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WO1997009406A1 - Detergent composition comprising clay flocculating polymer with particle size less than 250 microns - Google Patents

Detergent composition comprising clay flocculating polymer with particle size less than 250 microns Download PDF

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Publication number
WO1997009406A1
WO1997009406A1 PCT/US1996/014106 US9614106W WO9709406A1 WO 1997009406 A1 WO1997009406 A1 WO 1997009406A1 US 9614106 W US9614106 W US 9614106W WO 9709406 A1 WO9709406 A1 WO 9709406A1
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WO
WIPO (PCT)
Prior art keywords
clay
flocculating polymer
detergent composition
clay flocculating
particle size
Prior art date
Application number
PCT/US1996/014106
Other languages
French (fr)
Inventor
Michael Keith Fenney
Jean Wevers
Original Assignee
The Procter & Gamble Company
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 The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AT96929867T priority Critical patent/ATE221570T1/en
Priority to DK96929867T priority patent/DK0865480T3/en
Priority to BR9610465A priority patent/BR9610465A/en
Priority to EP96929867A priority patent/EP0865480B1/en
Priority to DE69622744T priority patent/DE69622744T2/en
Priority to JP51132997A priority patent/JP3894953B2/en
Publication of WO1997009406A1 publication Critical patent/WO1997009406A1/en

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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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions

Definitions

  • the invention relates to a granular detergent composition
  • a granular detergent composition comprising (i) a softening clay and (ii) a clay flocculating polymer, and to a process for making the composition.
  • the composition is particularly useful in "softening-through-the-wash" products.
  • Clay flocculating polymer such as polyethylene oxide having high molecular weight, is commercially available as a 100% active powder.
  • EP-A-0 299 575 discloses granular detergent compositions comprising softening clay and polymeric clay-flocculating polymer. It is stated that in preparing a granular detergent composition the polymeric clay- flocculating agent can be added in a variety of ways. It may be added to the crutcher mix prior to spray-drying; or it may be sprayed onto a granular detergent from a solution in water or an organic solvent; or it may be dry-mixed, in the form of particles, with a granular detergent. This application does not mention preferred particle size of clay flocculating polymer.
  • Patchy deposition is where visible lumps of clay deposit on a fabric surface. It is caused when the clay particles are flocculated very rapidly before they have had chance to disperse. This leads to the formation of lumps of clay which deposit on the fabric surface. Residues are caused when high local concentrations of the clay flocculating polymer, present in the formulation, form gels on contact with water, leading to poor dispensing ofthe product and an increased risk of product deposition on clothes.
  • clay flocculating polymers when handled in particulate form, give rise to handling and explosivity problems.
  • undesirable patchy clay deposition and residues are avoided by sieving or grinding the clay flocculating polymer such that at least 95% by weight of the clay flocculating polymer has a particle size of less than 250 micrometers, and preferably less than 150 micrometers, before adding it to the granular detergent composition.
  • the clay flocculating polymer is a polyethylene oxide with an average molecular weight of between 100 000 and 10 million, more preferably between 150 000 and 800 000.
  • a process for making a granular detergent composition comprising the step of premixing the clay flocculating polymer with a powder selected from the group consisting of aluminosilicate, silicate, carbonate, citrate, phosphate, or mixtures thereof, and subsequently mixing the premix with other detergent components.
  • the premix consists of the clay flocculating polymer and aluminosilicate in a ratio of from 1:20 to 20:1.
  • Softening clays may be either unmodified or organically modified. Those clays which are not organically modified can be described as expandable, three-layered clays, i.e., aluminosilicates and magnesium silicates, having an ion exchange capacity of at least 50 eq/lOOg. of clay and preferably at least 60 meq/100 g. of clay.
  • the starting clays for the organically modified clays can be similarly described.
  • the term "expandable" as used to describe clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water.
  • the three-layer expandable clays used herein are those materials classified geologically as smectites.
  • the family of smectite (or montmorillonoid) clays includes the following trioctahedral minerals: talc; hectorite; saponite; sauconite; vermiculite; and the following dioctahedral minerals: prophyllite; montmorillonite; volchonskoite and nontronite.
  • the clays employed in these compositions contain cationic counterions such as protons, sodium ions, potassium ions, calcium ions, and lithium ions. It is customary to distinguish between clays on the basis of one cation predominantly or exclusively absorbed. For example, a sodium clay is one in which the absorbed cation is predominantly sodium. Such absorbed cations can become involved in exchange reactions with cations present in aqueous solutions.
  • cation exchange capacity (sometimes termed “base exchange capacity") in terms of milliequivalents per 100 g. of clay (meq/lOOg).
  • base exchange capacity cation exchange capacity
  • the cation exchange capacity of clays can be measured in several ways, including by electrodialysis, by exchange with ammonium ion followed by titration, or by a methylene blue procedure, all as fully set forth in Grimshaw, "The Chemistry and Physics of Clays", pp. 264-265, Interscience (1971).
  • the cation exchange capacity of a clay material relates to such factors as the expandable properties ofthe clay, the charge ofthe clay (which in turn is determined at least in part by the lattice structure), and the like.
  • the ion exchange capacity of clays varies widely in the range form about 2 meq/ 100 g. of kaolinites to about 150 meq/100 g., and greater, for certain smectite clays.
  • Preferred smectite-type clays are sodium montmorillonite, potassium montmorillonite, sodium hectorite and potassium hectorite.
  • the clays used herein have a particle size range of up to about 1 micron.
  • any ofthe clays used herein may be either naturally or synthetically derived.
  • clay flocculating polymers are fairly long chained polymers and co-polymers derived from such monomers as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone and ethylene imine. Gums, like guar gum, are suitable as well. Preferred are polymers of ethylene oxide, acrylamide or acrylic acid. These polymers dramatically enhance the deposition of a fabric softening clay if their molecular weights are in the range of from 100 000 to 10 million. Preferred are such polymers having a weight average molecular weight of from 150000 to 5 million.
  • the most preferred polymer is poly (ethylene oxide).
  • Molecular weight distributions can be readily determined using gel permeation chromatography, against standards of poly (ethylene oxide) of narrow molecular weight distributions.
  • the particle size of the polymer is reduced by either a standard milling operation or through physical screening ofthe particles.
  • the raw material is then optionally mixed with a powder, such as fine aluminosilicate (Zeolite type A) in a mixer and then added to a finished product process.
  • a powder such as fine aluminosilicate (Zeolite type A) in a mixer and then added to a finished product process.
  • the zeolite acts as a carrier for the polymer, helping to aid its dispersion in the finished product making.
  • particle size alteration equipment can be used to reduce the mean particle size ofthe clay flocculating polymer to below 250 micrometers.
  • Continuous screens such as Russel Finex and Mogenson vibratory screens, or continuous scraper screens. Batch screening operations involving RoTap variants are also applicable for small quantities.
  • continuous air jet mills can be used that both size reduce and classify the material at the same time.
  • the polymer particles may be treated by micronisation to further reduce mean particle size.
  • the particulate components of the present invention will normally be inco ⁇ orated into finished detergent products, especially those comprising softening clay.
  • Other conventional detergent ingredients such as anionic and nonionic surfactants, builders, bleach, bleach activator, suds suppressor, enzymes (e.g. protease, amylase, cellulase, lipase), perfume brightener, soil release polymer will commonly be used.
  • enzymes e.g. protease, amylase, cellulase, lipase
  • perfume brightener soil release polymer
  • PEO Polyethyleneoxide polymer as supplied by Union Carbide as WSRN750 (Trade Name). Typical particle size distribution: 2% above 710 micrometers
  • PEO sized: As above but with 95% of the material above 150 micrometers removed via a size reduction process. Typical particle size distribution:
  • Zeolite A supplied by Industrial Zeolite Ltd., Thurrock, England. Typical mean particle size: 2-10 micrometers.
  • Light Soda Ash A light density sodium carbonate, typically
  • Example 1 A sample of PEO (as is) was converted to PEO (sized) by the procedure of RoTap batch screening on a 150 micrometer sieve. The resulting polymer was mixed to a homogeneous state in a small scale food processor with the ratio: 1 part PEO (sized) to 2 parts Zeolite A.
  • the PEO/Zeolite A premix was mixed in a batch rotary mixer together with the particulate components of a "softening through the wash" detergent composition shown below. Liquid components were then sprayed on. The finished composition has excellent clay deposition and softening properties.
  • Example 1 (% by weight)
  • Example 1 was repeated, except that the size reduction step was completed by passing PEO (as is) through a continuous Russel Finex vibratory screening system loaded with a 150 micrometer sieve.
  • Example 1 was repeated, except the size reduction procedure involves milling the PEO (as is) in a small batch coffee grinder and then completing the RoTap batch screening. This eliminates any PEO (as is) wastage.
  • Example 1 was repeated except size reduction procedure was carried out by passing PEO (as is) through a standard non-vibrating sieve deck loaded with a 150 micrometer screen and fitted with rotary brushes to improve screening efficiency.
  • Example 5
  • Example 1 was repeated, except size reduction procedure was carried out by passing PEO (as is) through a standard Air Jet Mill operating such that only particles below 150 micrometers are entrained in the air flow and removed for collection. This procedure eliminates wastage of PEO (as is) and is useful for large scale volume requirements.
  • Example 4 was repeated, except the PEO (sized) was mixed with Zeolite A in a batch vertomixer, or similar equipment, inco ⁇ orating a conical mixer with a screw rotating on its own axis which at the same time orbits the mixing chamber.
  • Example 6 was repeated, except the resultant premix contains a ratio of 1 part PEO (sized) to 1 part Zeolite A.
  • Example 6 was repeated, except the resultant premix contains a ratio of 1 part PEO (sized) to 10 parts Zeolite A.
  • Example 8 was repeated, except that the resultant premix contains a ratio of 1 part PEO (sized) to 10 parts fine light soda ash.
  • Example 6 was repeated except that the premix was added directly to a continuous detergent production process before any liquid spray ons.
  • Example 11
  • Example 6 was repeated, except that the premix was dusted onto the surface of a detergent produced on a continuous production process, after any liquid spray ons.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a granular detergent composition comprising (i) a softening clay and (ii) a clay flocculating polymer, and to a process for making the composition. The composition is particularly useful in 'softening-through-the-wash' products. The clay flocculating polymer is sieved or ground such that at least 95 % by weight of the clay flocculating polymer has a particle size of less than 250 micrometers, and preferably less than 150 micrometers, before adding it to the granular detergent composition.

Description

DETERGENT COMPOSITION COMPRISING CLAY FLOCCULATING POLYMER WITH PARTICLE SIZE LESS THAN 250 MICRONS.
The invention relates to a granular detergent composition comprising (i) a softening clay and (ii) a clay flocculating polymer, and to a process for making the composition. The composition is particularly useful in "softening-through-the-wash" products.
Clay flocculating polymer, such as polyethylene oxide having high molecular weight, is commercially available as a 100% active powder.
EP-A-0 299 575, published on 18th January 1989, discloses granular detergent compositions comprising softening clay and polymeric clay-flocculating polymer. It is stated that in preparing a granular detergent composition the polymeric clay- flocculating agent can be added in a variety of ways. It may be added to the crutcher mix prior to spray-drying; or it may be sprayed onto a granular detergent from a solution in water or an organic solvent; or it may be dry-mixed, in the form of particles, with a granular detergent. This application does not mention preferred particle size of clay flocculating polymer.
However, when polymeric clay flocculating polymers are dry mixed to granular detergents, undesirable patchy clay deposition or residues are observed. Patchy deposition is where visible lumps of clay deposit on a fabric surface. It is caused when the clay particles are flocculated very rapidly before they have had chance to disperse. This leads to the formation of lumps of clay which deposit on the fabric surface. Residues are caused when high local concentrations of the clay flocculating polymer, present in the formulation, form gels on contact with water, leading to poor dispensing ofthe product and an increased risk of product deposition on clothes.
Furthermore, clay flocculating polymers when handled in particulate form, give rise to handling and explosivity problems.
Summary ofthe Invention
According to the present invention undesirable patchy clay deposition and residues are avoided by sieving or grinding the clay flocculating polymer such that at least 95% by weight of the clay flocculating polymer has a particle size of less than 250 micrometers, and preferably less than 150 micrometers, before adding it to the granular detergent composition.
Preferably the clay flocculating polymer is a polyethylene oxide with an average molecular weight of between 100 000 and 10 million, more preferably between 150 000 and 800 000.
In a further aspect of the invention, a process for making a granular detergent composition is provided, comprising the step of premixing the clay flocculating polymer with a powder selected from the group consisting of aluminosilicate, silicate, carbonate, citrate, phosphate, or mixtures thereof, and subsequently mixing the premix with other detergent components.
Preferably the premix consists of the clay flocculating polymer and aluminosilicate in a ratio of from 1:20 to 20:1.
Detailed Description ofthe Invention
Softening clay
Softening clays may be either unmodified or organically modified. Those clays which are not organically modified can be described as expandable, three-layered clays, i.e., aluminosilicates and magnesium silicates, having an ion exchange capacity of at least 50 eq/lOOg. of clay and preferably at least 60 meq/100 g. of clay. The starting clays for the organically modified clays can be similarly described. The term "expandable" as used to describe clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water. The three-layer expandable clays used herein are those materials classified geologically as smectites. There are two distinct classes of smectite-type clays that can be broadly differentiated on the basis of the numbers of octahedral metal-oxygen arrangements in the central layer for a given number of silicon-oxygen atoms in outer layers. A more complete description of clay minerals is given in "Clay Colloid Chemistry" by H. van Olphen, John Wiley & Sons (Interscience Publishers), New York, 1963. Chapter 6, especially pages 66-69. The family of smectite (or montmorillonoid) clays includes the following trioctahedral minerals: talc; hectorite; saponite; sauconite; vermiculite; and the following dioctahedral minerals: prophyllite; montmorillonite; volchonskoite and nontronite.
The clays employed in these compositions contain cationic counterions such as protons, sodium ions, potassium ions, calcium ions, and lithium ions. It is customary to distinguish between clays on the basis of one cation predominantly or exclusively absorbed. For example, a sodium clay is one in which the absorbed cation is predominantly sodium. Such absorbed cations can become involved in exchange reactions with cations present in aqueous solutions. A typical exchange reaction involving a smectite-type clay is expressed by the following equation : smectite clay (Na)+ + NH4OH => smectite clay (NH4)"1" + NaOH. Since in the foregoing equilibrium reaction, an equivalent weight of ammonium ion replaces an equivalent weight of sodium, it is customary to measure cation exchange capacity (sometimes termed "base exchange capacity") in terms of milliequivalents per 100 g. of clay (meq/lOOg). The cation exchange capacity of clays can be measured in several ways, including by electrodialysis, by exchange with ammonium ion followed by titration, or by a methylene blue procedure, all as fully set forth in Grimshaw, "The Chemistry and Physics of Clays", pp. 264-265, Interscience (1971). The cation exchange capacity of a clay material relates to such factors as the expandable properties ofthe clay, the charge ofthe clay (which in turn is determined at least in part by the lattice structure), and the like. The ion exchange capacity of clays varies widely in the range form about 2 meq/ 100 g. of kaolinites to about 150 meq/100 g., and greater, for certain smectite clays.
Preferred smectite-type clays are sodium montmorillonite, potassium montmorillonite, sodium hectorite and potassium hectorite. The clays used herein have a particle size range of up to about 1 micron.
Any ofthe clays used herein may be either naturally or synthetically derived.
Clay Flocculating Polymer
Most clay flocculating polymers are fairly long chained polymers and co-polymers derived from such monomers as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone and ethylene imine. Gums, like guar gum, are suitable as well. Preferred are polymers of ethylene oxide, acrylamide or acrylic acid. These polymers dramatically enhance the deposition of a fabric softening clay if their molecular weights are in the range of from 100 000 to 10 million. Preferred are such polymers having a weight average molecular weight of from 150000 to 5 million.
The most preferred polymer is poly (ethylene oxide). Molecular weight distributions can be readily determined using gel permeation chromatography, against standards of poly (ethylene oxide) of narrow molecular weight distributions.
Process
The particle size of the polymer is reduced by either a standard milling operation or through physical screening ofthe particles. The raw material is then optionally mixed with a powder, such as fine aluminosilicate (Zeolite type A) in a mixer and then added to a finished product process. The zeolite acts as a carrier for the polymer, helping to aid its dispersion in the finished product making.
Many types of particle size alteration equipment can be used to reduce the mean particle size ofthe clay flocculating polymer to below 250 micrometers. Continuous screens such as Russel Finex and Mogenson vibratory screens, or continuous scraper screens. Batch screening operations involving RoTap variants are also applicable for small quantities. For larger scale operations, continuous air jet mills can be used that both size reduce and classify the material at the same time.
In a particular embodiment of the invention the polymer particles may be treated by micronisation to further reduce mean particle size.
Other detergent components
The particulate components of the present invention will normally be incoφorated into finished detergent products, especially those comprising softening clay. Other conventional detergent ingredients such as anionic and nonionic surfactants, builders, bleach, bleach activator, suds suppressor, enzymes (e.g. protease, amylase, cellulase, lipase), perfume brightener, soil release polymer will commonly be used. EXAMPLES In these examples all percentages are by weight unless otherwise specified, and the following abbreviations have been used:
PEO (as is): Polyethyleneoxide polymer as supplied by Union Carbide as WSRN750 (Trade Name). Typical particle size distribution: 2% above 710 micrometers
8% between 710 and 500 micrometers
20% between 500 and 250 micrometers
30% between 250 and 150 micrometers
40% below 150 micrometers
PEO (sized): As above but with 95% of the material above 150 micrometers removed via a size reduction process. Typical particle size distribution:
At least 100% below 300 micrometers
At least 95% below 150 micrometers
At least 50% below 106 micrometers
Zeolite A : supplied by Industrial Zeolite Ltd., Thurrock, England. Typical mean particle size: 2-10 micrometers.
Light Soda Ash A: light density sodium carbonate, typically
97% pure carbonate, a mean particle size of approx 100 micrometers, and an aerated density averaging 550 g/1.
Example 1 A sample of PEO (as is) was converted to PEO (sized) by the procedure of RoTap batch screening on a 150 micrometer sieve. The resulting polymer was mixed to a homogeneous state in a small scale food processor with the ratio: 1 part PEO (sized) to 2 parts Zeolite A.
The PEO/Zeolite A premix was mixed in a batch rotary mixer together with the particulate components of a "softening through the wash" detergent composition shown below. Liquid components were then sprayed on. The finished composition has excellent clay deposition and softening properties. Example 1 (% by weight)
PEO / Zeolite A premix 0.5
Softening clay 18
Anionic Surfactant Agglomerate 26
Cationic Surfactant Agglomerate 6
Nonionic Surfactant 3
Sodium Percarbonate 13
Layered Silicate / Citric Acid 12
Zeolite 4
Bleach Activator Particle 4
Suds Suppressor 3.5
Sodium Carbonate, Enzymes, Perfume, Soil Release balance to 100 Polymer, Brightener and other minors
Example 2
Example 1 was repeated, except that the size reduction step was completed by passing PEO (as is) through a continuous Russel Finex vibratory screening system loaded with a 150 micrometer sieve.
Example 3
Example 1 was repeated, except the size reduction procedure involves milling the PEO (as is) in a small batch coffee grinder and then completing the RoTap batch screening. This eliminates any PEO (as is) wastage.
Example 4
Example 1 was repeated except size reduction procedure was carried out by passing PEO (as is) through a standard non-vibrating sieve deck loaded with a 150 micrometer screen and fitted with rotary brushes to improve screening efficiency. Example 5
Example 1 was repeated, except size reduction procedure was carried out by passing PEO (as is) through a standard Air Jet Mill operating such that only particles below 150 micrometers are entrained in the air flow and removed for collection. This procedure eliminates wastage of PEO (as is) and is useful for large scale volume requirements.
Example 6
Example 4 was repeated, except the PEO (sized) was mixed with Zeolite A in a batch vertomixer, or similar equipment, incoφorating a conical mixer with a screw rotating on its own axis which at the same time orbits the mixing chamber.
Example 7
Example 6 was repeated, except the resultant premix contains a ratio of 1 part PEO (sized) to 1 part Zeolite A.
Example 8
Example 6 was repeated, except the resultant premix contains a ratio of 1 part PEO (sized) to 10 parts Zeolite A.
Example 9
Example 8 was repeated, except that the resultant premix contains a ratio of 1 part PEO (sized) to 10 parts fine light soda ash.
Example 10
Example 6 was repeated except that the premix was added directly to a continuous detergent production process before any liquid spray ons. Example 11
Example 6 was repeated, except that the premix was dusted onto the surface of a detergent produced on a continuous production process, after any liquid spray ons.

Claims

What is claimed is:
1. A granular detergent composition comprising (i) a softening clay and (ii) a clay flocculating polymer characterised in that at least 95% by weight of the clay flocculating polymer has a particle size of less than 250 micrometers.
2. A granular detergent composition according to claim 1 wherein at least 95% by weight of the clay flocculating polymer has a particle size of less than 150 micrometers.
3. A granular detergent composition according to either claim 1 or claim 2 wherein the clay flocculating polymer is a polyethylene oxide with an average molecular weight of between 100 000 and 10 million.
4. A granular detergent composition according to claim 3 wherein the clay flocculating polymer is a polyethylene oxide with an average molecular weight of between 150 000 and 800 000.
5. A process for making a granular detergent composition according to any of the previous claims, further comprising a powder selected from the group consisting of aluminosilicate, silicate, carbonate, citrate, phosphate, or mixtures thereof, and comprising the step of premixing the clay flocculating polymer with the powder to form a premix, and subsequently mixing the premix with other detergent components.
6. A process according to claim 5 wherein the premix consists ofthe clay flocculating polymer and aluminosilicate in a ratio of from 1:20 to 20:1.
PCT/US1996/014106 1995-09-01 1996-09-03 Detergent composition comprising clay flocculating polymer with particle size less than 250 microns WO1997009406A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AT96929867T ATE221570T1 (en) 1995-09-01 1996-09-03 DETERGENT CONTAINING A CLAY FLOCCULATION POLYMER WITH A PARTICLE SIZE OF LESS THAN 250 MICROMETERS
DK96929867T DK0865480T3 (en) 1995-09-01 1996-09-03 Detergent composition comprising a polymer clay flocculant having a particle size less than 250 Am
BR9610465A BR9610465A (en) 1995-09-01 1996-09-03 Detergent composition comprising flocculating clay polymer with particle size less than 250 microns
EP96929867A EP0865480B1 (en) 1995-09-01 1996-09-03 Detergent composition comprising clay flocculating polymer with particle size less than 250 microns
DE69622744T DE69622744T2 (en) 1995-09-01 1996-09-03 DETERGENT CONTAINING A TONE AS A FLOCOLATION POLYMER WITH A PARTICLE SIZE LESS THAN 250 MICROMETERS
JP51132997A JP3894953B2 (en) 1995-09-01 1996-09-03 Detergent composition comprising clay agglomerated polymer having a particle size of less than 250 microns

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP95306121.5 1995-09-01
EP95306121 1995-09-01

Publications (1)

Publication Number Publication Date
WO1997009406A1 true WO1997009406A1 (en) 1997-03-13

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EP (1) EP0865480B1 (en)
JP (1) JP3894953B2 (en)
CN (1) CN1105170C (en)
AT (1) ATE221570T1 (en)
BR (1) BR9610465A (en)
DE (1) DE69622744T2 (en)
DK (1) DK0865480T3 (en)
ES (1) ES2176486T3 (en)
MX (1) MX9801690A (en)
PT (1) PT865480E (en)
WO (1) WO1997009406A1 (en)

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WO2000060039A1 (en) * 1999-04-01 2000-10-12 The Procter & Gamble Company Fabric softening component
US6881717B1 (en) 1999-04-01 2005-04-19 The Procter & Gamble Company Fabric softening component
EP1561805A1 (en) * 2004-02-03 2005-08-10 The Procter & Gamble Company A solid particulate laundry detergent composition comprising clay and polydimethysiloxane
WO2005075618A1 (en) * 2004-02-03 2005-08-18 The Procter & Gamble Company A solid particulate laundry detergent composition comprising clay and polydimethylsiloxane
WO2019063402A1 (en) 2017-09-29 2019-04-04 Unilever Plc Laundry products
WO2019068472A1 (en) 2017-10-05 2019-04-11 Unilever Plc Methods and devices for individualized laundry
US11131055B2 (en) 2018-02-26 2021-09-28 Conopco, Inc. Methods and system for monitoring and replenishing one or more laundry components
US11910982B2 (en) 2019-11-01 2024-02-27 Conopco Inc. Recyclable auto-dosing container

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JP4744696B2 (en) * 1999-04-01 2011-08-10 ザ プロクター アンド ギャンブル カンパニー Fabric softening ingredient
JP2002541342A (en) * 1999-04-01 2002-12-03 ザ、プロクター、エンド、ギャンブル、カンパニー Fabric softening component
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WO2005075620A1 (en) * 2004-02-03 2005-08-18 The Procter & Gamble Company A solid particulate laundry detergent composition comprising clay and polydimethylsiloxane
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WO2019068472A1 (en) 2017-10-05 2019-04-11 Unilever Plc Methods and devices for individualized laundry
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US11807974B2 (en) 2017-10-05 2023-11-07 Conopco, Inc. Methods and devices for individualized laundry
US11131055B2 (en) 2018-02-26 2021-09-28 Conopco, Inc. Methods and system for monitoring and replenishing one or more laundry components
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EP0865480A1 (en) 1998-09-23
JP3894953B2 (en) 2007-03-22
JPH11515039A (en) 1999-12-21
CN1200142A (en) 1998-11-25
DK0865480T3 (en) 2002-09-02
ATE221570T1 (en) 2002-08-15
DE69622744D1 (en) 2002-09-05
EP0865480A4 (en) 1999-05-26
EP0865480B1 (en) 2002-07-31
CN1105170C (en) 2003-04-09
BR9610465A (en) 1999-03-02
ES2176486T3 (en) 2002-12-01
PT865480E (en) 2002-11-29
DE69622744T2 (en) 2003-04-03
MX9801690A (en) 1998-08-30

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