1998/000712 priority patent/WO1998053037A1/en
Priority to MA25083A priority patent/MA24550A1/en
Priority to ARP980102359 priority patent/AR015327A1/en
Publication of EP0879876A1 publication Critical patent/EP0879876A1/en
Withdrawn legal-status Critical Current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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates

Definitions

  • the present invention provides a process for the preparation of granular detergent composition or component comprising a water-soluble cationic surfactant, and also provides granular detergent composition or component obtainable by the process.
  • Cationic surfactants are well-known detergent ingredients which are used, in particular, for imparting a soft feel to fabrics after they have been washed.
  • the most commonly used cationic surfactants are commercially available as aqueous solutions, typically with a surfactant activity of about 35% or 40%.
  • Various techniques are known to dry the aqueous solutions to form powders, however these techniques have a number of disadvantages. Expensive equipment may be required, and the process may require temperatures which cause the cationic surfactant to degrade. The products prepared in this way tend to be sticky which makes subsequent handling and processing difficult.
  • simply adding cationic surfactant in the form a fine powder to a granular detergent matrix significantly impairs the dispensing properties of the product for example by forming sticky, viscous gels upon contact with water.
  • EP-A-0 714 976 published on 5th June 1996, describes a process for spray drying cationic surfactant in the presence of low levels of anionic surfactants.
  • the counter-current spray drying process described requires high temperatures which can cause some cationic surfactants to degrade.
  • the object of the invention is to provide a process for incorporating aqueous solutions of cationic surfactants into free-flowing, high bulk density, high active detergent granules and to avoid any degredation of the cationic surfactants, especially those with alkyl chains of C10 or less, due to high temperatures.
  • a further object of the invention is to provide detergent granule composition which comprise cationic surfactants and which provide good dispensing properties when used as a component of a laundry product.
  • drying step is carried out in a co-current spray dryer and the drying gas is air.
  • the aqueous solution or dispersion also comprises water-soluble silicate.
  • a suitable water-soluble silicate is sodium silicate having a ratio of SiO2 to Na2O is from 0.5 to 3.3, preferably from 1.0 to 2.4.
  • the water-soluble cationic surfactant is a quaternary ammonium salt having the general formula R1R2R3R4 N + and wherein R1 is a C6 to C10 alkyl chain and R2, R3, and R4 are C1 to C7 alkyl or hydroxy alkyl chains
  • the invention also relates to a granular detergent composition or component comprising:
  • the aqueous solution or dispersion of cationic surfactant is dried to remove water and form a free-flowing granular product.
  • the drying step is carried out with a drying gas having a temperature of less than 250°C, preferably in a concurrent spray dryer.
  • a drying gas having a temperature of less than 250°C, preferably in a concurrent spray dryer.
  • the aqueous solution or dispersion is atomised to form droplets, and the droplets are directed into a hot gas entering the drying chamber.
  • spray evaporation is rapid, the hot drying gas cools accordingly, and evaporation times are short.
  • the cationic surfactant is not subject to heat degradation.
  • Both rotary and nozzle-type atomisers can be used in co-current spray dryers. Most commonly the hot drying gas is air.
  • An alternative arrangement is a counter-current spray dryer in which the droplets and the hot gas pass through the drying chamber in generally opposite directions.
  • this arrangement often results in temperatures greater than 250°C which falls outside of the scope of the present invention.
  • Cationic surfactants useful in the present invention include water-soluble quaternary ammonium compounds of the form R 1 R 2 R 3 R 4 N + X - , in which R 1 is a hydroxyalkyl group having no greater than 6 carbon atoms; each of R 2 and R 3 is independently selected from C 1-4 alkyl or alkenyl; R 4 is a C 5-11 alkyl or alkenyl; and X - is a counterion.
  • the cationic surfactant comprises a mixture of cationic surfactants of formula I: R 1 R 2 R 3 R 4 N + X - in which R 1 is a hydroxyalkyl group having no greater than 6 carbon atoms; each of R 2 and R 3 is independently selected from C 1-4 alkyl or alkenyl; R 4 is a C 5-11 alkyl or alkenyl; and X - is a counterion which does not substantially exchange with a hydroxide ion in a 0.5% by weight aqueous solution of the detergent composition at 20°C and wherein, in the mixture of cationic surfactants of formula I, at least 10%, preferably at least 20 % or event at least 50% by weight of the cationic surfactant has R 4 which is C 5-9 alkyl or alkenyl.
  • the cationic surfactant comprises a mixture of surfactants of formula I wherein there is a longer alkyl chain surfactant having R 4 with n carbon atoms where n is from 8 to 11 and a shorter alkyl chain surfactant having (n-2) carbon atoms.
  • alkyl or alkenyl as used herein may be branched, linear or substituted.
  • Substituents may be for example, aromatic groups, heterocyclic groups containing one or more N, S or O atoms, or halo substituents.
  • Silicates are well-known detergent components, and are optional components of the present invention.
  • sodium silicate is often added to detergent compositions in order to act as a corrosion inhibitor.
  • Water-soluble silicates which are suitable for use in the present invention may be amorphous or layered.
  • Such silicates may be characterised by the ratio of SiO 2 to Na 2 O in their structure. In the present invention, this ratio may typically be less than 3.3:1, preferably less than 2.8:1, more preferably less than 2.4:1, most preferably about 2.0:1.
  • amorphous silicates are preferred to crystalline silicates.
  • crystalline silicates may be included in the paste compositions of the invention.
  • Crystalline layered sodium silicates have the general formula NaMSi x O 2x+1 . yH 2 O wherein m is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20.
  • 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. More preferably M is sodium.
  • Preferred examples of this formula comprise the ⁇ -, ⁇ -, ⁇ -, ⁇ - forms of Na 2 Si 2 O 5 . These materials are available from Hoechst AG, Germany, as, respectively, NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is ⁇ - Na 2 Si 2 O 5 , NaSKS-6.
  • aqueous solution or dispersion of the water-soluble cationic surfactant and the silicate, where present, in the process of the present invention may be carried out using any suitable mixing equipment.
  • One particularly suitable piece of mixing equipment is known in the industry as a "crutcher”.
  • Other materials may be added to the crutcher at this stage, especially inorganic materials such as aluminosilicate, sulphate etc.
  • the free-flowing granular product may be dry mixed or otherwise blended with other detergent components to form a finished detergent composition.
  • Typical components of a finished detergent composition include surfactants, soluble and insoluble builders, cheating agents, anti-redeposition and soil suspension agents, bleach and bleach activators, optical brighteners, soil release agents, suds suppressors, enzymes, fabric softening agents including clays, perfumes and colours, as well as other ingredients known to be useful in laundry detergents.
  • composition of Examples 1 to 3 were made by mixing aqueous solution of the quaternary ammonium salt (50% active) with an aqueous solution of the sodium silicate (45% active), and forming a homogeneous single phase mixture. The mixture was then passed through an atomising nozzle within a co-current spray-drying tower having an inlet air temperature of about 200°C. The hot granular compositions were collected at the bottom of the spray-drying tower and allowed to cool to ambient temperature. The resulting granular compositions were found to be free-flowing.

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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)
  • Detergent Compositions (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

The invention provides a process which comprises the step of drying an aqueous solution or dispersion, the aqueous solution or dispersion comprising a water-soluble cationic surfactant, in the presence of a drying gas wherein the maximum temperature of the drying gas is less than 250°C. Preferably the drying step is carried out in a co-current spray dryer and the drying gas is air.

Description

The present invention provides a process for the preparation of granular detergent composition or component comprising a water-soluble cationic surfactant, and also provides granular detergent composition or component obtainable by the process.
Cationic surfactants are well-known detergent ingredients which are used, in particular, for imparting a soft feel to fabrics after they have been washed. The most commonly used cationic surfactants are commercially available as aqueous solutions, typically with a surfactant activity of about 35% or 40%. Various techniques are known to dry the aqueous solutions to form powders, however these techniques have a number of disadvantages. Expensive equipment may be required, and the process may require temperatures which cause the cationic surfactant to degrade. The products prepared in this way tend to be sticky which makes subsequent handling and processing difficult. Furthermore, simply adding cationic surfactant in the form a fine powder to a granular detergent matrix significantly impairs the dispensing properties of the product for example by forming sticky, viscous gels upon contact with water.
EP-A-0 714 976, published on 5th June 1996, describes a process for spray drying cationic surfactant in the presence of low levels of anionic surfactants. However the counter-current spray drying process described requires high temperatures which can cause some cationic surfactants to degrade.
The object of the invention is to provide a process for incorporating aqueous solutions of cationic surfactants into free-flowing, high bulk density, high active detergent granules and to avoid any degredation of the cationic surfactants, especially those with alkyl chains of C10 or less, due to high temperatures.
A further object of the invention is to provide detergent granule composition which comprise cationic surfactants and which provide good dispensing properties when used as a component of a laundry product.
Summary of the Invention
According to the invention these objects are achieved by a process which comprises the steps of:
  • drying an aqueous solution or dispersion, the aqueous solution or dispersion comprising a water-soluble cationic surfactant, in the presence of a drying gas wherein the maximum temperature of the drying gas is less than 250°C.
    • Preferably the drying step is carried out in a co-current spray dryer and the drying gas is air.
    Preferably the aqueous solution or dispersion also comprises water-soluble silicate. A suitable water-soluble silicate is sodium silicate having a ratio of SiO2 to Na2O is from 0.5 to 3.3, preferably from 1.0 to 2.4. Preferably the water-soluble cationic surfactant is a quaternary ammonium salt having the general formula R1R2R3R4 N+ and wherein R1 is a C6 to C10 alkyl chain and R2, R3, and R4 are C1 to C7 alkyl or hydroxy alkyl chains
    The invention also relates to a granular detergent composition or component comprising:
  • from 15% to 40%, preferably 25% to 40% by weight of water-soluble cationic surfactant;
  • from 5% to 85%, preferably 50% to 70% by weight of water-soluble silicate; and
  • from 0% to 20%, preferably 5% to 10% by weight of water.
    • Detailed Description of the Invention
    In the process of the invention the aqueous solution or dispersion of cationic surfactant (and silicate, when present), is dried to remove water and form a free-flowing granular product. The drying step is carried out with a drying gas having a temperature of less than 250°C, preferably in a concurrent spray dryer. In a spray dryer the aqueous solution or dispersion is atomised to form droplets, and the droplets are directed into a hot gas entering the drying chamber. In typical co-current spray dryers the droplets and the hot drying gas pass through the spray dryer in the same direction. Spray evaporation is rapid, the hot drying gas cools accordingly, and evaporation times are short. The cationic surfactant is not subject to heat degradation. Both rotary and nozzle-type atomisers can be used in co-current spray dryers. Most commonly the hot drying gas is air.
    An alternative arrangement, is a counter-current spray dryer in which the droplets and the hot gas pass through the drying chamber in generally opposite directions. However this arrangement often results in temperatures greater than 250°C which falls outside of the scope of the present invention.
    Other means of drying the aqueous solution or dispersion of cationic surfactant may also be used provided that the maximum temperature that the cationic surfactant is exposed to does not exceed 250°C. Another such means is spray-granulation, which may be particularly advantageous because the maximum temperature may be kept below 200°C, and preferably below 150°C.
    Cationic surfactants useful in the present invention include water-soluble quaternary ammonium compounds of the form R1 R2R3R4N+X-, in which R1 is a hydroxyalkyl group having no greater than 6 carbon atoms; each of R2 and R3 is independently selected from C1-4 alkyl or alkenyl; R4 is a C5-11 alkyl or alkenyl; and X- is a counterion.
    In a preferred embodiment of the invention, the cationic surfactant comprises a mixture of cationic surfactants of formula I: R1R2R3R4N+X- in which R1 is a hydroxyalkyl group having no greater than 6 carbon atoms; each of R2 and R3 is independently selected from C1-4 alkyl or alkenyl; R4 is a C5-11 alkyl or alkenyl; and X- is a counterion which does not substantially exchange with a hydroxide ion in a 0.5% by weight aqueous solution of the detergent composition at 20°C and wherein, in the mixture of cationic surfactants of formula I, at least 10%, preferably at least 20 % or event at least 50% by weight of the cationic surfactant has R4 which is C5-9 alkyl or alkenyl.
    In accordance with this preferred embodiment of the invention, the cationic surfactant comprises a mixture of surfactants of formula I wherein there is a longer alkyl chain surfactant having R4 with n carbon atoms where n is from 8 to 11 and a shorter alkyl chain surfactant having (n-2) carbon atoms.
    Unless otherwise stated alkyl or alkenyl as used herein may be branched, linear or substituted. Substituents may be for example, aromatic groups, heterocyclic groups containing one or more N, S or O atoms, or halo substituents.
    Silicates are well-known detergent components, and are optional components of the present invention. In particular sodium silicate is often added to detergent compositions in order to act as a corrosion inhibitor. Water-soluble silicates which are suitable for use in the present invention may be amorphous or layered.
    Such silicates may be characterised by the ratio of SiO2 to Na2O in their structure. In the present invention, this ratio may typically be less than 3.3:1, preferably less than 2.8:1, more preferably less than 2.4:1, most preferably about 2.0:1.
    In terms of the present invention, amorphous silicates are preferred to crystalline silicates. However, crystalline silicates may be included in the paste compositions of the invention.
    Crystalline layered sodium silicates have the general 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. 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 purpose 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. Preferred examples of this formula comprise the α-, β-, γ-, δ- forms of Na2Si2O5. These materials are available from Hoechst AG, Germany, as, respectively, NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is δ- Na2Si2O5, NaSKS-6.
    The aqueous solution or dispersion of the water-soluble cationic surfactant and the silicate, where present, in the process of the present invention may be carried out using any suitable mixing equipment. One particularly suitable piece of mixing equipment is known in the industry as a "crutcher". Other materials may be added to the crutcher at this stage, especially inorganic materials such as aluminosilicate, sulphate etc.
    Finally the free-flowing granular product may be dry mixed or otherwise blended with other detergent components to form a finished detergent composition. Typical components of a finished detergent composition include surfactants, soluble and insoluble builders, cheating agents, anti-redeposition and soil suspension agents, bleach and bleach activators, optical brighteners, soil release agents, suds suppressors, enzymes, fabric softening agents including clays, perfumes and colours, as well as other ingredients known to be useful in laundry detergents.
    Examples
    Granular detergent compositions were prepared as follows:
    Example 1 Example 2 Example 3 Comparative Example 4
    Quaternary ammonium salt 20 28 28 20
    Sodium alkyl sulphate - - - 1.6
    Sodium silicate (Ratio = 2.0) 28 64 - -
    Filler 44 - 65 balance
    Water 8 8 7 5
    In these examples the following abbreviations have been used:
  • Quaternary ammonium salt is C8-C10 dimethyl hydroxy ethyl ammonium chloride.
  • Sodium alkyl sulphate is the sodium salt of a sulphated C12-C14 linear alcohol.
  • Filler is sodium sulphate or sodium aluminosilicate (zeolite 4A).
    • The composition of Examples 1 to 3 were made by mixing aqueous solution of the quaternary ammonium salt (50% active) with an aqueous solution of the sodium silicate (45% active), and forming a homogeneous single phase mixture. The mixture was then passed through an atomising nozzle within a co-current spray-drying tower having an inlet air temperature of about 200°C. The hot granular compositions were collected at the bottom of the spray-drying tower and allowed to cool to ambient temperature. The resulting granular compositions were found to be free-flowing.

    Claims (9)

    1. A process for the preparation of a granular detergent composition or component comprising a step of drying an aqueous solution or dispersion, the aqueous solution or dispersion comprising a water-soluble cationic surfactant, wherein the drying step is carried out using a drying gas, and characterised in that the drying gas has a maximum temperature of less than 250°C.
    2. A process according to claim 1 wherein the drying step is carried out in a co-current spray dryer.
    3. A process according to either claim 1 or claim 2 wherein the aqueous solution or dispersion further comprises water-soluble sodium silicate, and wherein the ratio of SiO2 to Na2O is from 0.5 to 3.3.
    4. A process according to claim 3 wherein the ratio of SiO2 to Na2O is from 1.0 to 2.4.
    5. A process according to claim 1 wherein the water-soluble cationic surfactant is a quaternary ammonium salt having the general formula R1R2R3R4 N+ and wherein R1 is a C6 to C10 alkyl chain and R2, R3, and R4 are C1 to C7 alkyl or hydroxy alkyl chains.
    6. A granular detergent composition or component comprising:
      from 15% by weight to 40% by weight of water-soluble cationic surfactant;
      from 5% by weight to 85% by weight of water-soluble silicate; and
      optionally, up to 20% by weight of water.
    7. A granular detergent composition or component according to claim 6 wherein the water-soluble silicate is sodium silicate, and wherein the ratio of SiO2 to Na2O is from 0.5 to 3.3, preferably from 1.0 to 2.4.
    8. A granular detergent composition or component according to claim 6 wherein the water-soluble cationic surfactant is a quaternary ammonium salt having the general formula R1R2R3R4 N+ and wherein R1 is a C6 to C10 alkyl chain and R2, R3, and R4 are C1 to C7 alkyl or hydroxy alkyl chains.
    9. A granular detergent composition or component according to any of claims 6 to 8 consisting essentially of:
      from 25% by weight to 40% by weight of water-soluble cationic surfactant;
      from 50% by weight to 70% by weight of water-soluble silicate; and
      from 5% by weight to 10% by weight of water.
    EP97201517A 1997-05-21 1997-05-21 Process for preparation of granular detergent composition or component comprising a water-soluble cationic surfactant Withdrawn EP0879876A1 (en)

    Priority Applications (4)

    Application Number Priority Date Filing Date Title
    EP97201517A EP0879876A1 (en) 1997-05-21 1997-05-21 Process for preparation of granular detergent composition or component comprising a water-soluble cationic surfactant
    PCT/IB1998/000712 WO1998053037A1 (en) 1997-05-21 1998-05-13 Process for preparation of granular detergent composition or component comprising a water-soluble cationic surfactant
    MA25083A MA24550A1 (en) 1997-05-21 1998-05-20 PROCESS FOR THE PREPARATION OF A GRANULAR DETERGENT COMPOSITION OR COMPONENT COMPRISING A CATIONIC WATER-SOLUBLE SURFACTANT
    ARP980102359 AR015327A1 (en) 1997-05-21 1998-05-21 PROCESS TO PREPARE A COMPOSITION OR DETERGENT GRANULATED COMPONENT THAT INCLUDES CATIONIC SURFACTANT SOLUBLE IN WATER

    Applications Claiming Priority (1)

    Application Number Priority Date Filing Date Title
    EP97201517A EP0879876A1 (en) 1997-05-21 1997-05-21 Process for preparation of granular detergent composition or component comprising a water-soluble cationic surfactant

    Publications (1)

    Publication Number Publication Date
    EP0879876A1 true EP0879876A1 (en) 1998-11-25

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    Application Number Title Priority Date Filing Date
    EP97201517A Withdrawn EP0879876A1 (en) 1997-05-21 1997-05-21 Process for preparation of granular detergent composition or component comprising a water-soluble cationic surfactant

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    EP (1) EP0879876A1 (en)
    AR (1) AR015327A1 (en)
    MA (1) MA24550A1 (en)
    WO (1) WO1998053037A1 (en)

    Families Citing this family (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    GB0009029D0 (en) 2000-04-12 2000-05-31 Unilever Plc Laundry wash compositions
    GB0009877D0 (en) 2000-04-20 2000-06-07 Unilever Plc Granular detergent component and process for its preparation
    BRPI1014709A2 (en) * 2009-04-28 2016-04-12 Clariant Brazil S A laundry detergent compositions

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    Publication number Priority date Publication date Assignee Title
    FR2101555A5 (en) * 1970-07-10 1972-03-31 Unilever Nv
    US4073735A (en) * 1976-02-19 1978-02-14 Colgate Palmolive Company Rinse cycle fabric softener
    SU732376A1 (en) * 1977-09-23 1980-05-05 Всесоюзный Научно-Исследовательский Институт Жиров Method of producing powdered synthetic detergent
    JPS5710699A (en) * 1980-06-24 1982-01-20 Dainichiseika Color Chem Production of additive for powder detergent
    DE3437721A1 (en) * 1984-10-15 1986-04-17 Süd-Chemie AG, 8000 München DETERGENT ADDITIVE
    WO1990004015A1 (en) * 1988-10-04 1990-04-19 Henkel Kommanditgesellschaft Auf Aktien Process for producing particulate detergents
    WO1993011212A1 (en) * 1991-11-30 1993-06-10 Henkel Kommanditgesellschaft Auf Aktien Powdery surface-active agent mixture

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    Publication number Priority date Publication date Assignee Title
    EP0002084A1 (en) * 1977-11-17 1979-05-30 THE PROCTER & GAMBLE COMPANY Granular detergent compositions for improved greasy soil removal
    US4806253A (en) * 1984-11-13 1989-02-21 The Procter & Gamble Company Laundry compositions
    US5259964A (en) * 1991-12-18 1993-11-09 Colgate-Palmolive Co. Free-flowing powder fabric softening composition and process for its manufacture
    US5703037A (en) * 1994-04-20 1997-12-30 The Procter & Gamble Company Process for the manufacture of free-flowing detergent granules

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    FR2101555A5 (en) * 1970-07-10 1972-03-31 Unilever Nv
    US4073735A (en) * 1976-02-19 1978-02-14 Colgate Palmolive Company Rinse cycle fabric softener
    SU732376A1 (en) * 1977-09-23 1980-05-05 Всесоюзный Научно-Исследовательский Институт Жиров Method of producing powdered synthetic detergent
    JPS5710699A (en) * 1980-06-24 1982-01-20 Dainichiseika Color Chem Production of additive for powder detergent
    DE3437721A1 (en) * 1984-10-15 1986-04-17 Süd-Chemie AG, 8000 München DETERGENT ADDITIVE
    WO1990004015A1 (en) * 1988-10-04 1990-04-19 Henkel Kommanditgesellschaft Auf Aktien Process for producing particulate detergents
    WO1993011212A1 (en) * 1991-11-30 1993-06-10 Henkel Kommanditgesellschaft Auf Aktien Powdery surface-active agent mixture

    Non-Patent Citations (2)

    * Cited by examiner, † Cited by third party
    Title
    DATABASE WPI Section Ch Week 8107, Derwent World Patents Index; Class D25, AN 81-11000D, XP002045322 *
    DATABASE WPI Section Ch Week 8209, Derwent World Patents Index; Class A97, AN 82-16388E, XP002045321 *

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    Publication number Publication date
    WO1998053037A1 (en) 1998-11-26
    AR015327A1 (en) 2001-05-02
    MA24550A1 (en) 1998-12-31

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