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EP0859826A1 - Compositions detergentes rheopexiques pigmentees dotees de proprietes thixotropes - Google Patents

Compositions detergentes rheopexiques pigmentees dotees de proprietes thixotropes

Info

Publication number
EP0859826A1
EP0859826A1 EP96925280A EP96925280A EP0859826A1 EP 0859826 A1 EP0859826 A1 EP 0859826A1 EP 96925280 A EP96925280 A EP 96925280A EP 96925280 A EP96925280 A EP 96925280A EP 0859826 A1 EP0859826 A1 EP 0859826A1
Authority
EP
European Patent Office
Prior art keywords
hypochlorite
alkali metal
sodium
weight
oxide
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Withdrawn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
EP96925280A
Other languages
German (de)
English (en)
Other versions
EP0859826A4 (fr
Inventor
David A. Chang
James W. Cavanagh
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.)
Reckitt Benckiser LLC
Original Assignee
Reckitt and Colman Inc
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
Priority claimed from GB9516372A external-priority patent/GB2304113B/en
Application filed by Reckitt and Colman Inc filed Critical Reckitt and Colman Inc
Publication of EP0859826A1 publication Critical patent/EP0859826A1/fr
Publication of EP0859826A4 publication Critical patent/EP0859826A4/fr
Withdrawn legal-status Critical Current

Links

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
    • C11D3/3956—Liquid compositions
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—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
    • C11D3/1266—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in liquid compositions
    • 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
    • C11D3/40—Dyes ; Pigments
    • 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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • This invention relates to thickened liquid bleach-containing compositions useful for hard surface cleaning, and particular to such compositions which include bleach-stable pigments.
  • Thickened bleach compositions possess a number of advantages over unthickened bleach compositions.
  • To provide a thickened hypochlorite composition having an acceptable shelf-life the rate of decomposition of alkali metal hypochlorite as well as the phase behaviour ofthe composition must be considered.
  • alkali metal hypochlorite degradation may be illustrated by the following equation:
  • bleach-containing cleaner compositions which have distinctive coloration.
  • the realm of bleach stable colourants is fairly small due to the tendency of organic dyes to degrade in the presence of strong oxidizers.
  • U.S. Patent No. 4,474,677 suggests the use of certain halogenated copper phthalocyanine pigments for aqueous alkali metal hypochlorite compositions. While this class of pigments is considered to be bleach-stable, slow degradation ofthe pigment molecule releases copper which catalyzes the degradation of hypochlorite.
  • U.S. Patent No. 4,271,030 (Brierley) describes a suspension of ultramarine blue using calcium soap floes. Use of calcium soap floes is not desirable due to the high concentration required, 50% by volume ofthe composition, or from a cleaning standpoint due to a tendency to precipitate onto hard surfaces.
  • This invention provides thickened hypochlorite compositions with enhanced rheological properties which are capable of stably suspending inorganic pigments.
  • the thickening system is a blend of surfactants and clay that is rheopectic at low shear rates, which helps to stably suspend the pigment, but thixotropic at higher shear rates, which allows the product to dispense easily from a container to aid in the cleaning of hard surfaces.
  • rheopexy and thixotropy are opposite flow properties. Having both properties present in a single fluid is quite advantageous.
  • Non-limiting examples of inorganic colourants that can be utilized include ultramarine blue, cobalt aluminate blue, titanium dioxide and calcium carbonate.
  • This invention focuses on the use of ultramarine blue which is preferred due to its consumer appeal, low toxicity, and colour intensity compared to other pigments.
  • the composition behaves as a highly structured liquid and exhibits some unique and unexpected flow properties. This occurs despite the low solids content, less than 10%, ofthe formula as compared to other structured liquids, some of which are known in the category of liquid laundry detergents. This characteristic helps to solve the problem of pigment sedimentation while still maintaining thin fluid flow properties which help to achieve good surface coverage for products such as liquid toilet bowl cleaners.
  • the composition also has good phase-stability and hypochlorite-stability.
  • compositions of this invention comprise:
  • an alkali metal salt preferably sodium chloride
  • a pH stabilizer to provide a pH of 11 or higher
  • the viscosity ofthe composition can range from about 200 cps to about 1000 cps.
  • the preferred range is from about 300 - 500 cps.
  • Figures 1 and 2 are graphs showing the rheological properties of a preferred embodiment of this invention.
  • Figures 3 and 4 are graphs showing certain rheological properties of a formulation according to this insertion ( Figure 3) and comparable properties of a similar composition without the clay ( Figure 4).
  • the inventive composition is a hypochlorite stable, single phase, thickened hypochlorite bleach composition capable of adhering to vertical or inclined surfaces longer than thinner compositions.
  • the composition is an effective agent for stain and soil removal as well as disinfection.
  • the high level of hypochlorite stability and single solution phase behaviour ofthe composition enables the composition to have an acceptable shelf life.
  • the compositions include also an organic pigment in suspension. In these pigmented compositions, the colour stability, particularly where the pigment is ultramarine blue, is uniquely advantageous.
  • the alkali metal ofthe alkali metal hypochlorite is selected from lithium, potassium or sodium.
  • sodium hypochlorite is currently preferred.
  • the alkali metal hypochlorite may have other by-products ofthe manufacturing process present without adversely affecting the composition.
  • the amount of alkali metal hypochlorite employed is within the range of about 0.5 weight % to about 10 weight %, preferably from 1.0 weight % to 5.0 weight %, and more preferably from 1.5 weight % to 3.0 weight %.
  • Bentonite clay is a colloidal hydrated aluminum silicate clay found in North America. It consists principally of montmorillonite (Al2 ⁇ 3»4Si ⁇ 2»H2 ⁇ ) and usually also contains some magnesium, iron and calcium carbonate. Bentonite clay is preferred for use in the compositions of this invention, but other clays of similar structure and/or properties may be used.
  • the amount of Bentonite clay in the composition should range from about 0.15 weight % to about 1.5 weight %, preferably from 0.25 weight % to 1.0 weight %.
  • the tertiary amine oxide is ofthe formula:
  • R 1 is an alkyl group containing from about 10 to about 16 carbon atoms and each of R 2 and R 3 is a lower alkyl group containing from 1 to 3 carbon atoms.
  • R 1 , R 2 and R 3 may be a straight or branched chain; R 1 may contain an odd or an even number of carbon atoms.
  • Amine oxides of mixed chain length may be used, which may contain a predominance of one or more chain lengths.
  • the tertiary amine oxide is selected from myristyldimethylamine oxide, lauryldimethylamine oxide, and mixtures thereof. Most preferably employed is myristyldimethylamine oxide.
  • the amount ofthe tertiary amine oxide employed is preferably in the range from about 0.5 weight % to about 2.5 weight %, more preferably from 0.9 weight % to 1.8 weight %, and most preferably from 1.0 weight % to 1.5 weight %.
  • the alkali metal salt may be selected from any number of water-soluble alkali metal salts and mixtures thereof, with the alkali metal preferably being lithium, potassium, or sodium, and the anion ion preferably being a halide (such as chloride, fluoride, bromide and iodide). More preferably the alkali metal salt is selected from the group consisting of sodium chloride, lithium chloride, potassium chloride, and mixtures thereof.
  • the alkali metal salt most preferred is sodium chloride and may be used in varying amounts to reduce hypochlorite degradation, limited only by the avoidance of a "salting out” ofthe solution (where the surfactants become insoluble in water).
  • sodium chloride the preferred amount is in the range of about 0.25 weight % to about 2.0 weight %, preferably from 0.5 weight % to 1.5 weight %.
  • An alkali metal hydroxide is the preferred pH stabilizer included in the composition, although any pH stabilizer may be employed as long as the stability and viscosity ofthe composition are not adversely affected.
  • the alkali metal of the preferred hydroxide may be lithium, potassium, or sodium. Sodium hydroxide and potassium hydroxide are particularly useful pH stabilizers due to cost and availability, with sodium hydroxide most preferred.
  • the alkali metal hydroxide is included in the composition in an effective amount to adjust the composition to a pH level of at least about 11, more preferably from 12 to 13.5, and most preferably within the range from 12 to 13.
  • alkali metal alkyl sarcosinate may be represented by the formula: CH 3
  • R 4 is a branched or straight chain C10-C16 alkyl group and M is an alkali metal cation (such as lithium, potassium or sodium).
  • Sodium lauroyl sarcosinate is most preferred.
  • the amount of alkali metal alkyl sarcosinate that may be used preferably ranges from about 0.10 weight % to about 0.75 weight %, more preferably 0.12 weight % to 0.60 weight %, and most preferably from 0.15 weight % to 0.30 weight %.
  • the alkali metal C 10 to C 14 straight chain alkylbenzene sulphonate is preferably defined wherein the alkali metal is potassium, lithium, or sodium. Most preferably employed is sodium dodecylbenzene sulphonate.
  • the amount of sulphonate used is within the range of from about 0.08 weight % to about 0.8 weight %, more preferably from 0.1 weight % to 0.5 weight %, and most preferably from 0.15 weight % to 0.4 weight %.
  • the preferred pigment is ultramarine blue which is an inorganic silicate.
  • this material is inert to hypochlorite oxidation and does not catalyze decomposition of hypochlorite, it is insoluble and requires suspension in the hypochlorite solution. Such suspension cannot be achieved merely by dispensing particles of ultramarine blue in hypochlorite solution, because the pigment has a density of 2.35 and settles out even when it is of very fine particle size.
  • the thickening system employed in the composition of this invention provides excellent suspension for ultramarine blue pigment particles.
  • the amount of ultramarine blue in the composition of this invention ranges from about 0.01 weight % to about 0.50 weight %, preferably about 0.05 weight %.
  • the molar ratio ofthe tertiary amine oxide to alkali metal alkylbenzene sulphonate should fall within the range of from about 5:1 to about 11 : 1.
  • the molar ratio is from 6:1 to 10:1, and more preferably from 7:1 to 9:1.
  • the composition offers improved viscosity for alkali metal hypochlorite bleaches while at the same time providing a commercially acceptable pigmented composition with excellent colour stability.
  • the primary interaction is between the clay and the amine oxide components ofthe formula.
  • the combination ofthe clay, sodium chloride, and the sodium hydroxide in solution causes the clay platelets to align in an edge-to-face structure.
  • Some ofthe amine oxide acts to stabilize the structure through both ionic and steric interaction.
  • Sulphonate and sarcosinate surfactants combine with the remaining amine oxide to form organic structures or micelles which boost viscosity. It is further theorized that these micelles interact with the clay structure to develop the unique rheology ofthe composition.
  • This invention provides a commercially advantageous coloured thickening system which exhibits thixotropic properties for easy dispensing, particularly from a spray container.
  • Cleaning products employing this thickening system have a sufficiently high level of quiescent viscosity to keep the inorganic pigment particles in suspension.
  • Example 1 A blue-pigmented hand surface cleaner was prepared which had the following ingredients, all percentages being by weight.
  • Ingredient bentonite clay (Gelwhite H) 1.00% ultramarine blue 0.05% sodium chloride 1.00% sodium hydroxide 2.50% myristyldimethylamine oxide 5.60% sodium hypochlorite 2.50% sodium dodecylbenzene sulphonate 0.72% sodium lauroyl sarcosinate 1.00% fragrance 0.065% deionized water q.s. to 100%
  • the cleaner composition was prepared by dispensing in the main vessel (1) Gelwhite H, a montmorillomite clay (Southern Clay Products) in water, using a homogenizer until the clay is fully hydrated, and adding the Ultramarine blue with further agitation.
  • a separate vessel (2) sodium chloride and a 25% solution of sodium hydroxide were dissolved in water. The contents of vessel (2) were added to vessel (1) with high agitation.
  • FIG. 1 The thixotropic character is evident at 50 sec -1 .
  • Figure 2 captures the stress growth behaviour at the inception of flow at the first shear rate, 1 sec -1 . Testing was conducted with the Rheometrics Scientific RFSII rheometer, 50 mm parallel plate, 0.9 mm spacing, 316SS tooling, 25C, 0.002 - 10 gr-cm force rebalance.
  • Comparative Example A cleaning composition containing ultramarine blue pigment, but without bentonite clay was prepared, and the pigment-settling characteristics were compared with the composition ofExample 1.
  • the comparative composition was prepared using the method ofExample 1. The two compositions were maintained in a quiescent state for a period of six weeks at 40°C.
  • the following table shows the ingredients ofthe compositions and the relevant rheological data.

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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)
  • Biological Depolymerization Polymers (AREA)

Abstract

Cette invention concerne un détergent pigmenté pour surfaces dures contenant un agent de blanchiment, ledit détergent comportant un hypochlorite de métal alcalin, de l'argile de bentonite, un oxyde d'amine mono-(alkyle à chaîne longue)-tertiaire, un sel de métal alcalin, un stabilisateur de pH permettant d'atteindre un pH supérieur ou égal à 11, un alkyle sarcosinate de métal alcalin, un alkylbenzènesulfonate et un pigment inorganique qui est de préférence du bleu d'outremer. Cette composition détergente présente une excellente stabilité de couleur ainsi qu'une bonne stabilité de phase et de l'hypochlorite.
EP96925280A 1995-08-10 1996-07-08 Compositions detergentes rheopexiques pigmentees dotees de proprietes thixotropes Withdrawn EP0859826A4 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB9516372A GB2304113B (en) 1995-08-10 1995-08-10 Hard surface cleaner
GB9516372 1995-08-10
US08/619,864 US5688435A (en) 1995-08-10 1996-03-18 Pigmented rheopectic cleaning compositions with thixotropic properties
US619864 1996-03-18
PCT/US1996/011409 WO1997006233A1 (fr) 1995-08-10 1996-07-08 Compositions detergentes rheopexiques pigmentees dotees de proprietes thixotropes

Publications (2)

Publication Number Publication Date
EP0859826A1 true EP0859826A1 (fr) 1998-08-26
EP0859826A4 EP0859826A4 (fr) 1999-11-24

Family

ID=26307551

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96925280A Withdrawn EP0859826A4 (fr) 1995-08-10 1996-07-08 Compositions detergentes rheopexiques pigmentees dotees de proprietes thixotropes

Country Status (9)

Country Link
EP (1) EP0859826A4 (fr)
CN (1) CN1102649C (fr)
AU (1) AU692718B2 (fr)
BR (1) BR9609898A (fr)
CA (1) CA2228674C (fr)
IN (1) IN189237B (fr)
MX (1) MX9801081A (fr)
NZ (1) NZ313386A (fr)
WO (1) WO1997006233A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19722809A1 (de) * 1997-05-30 1998-12-03 Henkel Kgaa Reinigungsmittel
GB9727517D0 (en) * 1997-12-31 1998-02-25 Jeyes Group Plc Liquid bleach composition
DE19821695A1 (de) * 1998-05-14 1999-11-25 Henkel Kgaa Gefärbte maschinelle Geschirrspülmittel
WO2000055291A1 (fr) * 1999-03-17 2000-09-21 R.T. Vanderbilt Company, Inc. Stabilisant pour produits de nettoyage contenant des agents de blanchiment
ATE350452T1 (de) * 2002-10-29 2007-01-15 Unilever Nv Verdickte flüssige bleichmittelzusammensetzungen
US20040254085A1 (en) * 2003-05-19 2004-12-16 Johnsondiversey, Inc. [high caustic contact cleaner]
DE102005058642B3 (de) * 2005-12-07 2007-07-26 Henkel Kgaa Erhöhung der Stabilität flüssiger hypochlorithaltiger Wasch- und Reinigungsmittel
DE102005062008B3 (de) 2005-12-22 2007-08-30 Henkel Kgaa Geruchsreduktion hypochlorithaltiger Mittel
DE102005063177A1 (de) 2005-12-30 2007-07-05 Henkel Kgaa Erhöhung der Stabilität hypochlorihaltiger Waschmittel
DE102006003336A1 (de) * 2006-01-23 2007-07-26 Henkel Kgaa Sprühbarer Allzweckreiniger
EP1911832A1 (fr) * 2006-10-13 2008-04-16 Unilever N.V. Composition de blanchiment
US20090197790A1 (en) * 2008-02-05 2009-08-06 Amcol International Corporation Drip resistant cleaning compositions
WO2018223368A1 (fr) * 2017-06-08 2018-12-13 The Procter & Gamble Company Compositions non homogènes

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4271030A (en) * 1977-11-18 1981-06-02 Lever Brothers Company Pourable liquid compositions

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4552680A (en) * 1983-11-04 1985-11-12 The Procter & Gamble Company Hypochlorite bleach containing surfactant and organic antifoamant
US4623476A (en) * 1984-03-30 1986-11-18 The Procter & Gamble Company Stable suspension of pigments in aqueous hypochlorite bleach compositions
US4714562A (en) * 1987-03-06 1987-12-22 The Procter & Gamble Company Automatic dishwasher detergent composition
US4789495A (en) * 1987-05-18 1988-12-06 The Drackett Company Hypochlorite compositions containing a tertiary alcohol
US5089162A (en) * 1989-05-08 1992-02-18 Lever Brothers Company, Division Of Conopco, Inc. Cleaning compositions with bleach-stable colorant
JP2594404B2 (ja) * 1992-12-22 1997-03-26 花王株式会社 液体漂白剤組成物
NZ277629A (en) * 1993-12-29 1997-07-27 Reckitt & Colman Inc Alkali metal hypochlorite compositions with enhanced viscosity containing tertiary amine, alkali metal sarcosinate and alkyl benzyl sulphonate; cleaning compositions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4271030A (en) * 1977-11-18 1981-06-02 Lever Brothers Company Pourable liquid compositions

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 9431 Derwent Publications Ltd., London, GB; AN 253131 XP002117097 "Liquid Bleacher composition having good viscosity.." & JP 06 184594 A (KAO CORP), 5 July 1994 (1994-07-05) *
See also references of WO9706233A1 *

Also Published As

Publication number Publication date
AU692718B2 (en) 1998-06-11
IN189237B (fr) 2003-01-11
AU6543196A (en) 1997-03-05
CA2228674A1 (fr) 1997-02-20
MX9801081A (es) 1998-04-30
NZ313386A (en) 1998-07-28
BR9609898A (pt) 1999-05-25
CA2228674C (fr) 2000-10-10
WO1997006233A1 (fr) 1997-02-20
CN1192775A (zh) 1998-09-09
CN1102649C (zh) 2003-03-05
EP0859826A4 (fr) 1999-11-24

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