EP0316152A1 - Utilisation de phosphates d'alkyle pour la stabilisation de compositions thixotropiques - Google Patents

Utilisation de phosphates d'alkyle pour la stabilisation de compositions thixotropiques Download PDF

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Publication number
EP0316152A1
EP0316152A1 EP19880310546 EP88310546A EP0316152A1 EP 0316152 A1 EP0316152 A1 EP 0316152A1 EP 19880310546 EP19880310546 EP 19880310546 EP 88310546 A EP88310546 A EP 88310546A EP 0316152 A1 EP0316152 A1 EP 0316152A1
Authority
EP
European Patent Office
Prior art keywords
alkali
metal
composition
builder
sulphate
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.)
Granted
Application number
EP19880310546
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German (de)
English (en)
Other versions
EP0316152B1 (fr
Inventor
Cornelis Bernard Donker
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.)
Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Publication of EP0316152A1 publication Critical patent/EP0316152A1/fr
Application granted granted Critical
Publication of EP0316152B1 publication Critical patent/EP0316152B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/342—Phosphonates; Phosphinates or phosphonites
    • 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
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites

Definitions

  • the present invention relates to machine dishwashing liquid detergent compositions suitable for use in cleansing food soils from cooking utensils, dishes and glasses. More particularly, the present invention relates to an aqueous thixotropic structured system comprising an alkaline source and builder salts.
  • liquid forms of detergent for machine dishwashing offers several advantages over powdered or granular forms. These advantages include greater ease of handling in dispensing and dosing, the elimination of lump formation, "caking" and dust, and improved solubility.
  • liquid detergents must meet certain requirements. Firstly, the liquid detergent must be a uniform mixture of ingredients to deliver the optimum combination of active components to the wash with each dose. In most current formulations, this requires that the liquid be shaken before each use to remix the components. A preferred product should be stable against physical separation and segregation of its active components. High viscosity at low shear rate contributes to physical stability of the liquid and protects against separation of the active components.
  • Physical stability can be achieved through the use of suspending or viscosifying systems to enhance the liquid rheological properties. These agents must maintain viscosity at low shear rate under the high ionic strength conditions present in a well-built liquid detergent, and must be chemically compatible with the other components of the formula, especially the chlorine bleach used to assist stain removal.
  • the liquid dishwashing detergent must be compatible with the dishwashing equipment presently available.
  • Home dishwashing machines use a detergent cup which has been designed to house powdered or granular solid detergent and deliver it to a specific wash cycle.
  • the cups are not designed to contain low viscosity liquids. Consequently, liquids for use as machine dishwashing detergents must possess high viscosity to be effectively retained in the cup and avoid leakage into the machine during cycles which precede the wash. Excessive leakage will lead to under-dosing in the wash cycle and may affect cleaning performance.
  • thixotropic liquid detergent composition suitable for use in a machine dishwasher which is structured by interaction between the components, giving a positive effect on the rheology of the components, without the need to include a conventional thickening agent. This effect is shown in viscosity increases and in yield point enhancement.
  • GB 1 527 706 discloses a slurry structured by the addition of synthetic polymers. However, it is thought that the low yield point in liquids containing, eg polyacrylate as the only structuring agent causes poor cup retention.
  • GB 2 140 450 discloses liquids structured with clay. The clay lowers the amount of active component which can be delivered in each dose. Furthermore, the presence of insoluble clay minerals at levels used for structuring can negatively affect glass spotting and filming performance.
  • the use of biopolymers or cellulosics within a liquid detergent base has also been proposed to provide thickened systems, eg US 4 226 736 and US 4 260 528. Since most biopolymers react readily with hypochlorite, these systems are unstable and exhibit a gradual loss in viscosity if hypochlorite is present.
  • Micellar structured liquids are known in other areas, eg in thickened bleach systems (GB 1 466 560), usually containing over 90 wt% hypochlorite solution and no builder. Systems thickened by synergistic action with urea (eg GB 1 579 668) are also known.
  • GB 2 185 037 describes aqueous, thixotropic machine dishwashing detergents which are structured by fatty mono- or polycarboxylic acid.
  • an aqueous, thixotropic liquid cleaning composition comprising an alkali-metal builder and an alkali metal silicate and a stabiliser comprising from 0.05 to 5% by weight of an alkyl phosphate, phosphonate, sulphate or sulphonate, said composition optionally comprising a detergent active.
  • the present invention is based upon the discovery that the alkyl derivatives named may be used as liquid stabilisers.
  • Alkyl phosphates have previously been described for use in machine dishwashing compositions as foam depressors, but we do not believe that their use as liquid stabilisers has previously been described. Structuring occurs independently of the presence of active detergent.
  • compositions according to the present invention may also preferably incorporate a bleach, eg. a hypochlorite.
  • a bleach eg. a hypochlorite.
  • the system is stable when these bleaches are included in comparison to some systems of the prior art, wherein the presence of hypochlorite destroys system stability.
  • composition according to the present invention has improved rheology and stability and can deliver a high and uniform dosage of active ingredients to the machine wash cycle.
  • An improvement of the structuring also results in easier dispensing from the product container to the dispenser and from the dispenser to the machine wash at the appropriate time.
  • the system of the present invention has good stability against physical separation upon storage, providing a more uniform product. Poor physical stability can lead to development of a stratified liquid through separation of a fluid layer and a solids layer. This requires remixing by the end user through vigorous shaking of the container.
  • the structuring system of the invention may also be adjusted to develop optimum fluid rheology in terms of low shear rate attributes, giving physical stability, cup retention and moderate shear rate flow behaviour during dispensing into the wash cycle.
  • the product according to the present invention is a thixotropic machine dishwashing detergent in the form of a slurry-like paste.
  • the product possesses a yield point of between 5-50 Pa and a viscosity between 500-5000mPas at 20 ⁇ 1s (Haake RV2 at 20°C, MV2 rotor).
  • the stabilisers according to the present invention are long chain alkyl, ie C10-C22, sulphates, sulphonates, phosphates, phosphites or phosphonates.
  • Preferred are phosphorous based compounds. Particularly preferred are compounds selected from those listed in Table 1 below, or mixtures thereof:
  • ALF-5 (Lancro Chemicals Limited).
  • the higher alkyl phosphates and phosphonic acids are also preferred due to their tendency to reduce corrosion of metals and erosion of vitreous enamel surfaces.
  • sulphates or sulphonates are to be used, such as alkyl benzene sulphonates, it is preferred to additionally use a phosphate or phosphonate.
  • An alkali-metal condensed phosphate may be present in the formula as a water hardness sequestering agent or builder.
  • Tripolyphosphate is the preferred sequestrant although pyrophosphate, hexametaphosphate, or other condensed phosphates may be used.
  • the sequestrant should be present in the formula from 0.1 to 35 wt% with 15 to 30 wt% preferred.
  • Use of the sequestrant, such as sodium tripolyphosphate, in excess of its solubility limit within the formula requires that the solid be present as fine particles which are suspended by the structuring system. The presence of solids will affect the viscosity of the liquid and may modify the range of the structurants needed to deliver the proper rheology. Zeolites may also be used as builders.
  • An alkali-metal carbonate may be used as an alkaline buffering agent and may be present from 0 to 30 wt%, or more preferably from 2 to 10 wt%.
  • alkali-metal metasilicates or alkali-metal silicates with a molar ratio of SiO2/Na2O and/or K2O of from 1.0 to 3.25 may be used as alkaline sources and as anti-corrosion agents to protect metal and china surfaces against the harshly alkaline environments present in the wash.
  • the silicate may be used in the form of an aqueous liquor or a solid and may be present in the formula from 0.1 to 30 wt%, more preferably from 2 to 20 wt%.
  • An alkali-metal hydroxide may be used as an alkaline source and as a means to boost the pH of the liquid detergent concentrate to stabilise the hypochlorite.
  • Sodium or potassium hydroxide in the form of an aqueous liquor or as a solid may be used in the formula at from 0.1 to 25 wt%, preferably from 0.5 to 15 wt%.
  • Polymers may be added to the system to provide a further building effect.
  • the polymer used should be of a synthetic type and be water-soluble.
  • Examples of applicable polymers are polyacrylic acid and its alkali-metal salts, polymethacrylic acid and its alkali-metal salts, and copolymers of these with alkyl acrylates and alkyl methacrylates, copolymers of these with maleic anhydrides, polyacrylamide and partially hydrolysed polyacrylamide, polyacrylonitrile and its partially hydrolysed forms, polymethacrylonitrile and its partially hydrolysed forms, polystyrenesulphonic acid and its alkali-metal salts, polymaleic anhydride and its alkali-metal salts, poly n-vinyl lactams (poly-vinyl pyrrolidone, poly(N-vinyl caprolactam, etc), and polymers of N-substituted acrylamides or mixtures thereof.
  • polymers have a weight average molecular weight of from 1,000 to 15,000,000 with a molecular weight of from 10,000 to 400,000 preferred, and 100,000 to 250,000 most preferred. These polymers may be used in the acid or the neutralised form.
  • the polymers should be of a hypochlorite-stable type with polyacrylate and polymethacrylate being most preferred.
  • the polymer should be of a purity such that it contains a minimum of unsaturated monomers, chemically reactive initiators, terminators, or surfactants present which will hasten the rate of hypochlorite decomposition.
  • the polymer may be present in the formula from 0.05 to 10 wt%, preferably 0.1-0.5 wt%.
  • Clays such as hectorites and mortmorillonites may be included in the compositions of the invention. These assist in reduction of spot formation on glassware, and may be present at from 0.5 to 20 wt%. It has also been found that the presence of the structuring agents characterising the present invention assists in the production of low-viscosity, stable, clay-structured products described in the art without the need to incorporate known structuring agents, such as polymers, actives, etc. Particularly preferred is the addition of laponite clay at 0.5-2 wt%. An increase in solds level implies a need for lower levels of stabiliser to achieve stability.
  • the system may incorporate a bleach generating system, such as a hypochlorite, at from 0.5 to 5 wt% active chlrine.
  • Actives may optionally be included within the system. Preferred are nonionic actives. However, low levels of anionic actives such as secondary alkyl sulphates may be included.
  • the product according to the invention may be prepared by initial formulation of a premix comprising the stabilising component and water, the addition of this premix to a silicate and alkali-metal hydroxide mixture, and the subsequent addition of builder and hypochlorite.
  • the process is preferably carried out at above 40°C.
  • the product according to the invention has been shown to possess a high degree of stability at room temperature, whilst also demonstrating a suitably low viscosity to assist dispensing.
  • the pH of the composition may range from 10-14, preferably 12-13.5. It also demonstrates an improved washing performance in comparison to other thickened machine dishwashing systems.
  • a basic machine dishwashing liquid system was formulated, and viscosity and stability investigated at different levels of ALF-5 addition.
  • Base system STP 20.0 Na-disilicate 19.0 Na-carbonate 6.0 Na-OH 2.5 Hypochlorite (Av.Cl2) 1.0 Water to 100.0 ALF-5 Viscosity (20 sec ⁇ 1) Separation (%) (wt%) (mPas) 1 week 37°C RT 8 week 37°C RT 0 993 1 1 6 5 0.16 1300 0 0 0 0 0.50 990 0 0 0 0 1.00 1273 0 0 0 0 0 0
  • compositions were prepared and found to be stable for 8 weeks at RT and 37°C: wt% STP (anhydrous) 20 25 Na Disilicate 19 16 Na Carbonate 6 2 Na OH 2.5 2.5 Ti O2 0.2 - SAS - 0.2 HOCl (as Av.Cl2) 1.0 1.0 ALF-5 0.16 0.16 Water to 100

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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)
  • Detergent Compositions (AREA)
EP88310546A 1987-11-10 1988-11-09 Utilisation de phosphates d'alkyle pour la stabilisation de compositions thixotropiques Expired - Lifetime EP0316152B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8726308 1987-11-10
GB878726308A GB8726308D0 (en) 1987-11-10 1987-11-10 Machine dishwashing composition

Publications (2)

Publication Number Publication Date
EP0316152A1 true EP0316152A1 (fr) 1989-05-17
EP0316152B1 EP0316152B1 (fr) 1993-05-12

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EP88310546A Expired - Lifetime EP0316152B1 (fr) 1987-11-10 1988-11-09 Utilisation de phosphates d'alkyle pour la stabilisation de compositions thixotropiques

Country Status (9)

Country Link
EP (1) EP0316152B1 (fr)
JP (1) JPH0757879B2 (fr)
AU (1) AU616218B2 (fr)
BR (1) BR8807287A (fr)
DE (1) DE3880967T2 (fr)
ES (1) ES2054827T3 (fr)
GB (1) GB8726308D0 (fr)
WO (1) WO1989004359A1 (fr)
ZA (1) ZA888398B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994010272A1 (fr) * 1992-11-03 1994-05-11 The Procter & Gamble Company Nettoyage a l'aide d'agents tensio-actifs a courtes chaines
WO1999003958A1 (fr) * 1997-07-17 1999-01-28 Henkel Kommanditgesellschaft Auf Aktien Utilisation de melanges d'electrolytes comme agents sequestrants

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4794920B2 (ja) * 2005-06-21 2011-10-19 花王株式会社 水性液体洗浄剤組成物
JP5138188B2 (ja) * 2006-07-21 2013-02-06 株式会社Ａｄｅｋａ 洗浄剤組成物
US20080108537A1 (en) * 2006-11-03 2008-05-08 Rees Wayne M Corrosion inhibitor system for mildly acidic to ph neutral halogen bleach-containing cleaning compositions

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2193871A1 (fr) * 1972-07-25 1974-02-22 Colgate Palmolive Co
FR2330763A1 (fr) * 1975-11-07 1977-06-03 Unilever Nv Composition de nettoyage en particulier pour le lavage de la vaisselle
FR2520004A1 (fr) * 1982-01-18 1983-07-22 Colgate Palmolive Co Compositions du type de gel douees de proprietes thixotropes pour machines a laver la vaisselle automatiques
US4431559A (en) * 1981-10-06 1984-02-14 Texize, Division Of Mortonthiokol Dishwashing composition and method
GB2140450A (en) * 1983-05-24 1984-11-28 Colgate Palmolive Co Thixotropic automatic dishwasher composition with chlorine bleach
EP0142197A2 (fr) * 1983-11-04 1985-05-22 The Procter & Gamble Company Composition de blanchiment à l'hypochlorite contenant des agents tensio-actifs et des agents antimousses
GB2163448A (en) * 1984-08-13 1986-02-26 Colgate Palmolive Co Detergent for automatic dishwasher

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA83272B (en) * 1982-01-18 1984-08-29 Colgate Palmolive Co Gell-type automatic dishwasher compositions having thixotropic properties
GR862954B (en) * 1986-01-07 1987-05-08 Colgate Palmolive Co Thixotropic aqueous suspensions
DE3863131D1 (de) * 1987-06-12 1991-07-11 Unilever Nv Fluessige reinigungsmittelzusammensetzung fuer geschirrspuelmaschinen.
EP0314061A3 (fr) * 1987-10-28 1991-03-20 Colgate-Palmolive Company Composition détergente liquide aqueuse thixotropique pour le lavage automatique de la vaisselle

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2193871A1 (fr) * 1972-07-25 1974-02-22 Colgate Palmolive Co
FR2330763A1 (fr) * 1975-11-07 1977-06-03 Unilever Nv Composition de nettoyage en particulier pour le lavage de la vaisselle
US4431559A (en) * 1981-10-06 1984-02-14 Texize, Division Of Mortonthiokol Dishwashing composition and method
FR2520004A1 (fr) * 1982-01-18 1983-07-22 Colgate Palmolive Co Compositions du type de gel douees de proprietes thixotropes pour machines a laver la vaisselle automatiques
GB2140450A (en) * 1983-05-24 1984-11-28 Colgate Palmolive Co Thixotropic automatic dishwasher composition with chlorine bleach
EP0142197A2 (fr) * 1983-11-04 1985-05-22 The Procter & Gamble Company Composition de blanchiment à l'hypochlorite contenant des agents tensio-actifs et des agents antimousses
GB2163448A (en) * 1984-08-13 1986-02-26 Colgate Palmolive Co Detergent for automatic dishwasher

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994010272A1 (fr) * 1992-11-03 1994-05-11 The Procter & Gamble Company Nettoyage a l'aide d'agents tensio-actifs a courtes chaines
TR28396A (tr) * 1992-11-03 1996-05-30 Procter & Gamble Kisa zincirli yüzey aktif cisimleriyle temizlik.
US6180583B1 (en) 1992-11-03 2001-01-30 The Procter & Gamble Company Cleaning compositions containing short-chain surfactants
WO1999003958A1 (fr) * 1997-07-17 1999-01-28 Henkel Kommanditgesellschaft Auf Aktien Utilisation de melanges d'electrolytes comme agents sequestrants

Also Published As

Publication number Publication date
GB8726308D0 (en) 1987-12-16
WO1989004359A1 (fr) 1989-05-18
AU616218B2 (en) 1991-10-24
ES2054827T3 (es) 1994-08-16
EP0316152B1 (fr) 1993-05-12
DE3880967T2 (de) 1993-08-26
AU2498888A (en) 1989-05-11
JPH02502025A (ja) 1990-07-05
JPH0757879B2 (ja) 1995-06-21
ZA888398B (en) 1990-07-25
BR8807287A (pt) 1990-03-27
DE3880967D1 (de) 1993-06-17

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