EP0331370B2 - Verfahren zur Herstellung einer Detergentzusammensetzung - Google Patents

Verfahren zur Herstellung einer Detergentzusammensetzung Download PDF

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Publication number
EP0331370B2
EP0331370B2 EP89301851A EP89301851A EP0331370B2 EP 0331370 B2 EP0331370 B2 EP 0331370B2 EP 89301851 A EP89301851 A EP 89301851A EP 89301851 A EP89301851 A EP 89301851A EP 0331370 B2 EP0331370 B2 EP 0331370B2
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EP
European Patent Office
Prior art keywords
composition
making
weight
final composition
present
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.)
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Application number
EP89301851A
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English (en)
French (fr)
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EP0331370A3 (en
EP0331370A2 (de
EP0331370B1 (de
Inventor
Jakob Van Dijk
Hidde Frankena
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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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0331370A2 publication Critical patent/EP0331370A2/de
Publication of EP0331370A3 publication Critical patent/EP0331370A3/en
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Publication of EP0331370B1 publication Critical patent/EP0331370B1/de
Publication of EP0331370B2 publication Critical patent/EP0331370B2/de
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

  • the present invention relates to detergent compositions.
  • it relates to the making of liquid machine dishwashing detergent compositions suitable for use in cleansing food soils from cooking utensils, dishes, glasses and similar ware.
  • the present invention relates to a method of making a stable, pourable, aqueous system comprising at least partially undissolved builder salts and a dissolved alkali silicate, the composition being essentially free of conventional structuring agents.
  • the system is characterised by its thixotropic nature.
  • Detergents for use in domestic machine dishwashers are generally available in powdered or granular forms.
  • solid compositions exhibit a number of disadvantages for the producer and user.
  • the compositions cannot generally be spray-dried, and thus separate manufacturing facilities to those generally used for powdered detergents must be built.
  • the powders often incorporate large lumps caused by caking during storage at high humidity. This can cause difficulties in dispersion. Powdered forms of the product are often very dusty, which can affect dispensing as well as causing irritation.
  • liquid detergents must meet certain requirements. Firstly, the liquid must be a uniform mixture of ingredients in order to deliver the optimum combination of active components to the wash with each dose.
  • active components we mean those components which actually take part in the cleaning, rather than those acting as fillers. In many formulations described in the art, this requires that the liquid be shaken before each use in order to re-mix the different components.
  • a preferred product should be stable against physical separation and segregation of the active components during storage.
  • Particulate solids for example detergency builders, should remain suspended in liquid detergents.
  • some kind of structuring system is necessary. In aqueous detergent liquids this may be achieved either by "external structuring", ie adding an additional component such as a polymer or clay, or using the interaction of the water in the liquid and the detergent actives themselves, to form an "internal structure" to support the solids (eg secondary alkane sulphonates and phosphonates).
  • external structuring ie adding an additional component such as a polymer or clay, or using the interaction of the water in the liquid and the detergent actives themselves, to form an "internal structure" to support the solids (eg secondary alkane sulphonates and phosphonates).
  • microscopic investigation indicates that some type of suspending network is formed.
  • the phrase 'structuring agent' as used herein is taken to mean any component, e.g. clay, polymer or biocellulosic, which at suitable amounts within a liquid imparts a structure to said liquid, usually by network formation.
  • the use of such agents, particularly clay, in lower amounts is not to be taken as being excluded from compositions. Such low amounts may act as builders or rinse aids.
  • the critical amount of the component in question may only be determined by reference to experiments or the prior art.
  • the detergent For use with machine dishwashers, the 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 usually held vertically on the dishwasher door and are not designed to contain low viscosity liquids. Consequently. liquids for use as machine dishwashing detergents must possess sufficient 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. However, they must not be so viscous that they cannot be washed out of the dispensing cup at the appropriate time.
  • GB 1 527 706 discloses a slurry structured by the addition of synthetic polymers.
  • GB 2 140 450 discloses liquids structured with clay. The clay lowers the amount of active component which can be delivered in each dose.
  • the presence of insoluble clay minerals 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.
  • GB 2 185 037 has disclosed the use of long-chain fatty acids to provide a thickening effect.
  • the present invention makes use of different principles to obtain pourable and stable liquid systems.
  • the present invention does not involve the use of a network-forming structurant. Due to the absence of such a structurant, which in the current state of the art is judged to be essential for keeping the solid particles well suspended, the present invention involves liquid systems (dispersions) which are Newtonian (eg not shear thinning) over a broad range of shear rate values: 1-100 sec -1 .
  • compositions made according to the present invention the solids are present as individual particles and not as flocculates.
  • the deflocculation effect can be illustrated by the following observation: the addition of 40% zeolite 4A to a 20% sodium disilicate (ratio 3.6) solution results in the formation of a viscous, shear thinning unusable paste outside the scope of the invention. Adjusting the silicate ratio with NaOH or KOH the viscosity will drop considerably and a thin, pourable, pseudo-Newtonian system is obtained by deflocculation of the particles.
  • the preferred rheological behaviour is identified by the Thixotropic Index (TI) which has to be between 0.5 and 2.5.
  • the Thixotropic Index is herein defined as the ratio of the apparent LVT Brookfield viscosity of a sample after 3 minutes at room temperature using a No 4 spindle at (a) 3 rpm and (b) 30 rpm.
  • compositions made according to the present invention are formulated for ware washing, in particular for use in machine dishwashers. They have improved rheology and stability in comparison to compositions of the prior art and can deliver a high and uniform dosage of active ingredients to the machine wash cycle
  • the detergent builder material may preferably be a non-phosphate builder salt.
  • Such builders include water-soluble inorganic carbonate and bicarbonate
  • Water-soluble organic builders which may be used include polyacetates, carboxylates, polycarboxylates and polyhydroxy sulphonates, at least a proportion of the salt remaining undissolved.
  • Particularly preferred as builders are zeolite and amorphous silica alumina builders.
  • Aluminosilicates of the zeolite type may be prepared as described in US 2 882 243 (Union Carbide) or of the amorphous type as described in EP 0 097 512 (Unilever)
  • the aluminosilicate is preferably of the formula 0.8-1 5 Na 2 O; Al 2 O 3 ; 1.7 - 3.0 SiO 2 ; 2 - 6 H 2 O.
  • NTA NTA
  • EDTA EDTA
  • CMOS complementary metal-oxide-semiconductor
  • DPA DPA
  • the builder constitutes from 5-60%, preferably from 20-40%.
  • the second essential component of the compositions made according to the present invention is a silicate material.
  • disilicates are partic arly preferred, although metasilicates may also be included.
  • the alkali-metal silicates which are used serve as anti-corrosion agents. protecting metal and china surfaces against harshly alkaline environments present during a dishwashing cycle.
  • the silicate-based material constitutes from 3-40%, preferably from 5-20%.
  • the present invention provides compositions which do not necessarily contain any detergent surfactants.
  • the compositions may be used for the delivery of caustic agents to the wash liquor during mechanical dishwashing operations.
  • one or more detergent surfactant agents may be selected from one or more of nonionic, anionic, cationic, zwitterionc and amphoteric agents.
  • Such agents are commercially available and will be well known by those skilled in the art; for instance, they are fully described in the literature, such as in "Surface Active Agents and Detergents", Volumes I and II by Schwarz, Perry and Berch.
  • any detergent active material comprises one or more nonionic agents, for example the condensation products of alcohols having from 8-16 carbon atoms, and alkyl phenols with alkylene oxides including ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
  • the alcohols are linear, having from 12-15 carbon atoms, and are condensed with 2-10 mols of ethylene oxide.
  • Most preferred are those compounds which are generally regarded as "low-foaming", especially those where the alkylene oxide chain is terminated by a moiety other than hydrogen.
  • compositions made according to the present invention are prepared by admixture of the various components.
  • An alkali-metal hypochlorite may be present in the formula as an agent for removing tea, coffee and other food stains from cups, dishes, flatware, etc.
  • the bleach source may be present in the mixture at from 0.1-10 wt %, with the most preferred range being from 0.1-2 wt % (percentages as active chlorine).
  • Electrolytes such as NaCI, Nal, Na 2 SO 4 may be included in the composition at from 0.1 to 10 wt %.
  • Defoamers may be included in the composition. These defoamers may be of the general type of slightly soluble alkyl carboxylates, alkyl phosphates, hydrophobic silicas, silicone defoamers, or many others. In addition to being an effective defoamer, the species should be stable to hypochlorite.
  • the defoamer may optionally be present in the composition at from 0-5 wt %, more preferably from 0.1-1 wt %, and most preferably from 0.1-0.5 wt %.
  • the products made according to the present invention exhibit a high degree of stability at room temperature. in comparison to other systems. Unlike known liquids, the products produced in accordance with the present invention do not require shaking in order to redisperse the ingredients. Furthermore, compositions formulated in accordance with the present invention exhibit a higher density (1.7-1.8) than comparable products of the prior art. This is particularly important when considering transportation. A more concentrated liquid benefits from lower packing and transport costs. Also, a unit dose will deliver more active ingredients per unit dose than products produced in accordance with the art.
  • Liquid systems made according to the present invention are not susceptible to setting after storage. Even after prolonged storage the product does not solidify and no setting has been observed. The inference is that the product can be dosed without shaking or squeezing the bottle which is required for the current liquids with an external structurant. Dealing with bottles of 1.5-2.5 kg this benefits the convenience aspect of the product.
  • compositions made according to the present invention provide a liquid system which is very convenient for consumers whilst being also perfectly suitable for an automatic dosing application.
  • the automatic dosing principle can be used for domestic as well as industrial dishwashing machines.
  • compositions made according to the present invention are pourable from rest without need for shear thinning. Dispenser behaviour is strongly determined by the rheological properties of the liquid. In the prior art, Newtonian liquids are not considered to be suitable. Some of the liquids made according to the present invention have been tested to measure dispenser cup leakage in a number of commercially-available dispenser types. It was found that the degree of dispenser cup leakage was acceptable if the liquid had a viscosity of at least 2000 mPAS.
  • dishwashing compositions formulated according to the present invention show less tendency to cause spot formation on glass than other conventionally structured (eg by polymers or clavs) liquid deterqent systems. This is particularly noticeable after a number of wash cycles.
  • a further possible use of the system of the invention arises when considering systems incorporating zeolite as the builder.
  • Zeolite slurrys of the prior art are known to be unstable.
  • JP-A-54/64504 discloses generally a zeolite slurry for detergent products, having good stability and high fluidity and consisting of an aqueous solution of a zeolite builder and a soluble alkali-metal silicate having a silica to alkali molar ratio of from 2.0 to 3.5.
  • the liquids made according to the present invention provide a stable zeolite slurry which does not separate on standing.
  • the slurry can be spray dried as a basis for formulating powders for ware washing.
  • the stability of liquid compositions made according to the present invention was measured as the percentage of separation at 1, 2, 3 and 4 weeks after storage at 20°C.
  • the build-up of spots over 4 washes is measured as the number of spots on a glass tumbler: 0 1 1-5 2 6-10 3 11-20 4 >20 5
  • composition wt% Zeolite 4A 42 Sokalan Polymer (20% slurry) 5 Disilicate (ratio 2.0) 20 K OH (85% soln) 5 HOCI (as Cl 2 ) 1 Water to 100
  • composition was found not to have separated over a period of weeks and was suitable for cleaning dishes in a machine dishwasher.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)

Claims (6)

  1. Verfahren zur Herstellung einer stabilen, viskosen flüssigen Zusammensetzung, angepaßt für die Verwendung in einer automatischen Geschirrspülmaschine, umfassend das Mischen folgender Bestandteile:
    (a) 5 bis 60 Gewichtsprozent, bezogen auf die Endzusammensetzung, eines Detergentbuilders, der in der Endzusammensetzung zumindest teilweise in unlöslicher Form vorliegt;
    (b) 3 bis 40 Gewichtsprozent, bezogen auf die Endzusammensetzung, eines Alkalimetallsilicats;
    (c) ein Alkalimetallhydroxid; und
    (d) Wasser bis 100 Gewichtsprozent, bezogen auf die Endzusammensetzung,
    dadurch gekennzeichnet, daß das Alkalimetallhydroxid in einer wirksamen Menge zugegeben wird, so daß in der Endzusammensetzung das Alkalimetallsilicat ein Kieselerde-zu-Alkali-Verhältnis von 0,6 bis 1,9 aufweist, die Zusammensetzung nicht Scherung-verringernd über einen Schergeschwindigkeitswert-Bereich von 1 bis 100 s-1 ist, und die Zusammensetzung einen thixotropen Index von 2,5 bis 0,5 besitzt, wobei die Zusammensetzung im wesentlichen frei von einem externen Netzwerk-bildenden Strukturierungsmittel ist.
  2. Verfahren zur Herstellung einer stabilen flüssigen Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß die zugegebene Menge des Alkalimetallhydroxids im Bereich von 4,25 bis 20 Gewichtsprozent, bezogen auf die Endzusammensetzung, liegt.
  3. Verfahren zur Herstellung einer stabilen flüssigen Zusammensetzung nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, daß zu den anderen Bestandteilen der Zusammensetzung ferner 0,1 bis 10 Gewichtsprozent, bezogen auf die Endzusammensetzung, eines Alkalimetallhypochlorit-Bleichmittels, ausgedrückt als aktives Chlor, zugegeben werden.
  4. Verfahren zur Herstellung einer stabilen flüssigen Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Detergentbuilder ein Aluminosilicat ist.
  5. Verfahren zur Herstellung einer stabilen flüssigen Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß zu den anderen Bestandteilen der Zusammensetzung ferner von 0,1 bis 10 Gewichtsprozent, bezogen auf die Endzusammensetzung, eines Elektrolyts zugegeben werden.
  6. Verfahren zur Herstellung einer stabilen flüssigen Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Zusammensetzung einen thixotropen Index von 1,5 bis 0,8 aufweist.
EP89301851A 1988-02-26 1989-02-24 Verfahren zur Herstellung einer Detergentzusammensetzung Expired - Lifetime EP0331370B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB888804590A GB8804590D0 (en) 1988-02-26 1988-02-26 Detergent compositions
GB8804590 1988-02-26

Publications (4)

Publication Number Publication Date
EP0331370A2 EP0331370A2 (de) 1989-09-06
EP0331370A3 EP0331370A3 (en) 1990-07-25
EP0331370B1 EP0331370B1 (de) 1994-10-05
EP0331370B2 true EP0331370B2 (de) 1999-06-09

Family

ID=10632461

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89301851A Expired - Lifetime EP0331370B2 (de) 1988-02-26 1989-02-24 Verfahren zur Herstellung einer Detergentzusammensetzung

Country Status (9)

Country Link
EP (1) EP0331370B2 (de)
JP (1) JPH07799B2 (de)
AU (1) AU615517B2 (de)
BR (1) BR8900868A (de)
CA (1) CA1312521C (de)
DE (1) DE68918612T3 (de)
ES (1) ES2063812T5 (de)
GB (1) GB8804590D0 (de)
ZA (1) ZA891459B (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU4806893A (en) * 1992-08-19 1994-03-15 Colgate-Palmolive Company, The Structured silicates and their use in automatic dishwashers
MY111592A (en) * 1992-08-19 2000-09-27 Colgate Palmolive Co Automatic dishwashing detergent containing an organic compound having at least one hydroxyl group
ZA935663B (en) * 1992-08-19 1995-02-06 Colgate Palmolive Co Cleaning composition
TR28439A (tr) * 1993-08-18 1996-06-24 Colgate Palmolive Co Yapilandirilmis silikatlar ve otomatik bulasik makinelerinde kullanimlari.
DE69434635D1 (en) 1993-10-08 2006-04-27 Novo Nordisk As Amylasevarianten
DE19526380A1 (de) * 1995-07-19 1997-01-23 Henkel Ecolab Gmbh & Co Ohg Pastöses Geschirreinigungsmittel und seine Herstellung
JP6443965B2 (ja) * 2014-07-31 2018-12-26 花王株式会社 液体漂白剤組成物
JP6655388B2 (ja) * 2015-12-28 2020-02-26 ライオン株式会社 食器洗い機用洗浄剤及びその製造方法、並びにスクイズ容器入り洗浄剤製品

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT330930B (de) * 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
JPS5464504A (en) * 1977-11-01 1979-05-24 Nippon Chem Ind Co Ltd:The Zeolite slurry for detergents
JPS5464531A (en) * 1977-11-02 1979-05-24 Nippon Zeon Co Ltd Water-dilutable coating composition
US4530780A (en) * 1981-11-16 1985-07-23 Lever Brothers Company Liquid detergent composition containing stabilizing electrolyte mixtures
MX167884B (es) * 1983-12-22 1993-04-20 Albright & Wilson Composicion detergente liquida
GB8334250D0 (en) * 1983-12-22 1984-02-01 Albright & Wilson Liquid detergent compositions

Also Published As

Publication number Publication date
ES2063812T3 (es) 1995-01-16
BR8900868A (pt) 1989-10-17
JPH01261500A (ja) 1989-10-18
CA1312521C (en) 1993-01-12
GB8804590D0 (en) 1988-03-30
EP0331370A3 (en) 1990-07-25
EP0331370A2 (de) 1989-09-06
DE68918612T2 (de) 1995-02-09
AU3029989A (en) 1989-08-31
DE68918612D1 (de) 1994-11-10
EP0331370B1 (de) 1994-10-05
DE68918612T3 (de) 1999-08-19
AU615517B2 (en) 1991-10-03
JPH07799B2 (ja) 1995-01-11
ES2063812T5 (es) 1999-08-16
ZA891459B (en) 1990-10-31

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