EP0407187A2 - Composition de nettoyage aqueuse thixotropique - Google Patents

Composition de nettoyage aqueuse thixotropique Download PDF

Info

Publication number
EP0407187A2
EP0407187A2 EP19900307343 EP90307343A EP0407187A2 EP 0407187 A2 EP0407187 A2 EP 0407187A2 EP 19900307343 EP19900307343 EP 19900307343 EP 90307343 A EP90307343 A EP 90307343A EP 0407187 A2 EP0407187 A2 EP 0407187A2
Authority
EP
European Patent Office
Prior art keywords
clay
cleaning composition
composition
builder
silicate
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Withdrawn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
EP19900307343
Other languages
German (de)
English (en)
Other versions
EP0407187A3 (en
Inventor
Robert John Corring
Machiel Goedhart
Steven Patrick Christiano
Jerry Jaroslav Krupa
Hendrik Simon Kielman
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
Original Assignee
Unilever PLC
Unilever NV
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 Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0407187A2 publication Critical patent/EP0407187A2/fr
Publication of EP0407187A3 publication Critical patent/EP0407187A3/en
Withdrawn legal-status Critical Current

Links

Images

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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/1253—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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • Powder dishwashing compositions are recognized to have a very good cleaning performance.
  • powders have several aspects which makes their use inconvenient. Thus, powders may spill or sift from the box or pouring spout, creating deposits of powder in undesired places. Also, powders are difficult to dose into dishwashing machines because they pour very quickly into the small dispensing cups of dishwashing machines. Further, the powders are subject to caking when stored over time in conditions of high ambient temperature or humidity.
  • autodish liquids themselves are subject to several problems.
  • a major drawback to such liquids is their tendency to undergo phase separation, or syneresis.
  • phase separation occurs, the solids suspended in the liquid, such as thickening agents, builder salts or china glaze protection agents, settle from the liquid.
  • the resultant product has a clear or translucent layer and an opaque, moist layer of solids.
  • This phase separation is unattractive to consumers, in that it seems to suggest the product is somehow impaired or defective.
  • one object of the present invention is to make an autodish liquid with improved phase stability.
  • Autodish liquids are usually aqueous compositions. Chlorine bleach is generally incorporated into these compositions for improved cleaning performance. However, the longer chlorine bleach is stored in an aqueous environment, the more decomposition of bleach occurs, with concomitant loss of bleach activity. Thus, a further object of the present invention is making an autodish liquid composition having reduced chlorine bleach loss.
  • compositions containing nonphosphate builders not only lose builder, but also substantial amounts of their chlorine bleach. These drawbacks have conventionally resulted in poorer cleaning by compositions which are substantially free of phosphate builder.
  • yet another object of the present invention is an autodish liquid which is substantially free of phosphate yet has cleaning performance and chemical stability to chlorine bleach which is comparable to phosphate built compositions.
  • compositions of the invention are aqueous liquid cleaning compositions which incorporate as thickeners a combination of certain clays and polymeric thickener agents. This combination is superior to either the clay or polymeric thickener alone in that it imparts not only beneficial viscosity to the compositions, but also improves phase stability and reduces loss of chlorine bleach in the aqueous environment. Moreover, the non-phosphate cleaning compositions of the invention have surprisingly effective cleaning performance.
  • the clay is a synthetic hectorite and the polymeric thickener is a cross-­linked polyacrylate of molecular weight of 500,000 to 5,000,000.
  • the builder is a polymeric poly­carboxylate, although of much smaller size than the polymeric thickener, having molecular weight of 2,000 to 6,000.
  • the composition is thixotropic and has viscosity of from 1,000 to 500,00 cps at 5 sec ⁇ 1.
  • composition is an automatic dishwashing detergent.
  • Two further embodiments of the composition may contain colorant and/or opacifying agent; and surfactant, respectively.
  • the amount of silicate and clay are present in the composition at a ratio of from 9:1 to 2:1, preferably 7:1 to 2:1 and most preferably 5:1 to 2:1.
  • the ratio of silicate to clay may be from 12:1 to 2:1, preferably 10:1 to 2:1 and most preferably from 8:1 to 2:1.
  • a further aspect of the invention is a method of imparting phase or bleach stability to a chlorine-containing thixotropic cleaning composition.
  • This method comprises incorporating into the composition the stabilizing system of clay and polymeric thickener in particular amounts and in a relative weight ratio to one another.
  • improved cleaning performance is imparted to a non-phosphate cleaning composition by adding the stabilizing system plus the polyacrylic builder described above.
  • Yet another aspect of the invention is a method of producing the thixotropic aqueous cleaning composition.
  • the clay is dispersed in water to form a slurry, heated to 40°C and stirred, after which polymeric thickener then silicate are added and stirred.
  • the water may first be heated and clay then added.
  • an amount of non-phosphate builder is added to the water prior to the clay to impart better viscosity to the composition during handling.
  • the clay and polymeric thickener of the composition together constitute a stabilizing system. When they are both present in a certain relative weight ratio to one another, the clay and polymeric thickener impart not only improved product stability but also reduced loss of the bleach in the aqueous environment.
  • the size of the clay particles renders them suitable for use in the present compositions.
  • the very fine synthetic hectorite clays are especially preferred because their small particle is found to be especially useful in imparting the desired properties to the compositions thickened and stabilized with the two-component stabilizing system.
  • particle size is understood to mean the size of the discrete grains of dry clay after they have been moistened.
  • a suitable particle size for the clays of the invention is from 0.001 to 1.0 micron, more preferably from 0.005 to 0.5 micron, and most preferably from 0.01 to 0.1 micron. If the clay materials mentioned below have particle size larger than desired, the materials may be subjected to grinding or crushing in order to help bring the average size of the particles within the desired size range.
  • Suitable clays for the thickening system and the cleaning compositions may include organophilic and layered clay minerals belonging to the geological classes of the smectites, the kaolins, the illites, the chlorites, the attapulgites and the mixed layer clays.
  • organophilic and layered clay minerals belonging to the geological classes of the smectites, the kaolins, the illites, the chlorites, the attapulgites and the mixed layer clays are Typical examples of specific clays belonging to these classes are: 1) smectites, e.g.
  • montmorillonite bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talc, beidellite; 2) illites, e.g., bravaisite, muscovite, paragonite, phlogopite; 3) chlorites, e.g., corrensite, penninite, donbassite, sudoite; 4) attapulgites, e.g., sepiolite, and polygorskyte.
  • the layered clay minerals may be either naturally occurring or synthetic.
  • Preferred clay minerals for use in the present invention are natural or synthetic smectites and atta­pulgites, (particularly the hectorites, montmorillonites and bentonites,) and of these the hectorites are especially preferred.
  • Many of the above clays are available commercially, and typical examples of commercial hectorites are the Laponites ex Laporte Industries Ltd. , England; Veegum Pro and Veegum F ex R. T. Vanderbilt, USA; and the Barasyms, Macaloids and Propaloids ex Baroid Division, National Lead Company, USA.
  • Particularly preferred commercial hectorites are the synthetic hectorites Laponite S, Laponite XLS, Laponite RD and Laponite RDS, of which Laponite XLS is especially preferred.
  • This is a synthetic hectorite having the following characteristics: analysis (dry basis) SiO2 59.8%, MgO 27.2%, Na2O 4.4%, Li2O 0.8%, structural H2O 7.8%, with the addition of tetrasodium pyrophosphate (6%); specific gravity 3.54; and bulk density 1.0.
  • the effective level of the layered clay in the compositions having the stabilizing system is from about 1% to about 5% by weight, preferably from about 2.0% to about 4.5% by weight, and most preferably from about 2.5% to about 3.5% by weight.
  • the polymeric thickener of the stabilizing system may suitably be a polycarboxylic polymer that has been inter-­polymerized with a multi-vinyl or multi-allylic functionalized cross-linking agent.
  • the polycarboxylic polymer is interpolymerized with a polyalkenyl polyether of a polyhydric compound.
  • the polyhydric compound should have at least 4 carbons and 3 hydroxy groups.
  • the thickeners are water-dispersible copolymers of an alpha-beta monoolefinically unsaturated lower aliphatic carboxylic acid cross-linked with a polyether of a polyol.
  • the polyol may be selected from the group consisting of oligosaccharides, reduced derivatives thereof in which the carbony; group is converted to an alcohol group, and pentaerythritol.
  • the hydroxy grops of said polyol are etherified with allyl groups, said polyol having at least two allyl groups per polyol molecule.
  • a suitable copolymer is one of acrylic acid with low percentages (0.71 to 1.5%) poly allyl sucrose.
  • Molecular weights of the cross-linked polymeric thickener may range from about 400,000 up to 10,000,000, preferably between 500,000 and 5,000,000, most preferably from about 1,000,000 to 4,000,000.
  • Examples of commercially available cross-linked polymers based upon allyl sucrose modified polyacrylic acid are the Carbopol resins manufactured by the B. F. Goodrich Chemical Company. These materials include Carbopol 941R (m.w. 1,250,000), Carbopol 934R (m. w. 3,000,000) and Carbopol 940R (m.w. 4,000,000). Carbopol 950 R, Carbopol 951 R and Carbopol 954 R. Most preferred is Carbopol 934R .
  • the polymeric thickener of this invention may be present in an amount from about 0 to about 5% by weight, preferably from about 0.1 to about 1% by weight, and most preferably from about 0.15 to about 0.4% by weight of the composition.
  • the layered clay and polymeric thickener when they are both present, they should be present in a relative weight ratio of from about 40:1 to about 5:1, preferably 35:1 to 10:1, and most preferably from about 30:1 to 15:1.
  • the instant clay and polymer system does not require the presence of a multivalent ion, a long chain fatty acid or a combination thereof in order to thicken compositions. It is believed that no other element is necessary here to thicken.
  • the cleaning composition incorporating the stabilizing system may, when formulated, be substantially free of multivalent ions or long chain fatty acids or a conbination thereof or other thickening agents except the layered clay and cross-linked polymeric thickener.
  • the cleaning composition includes a builder element in order to sequester hardness ions, ie calcium and magnesium which are present in the wash water. If these cations are not sequestered, they can form undesirable precipitates with soil and surfactant molecules. These precipitates can remain on the surfaces to be cleaned and cause spotting or filming.
  • a builder element in order to sequester hardness ions, ie calcium and magnesium which are present in the wash water. If these cations are not sequestered, they can form undesirable precipitates with soil and surfactant molecules. These precipitates can remain on the surfaces to be cleaned and cause spotting or filming.
  • the builder element of the composition may be a phosphate-containing compound.
  • These compounds include salts of orthophosphates, pyrophosphates and polyphosphates, as well as organophosphates.
  • Suitable counterions include alkali metal ions, and ammonium or substituted ammonium.
  • the preferred phosphate builders are polyphosphate salts, because these have the greatest solubility and hardness ion sequestering effect. Most preferred are hydrated alkali metal salts of polyphosphate. These hydrated salts form needle-like crystals, as opposed to the cubic crystals formed by unhydrated phosphates. These needle-like crystals are less likely to coalesce into larger crystals.
  • non-hydrated phosphate salt crystals do coalesce, they cause a rise in viscosity of the liquid over time. Rather than have this uncontrolled increase in viscosity, it is preferred to avoid such a rise in viscosity by using hydrated phosphate salts at the outset.
  • the cleaning composition may further or alternatively comprise a non-phosphate builder.
  • a non-phosphate builder Such builders may suitably be inorganic, such as alkali metal carbonates such as are well known.
  • the builder material may be organic, such as alkali metal salts of citric acid or other polycarboxylic compounds. It is found that polymeric polycarboxylic molecules of molecular weight of from about 1,000 to 100,000 are most preferred as non-phosphate builders, especially those having bleach stability, with molecular weights of 2,000 to 20,000 being preferred and 3,000 to 10,000 being most preferred. Suitable polycarboxylic polymeric compounds include homopolymers of acrylic acid, maleic acid, itaconic acid and the like, as well as copolymers of such monomeric materials.
  • Commercially available non-phosphate builder materials include Alcosperse 602N ex Alco Chemical Company (MW 4,500 having 45% solids); and Sokalan PA-30 (MW 8,000).
  • the builder compounds are present in the composition at from about 0.1 to about 4.0%, preferably from 0. 5 to 20% and most preferably from 2 to about 10%.
  • the cleaning composition When used as an automatic dishwashing formulation, it will normally also contain an oxidizing agent.
  • liquid dishwashing compositions have for this purpose used sodium hypochlorite because it is inexpensive.
  • Other oxidizing agents may however be used.
  • heterocyclic N-bromo and N-chloro imides such as trichlorocyanuric, tribromocyanuric, dibromo and dichlorocyanuric acids, and salts thereof with water solubilizing cations such as potassium and sodium.
  • An example of a hydrated dichlorocyanurate acid is Clearon CDB 56, a product manufactured by the Olin Corporation.
  • the oxidizing material will be present in the composition such that from about 0.1 to 1.5% available chlorine is produced.
  • Preferred compositions will have 0.5 to 1.2% available chlorine.
  • Automatic dishwashing detergent compositions based upon this invention will also contain alkali metal silicate.
  • This material is employed as a cleaning ingredient, source of alkalinity, metal corrosion inhibitor, and protector of glaze on china tableware.
  • sodium silicate having a ratio of SiO2:Na2O from about 1.0 to about 3.3, preferably from about 2 to about 3.2.
  • the silicate may be used in the form of an aqueous liquor or a solid. lt will be present from about 1 to 50 % by weight, more preferably from about 5 to about 20% by weight of the composition.
  • Amounts of water present in the liquid compositions should neither be so high as to produce unduly low viscosity and fluidity, nor so low as to produce unduly high viscosity and low flowability, thixotropic properties in either case being diminished or destroyed. Water will therefore generally be present in an amount ranging from about 25 to 80%, preferably from about 45 to 75%, and most preferably from about 55 to 65% by weight of the composition.
  • One or more bleach-stable surfactants may optionally be incorporated in the cleaning compositions. These surfactants should be of the low-foaming type, since foam interferes with the dishwasher cleaning action. Suitable low foaming anionic surfactants may be very useful for the cleaning compositions, especially when combined with effective defoaming materials. Anionics are desirable because they are more stable toward hypochlorite than many nonionic surfactants.
  • Suitable anionic surfactants are alkyl diphenyloxide sulfonate, alkyl naphthalene sulfonate, sodium 2-acetamidohexadecane sulfonate and nonionic alkoxylates having a sodium alkylene carboxylate moiety linked to a terminal hydroxy group of the nonionic through an ether bond.
  • Suitable nonionics which have bleach stability, are those described in our copending U.S. patent application by Gabriel et al. , Serial No. 183,512, filed April 14, 1988, which is hereby incorporated by reference.
  • surfactants are employed at an amount from about 0.1 to about 10%, preferably from about 0.15 to 5%, and most preferably from about 0.2 to 3% by weight of the composition.
  • Defoaming of the wash may be accomplished by the presence of any of number of commercially available defoaming agents. These agents may be of the general type of slightly soluble alkyl carboxylates, alkyl phosphates, hydrocarbon waxes, hydrophobic silicas, silicone defoamers or many others. In addition to being an effective defoamer, the preferred species are stable to hypochlorite. Because some defoaming agents tend to deposit on glassware washed with the instant composition, thereby causing unsightly filming, preferred defoaming agents are those which do not deposit on glassware.
  • the defoamer will optionally be present in the composition from about 0.05 to 5%, preferably from about 0.1 to 1%, and most preferably from about 0.1 to 0.5% by weight of the composition.
  • the composition may further include perfumes, colorants, opacifying agents (e.g. titanium dioxide), flow control agents, soil suspending agents, alkaline agents, antiredeposition agents, anti-tarnish agents, enzymes and other functional additives.
  • opacifying agents may be used at levels of 0.05-05%.
  • the composition is found to have surprisingly good cleaning performance. Glass appearance is usually an indication of cleaning performance. Cleaning by phosphate built compositions is usually superior to that by non-phosphate compositions. This is because phosphate is such an effective hardness ion sequestrant and soil suspending agent.
  • the compositions described herein having non-phosphate builder impart an improved glass appearance to washed glasses. This improved glass appearance can be equal to that of phosphate-built compositions. Even at high levels of water hardness, where calcium and magnesium are likely to cause filming and spotting precipitates, the non-phosphate built compositions are found to have spotting and filming at an acceptably low level.
  • non-phosphate compositions described herein also have robust cleaning performance with respect to difficult soils. Thus, these compositions are found to remove egg yolk and dried cereal as effectively or better than phosphate-built compositions. This parity performance is surprising in that non-phosphate cleaning compositions conventionally do not clean as well as phosphate-built ones.
  • the base cleaning composition may be utilized for other purposes.
  • the cleaning composition of this invention may be useful in products such as fabric washing formulations, hand dishwashing liquids, toilet bowl scrubs, pot/pan cleaners, fabric softeners, and denture cleaners.
  • the cleaning composition may be made by mixing the components in water in any order.
  • the clay and polymeric mixer may be mixed in dry form then added to water and stirred for 10 to 15 minutes. This stirring disperses the clay and thickener and allows the clay to swell and the polymeric thickener to be hydrated. Stirring is preferably performed at high speeds on conventional mixing equipment.
  • alkaline salts of the composition are added to the aqueous mixture. These are stirred until dissolved, usually for about 10 minutes.
  • the builder is added and stirred until dispersed.
  • Polymeric builder is usually in liquid form and so requires short mixing time.
  • the aqueous mixture is allowed to cool to about room temperature, and the bleach component is added and stirred.
  • the invention further comprises a method of producing the thixotropic aqueous cleaning composition, the method comprising:
  • the resulting composition has good phase stability. It is noted however, that regardless of the order of addition used, there is an increase in the viscosity of the slurry when the clay is added. Thus, the viscosity increases observed are in proportion to the amount of clay or the type of clay added. These viscosity increases may render processing more difficult.
  • a liquid autodish composition is made according to the following formulation Sodium tripolyphosphate 8.5% Potassium tripolyphosphate 5.4% Sodium metasilicate 21.0% Sodium hypochlorite (aq) (as av Cl2) 1.3% Laponite XLS clay 3.5% Carbopol 934 polyacrylate 0.2% Water balance
  • the water is added to a glass beaker placed in a 40°C water bath.
  • the Laponite clay and Carbopol are mixed together and then added to the water over 1 minute.
  • Mixing in the water is provided by a Talboy stirrer fitted with a propellor-­type agitator.
  • the mixture is stirred for a few minutes to hydrate and swell the thickeners.
  • the metasilicate is then added over 5 minutes, after which the mixture is stirred for another 5 minutes.
  • the sodium tripolyphosphate and potassium tripolyphosphate over are then added over 10 minutes. The complete mixture is then stirred for a further 10 minutes to dissolve most of the phosphates.
  • the mixture is then cooled to 30°C with a 20°C water bath, and the hypochlorite solution is then added slowly.
  • the resulting autodish liquid is a thick, pasty, opaque liquid which flows slowly.
  • An important consideration in formulating an autodish liquid is its retention in the dispensing cup of the machine dishwasher.
  • the viscosity of the autodish liquid must be high enough to retain the liquid in the cup during a series of pre-washes and rinses.
  • compositions from Example 2 are prepared, however further incorporating into the composition having the stabilizing system a non-phosphate builder: ie, 4.5% by weight of Alcosperse 602N, a sodium salt of polyacrylic acid having average molecular weight of from 4,500.
  • a sample of both autodish liquids is stored at room temperature, 40°C and 50°C. The samples are stored at these temperatures for sixteen weeks, at which time the volume in each sample which has undergone syneresis is measured. As shown in Fig.
  • the percentage of syneresis is as follows: RT 40°C 50°C Nonphosphate autodish liquid 12% 4% 6% Commercial autodish liquid 16% 28% 32%
  • the physical stability of the composition containing the layered clay/polymeric thickener stabilizing system is superior to that of the commercial clay-thickened autodish liquid.
  • the non-phosphate composition made in Example 3 is made holding the amount of Carbopol 934 constant at 0.2% by weight while varying the amount of Laponite XLS from 0 to 4% by weight of tho composition, in 1.0% increments.
  • the viscosity of each composition is measured using a Haake viscometer at 5 sec ⁇ 1 and 21 sec ⁇ 1. The viscosity measurements are shown in Fig. 2.
  • Example 3 the non-phosphate composition made in Example 3 is made holding the amount of Laponite XLS constant at 3.5% while varying the amount of Carbopol 934 from 0 to 0.4% by weight. Viscosity is again measured at 5 and 21 sec ⁇ 1; these viscosity measurements are illustrated in Fig. 3.
  • the desirable viscosity range for autodish liquids extends from 3 to 8 Pa S at 5 sec ⁇ 1.
  • Fig. 3 shows the useful range of Carbopol 934 is from 1.5 to 3.5% by weight of the composition.
  • a batch of the commercial autodish liquid from Example 2 and of the nonphosphate autodish liquid composition of claim 3 (4.5% Alcosperse 602N and 1% available chlorine) are formulated.
  • a sample of each is stored at three different temperatures: room temperature, 40°C and 50°C.
  • room temperature 40°C and 50°C.
  • 15 ml samples are drawn from each 500 ml sample and tested by standard iodometric titration for % available chlorine. The results of this test are illustrated in Figs. 4 and 5.
  • the non-phosphate composition (Fig. 4) has about 70% of its chlorine. Less is retained at the higher temperatures.
  • the heat is lowered and 24 g of cream of wheat are added.
  • the cereal is cooked over low heat for 10 minutes with stirring then cooled to room temperature.
  • 200 g of the cooked cereal is then blended with 100 ml of distilled water in an OsterizerR blender for 2 minutes.
  • the resulting mixture is strained through a 32 mesh screen.
  • Egg yolk soil is prepared by separating yolks from 10 large raw eggs, and blending 200 ml of yolk and 45 ml of distilled water for 3 minutes in an OsterizerR blender.
  • a thin layer of one of the soils (about 0.5 g) is applied to clean dishes with a Black & Decker paint sprayer. The dish is allowed to dry for 10 to 15 minutes, and a second layer of the same soil is applied. Dishes soiled with cream of wheat are dried overnight; dishes soiled with egg yolk are baked in an oven preheated to 100°C for 50 minutes, then aged overnight.
  • the soiled dishes are placed randomly in a Bosch S 512 Economic model dishwasher. Either the autodish liquid from Example 2 or the one shown above is used to clean the dishes in a normal wash cycle. Dishes soiled with cream of wheat are scored for soil removal by dipping in a 1:10 aqueous solution of iodine and evaluating the amount of soil remaining. Dishes soiled with egg yolk are evaluated as is. Both are scored on a scale of 0 to 5, with 0 being no soil removal and 5 corresponding to complete soil removal. Results appear in Fig. 8 and indicate that even though the formulation from Example 2 is a non-phosphate formulation, it has a cleaning performance comparable to phosphate-built formulations.
  • the level of silicate is at least 10% and silicate and clay are present in the composition at a ratio of from 7:1 to 2:1, preferably 5:1 to 2:1 and most preferably 4:1 to 2:1.
  • Silicate at these levels with the clay imparts viscosity and. phase stability to the composition. Above the 7:1 ratio however, silicate (in the absence of polymeric thickener) does not always impart phase stability.
  • the ratio of silicate to clay may be above 7:1, i.e. from 12:1 to 2:1, preferably 10:1 to 2:1 and most preferably from 8:1 to 2:1.
  • the amounts of silicate and clay are within these higher ratios, the physical stability of the resulting composition is improved, as demonstrated in the following Examples.
  • the sample is prepared on a 1000 g batch scale using a 1 L beaker and a mechanical stirrer fitted with a variable speed control and a simple turbine style blade with about a 1.5 inch radius.
  • the Laponite clay is sifted into the water with sufficient agitation to provide moderate vortexing.
  • the clay is allowed to disperse initially in water at or somewhat below room temperature but then the aqueous clay slurry is heated up to about 40°C. Stirring is continued at this temperature for about 40 minutes.
  • Laponite XLS slurries are relatively low viscosity homogeneous liquids and appear to be free of lumps.
  • the beaker is then allowed to cool to room temperature during the remaining addition steps.
  • the speed of agitation is increased and the Carbopol polymer is sifted in as a free flowing powder. About 30 minutes is allowed for dispersion and swelling of the polymer.
  • the physical stability and the viscosity of the nineteen samples are measured at a lower and higher shear rates (5 s ⁇ 1 and 21 s ⁇ 1). Physical stability is measured as a function of volume % separation after 4 weeks of storage at room temperature. Viscosity is measured using a Haake Rotovisco RV100 coupled with a M150 test unit. The measurement is performed using the shear rate sweep mode at a rate of 0. 25 s ⁇ 2.
  • Table 2 demonstrates that raising silicate levels above a ratio of 9:1 substantially increases physical instability of the formulations with great physical instability resulting at ratios in excess of 12:1. However, in the presence of 0.2% polymeric thickener, a silicate:clay ratio of as high as 14.2 is tolerated without significant physical separation.
  • the invention further comprises a method of producing the thixotropic aqueous cleaning composition, the method comprising:
  • the resulting composition has good phase stability. It is noted however, that there may be a large increase in the viscosity of the slurry being mixed when the silicate is added. Such increases in viscosity can retard production rates of cleaning compositions of the invention; any method of avoiding such slow downs would therefore result in higher production rates.
  • Increases in viscosity during production of the cleaning composition may be minimized by altering the order of mixing to put some of the low molecular weight polymeric builder into the batch prior to addition of Laponite RD.
  • the following order of addition is followed in making a 1000 g sample.
  • the batch is prepared as described in Example 10 above except a fraction of the total of the Alcosperse polymer is added to the water prior to the Laponite clay. This amount is 0. 15% of the total composition. This order of addition has the effect of lowering the viscosity of the clay slurry during processing.
  • Table 4 contains measurements of the viscosity of the Laponite slurry at various levels of polymer addition prior to the clay. Viscosity is measured at 0.9 sec ⁇ 1 and 20 sec ⁇ 1. The Quality of the clay dispersion is reflected in the final column: a "+"sign indicates a good quality dispersion having a high final batch viscosity; a"-" sign indicates a partly flocculated dispersion leading to a thin batch with less than acceptable final viscosity and which tends to rapidly physically separate.

Landscapes

  • 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)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)
EP19900307343 1989-07-07 1990-07-05 Aqueous thixotropic cleaning composition Withdrawn EP0407187A3 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US37646889A 1989-07-07 1989-07-07
US376468 1989-07-07
US47470890A 1990-01-29 1990-01-29
US474708 1990-01-29

Publications (2)

Publication Number Publication Date
EP0407187A2 true EP0407187A2 (fr) 1991-01-09
EP0407187A3 EP0407187A3 (en) 1991-07-17

Family

ID=27007422

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900307343 Withdrawn EP0407187A3 (en) 1989-07-07 1990-07-05 Aqueous thixotropic cleaning composition

Country Status (4)

Country Link
EP (1) EP0407187A3 (fr)
JP (1) JPH0374498A (fr)
AU (1) AU637383B2 (fr)
CA (1) CA2020647A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0517310A1 (fr) * 1991-06-07 1992-12-09 Colgate-Palmolive Company Composition détergente aqueuse liquide contenant un agent d'épaississement polymère
EP0519603A1 (fr) * 1991-05-20 1992-12-23 Colgate-Palmolive Company Composition détergente exempte de phosphate, sous forme de gel pour le lavage de la vaiselle en machine
GR1001212B (el) * 1992-05-29 1993-06-21 Colgate Palmolive Co Συνθεση υδατικου υγρου απορρυπαντικου, εχουσα ενα πολυμερικο πυκνωτικο.
WO1993022412A1 (fr) * 1992-04-30 1993-11-11 Unilever N.V. Produits nettoyants liquides
WO1997011147A1 (fr) * 1995-09-19 1997-03-27 Reckitt & Colman S.A. Compositions de nettoyage a rheologie amelioree
DE19700799A1 (de) * 1997-01-13 1998-07-16 Henkel Kgaa Wäßrige Bleichmittel
WO2000011128A1 (fr) * 1998-08-19 2000-03-02 Jeyes Group Limited Compositions liquides de blanchiment
DE19854960A1 (de) * 1998-11-29 2000-05-31 Clariant Gmbh Maschinengeschirrspülmittel
WO2001027236A1 (fr) * 1999-10-08 2001-04-19 Henkel Kommanditgesellschaft Auf Aktien Agent nettoyant aqueux thixotrope
WO2001032820A1 (fr) * 1999-10-30 2001-05-10 Henkel Kommanditgesellschaft Auf Aktien Detergents ou nettoyants
WO2001083662A1 (fr) * 2000-05-04 2001-11-08 Henkel Kommanditgesellschaft Auf Aktien Utilisation de particules nanoscopiques pour faciliter l'enlevement des salissures
EP1162255A2 (fr) * 2000-06-07 2001-12-12 Kao Corporation Composition détergente liquide
WO2007079880A1 (fr) * 2005-12-22 2007-07-19 Henkel Kommanditgesellschaft Auf Aktien Détergent pour laver la vaisselle à la main
WO2008023295A2 (fr) * 2006-08-24 2008-02-28 Kimberly-Clark Worldwide, Inc. Formule nettoyante liquide aux propriétés de suspension et de formation de mousse
WO2009040728A1 (fr) * 2007-09-24 2009-04-02 The Procter & Gamble Company Procédé de lavage de vaisselle

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4116851A (en) * 1977-06-20 1978-09-26 The Procter & Gamble Company Thickened bleach compositions for treating hard-to-remove soils
EP0075813A2 (fr) * 1981-09-26 1983-04-06 Henkel Kommanditgesellschaft auf Aktien Application d'un agent de nettoyage pâteux dans machines à laver la vaisselle
GB2140450A (en) * 1983-05-24 1984-11-28 Colgate Palmolive Co Thixotropic automatic dishwasher composition with chlorine bleach
FR2568888A1 (fr) * 1984-08-13 1986-02-14 Colgate Palmolive Co Detergent pour machine a laver la vaisselle automatique
EP0264975A1 (fr) * 1986-08-18 1988-04-27 The Procter & Gamble Company Compositions aqueuses épaissisantes pour le lavage de la vaiselle
EP0329419A2 (fr) * 1988-02-17 1989-08-23 Unilever Plc Compositions détergentes contenant des épaississeurs polymériques réticulés et un agent de blanchiment à base d'hypochlorite

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8328078D0 (en) * 1983-10-20 1983-11-23 Unilever Plc Dishwashing compositions
JPH02501488A (ja) * 1987-11-12 1990-05-24 ユニリーバー・ナームローゼ・ベンノートシヤープ 自動皿洗い機用液体洗剤の物理的安定性の改良

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4116851A (en) * 1977-06-20 1978-09-26 The Procter & Gamble Company Thickened bleach compositions for treating hard-to-remove soils
EP0075813A2 (fr) * 1981-09-26 1983-04-06 Henkel Kommanditgesellschaft auf Aktien Application d'un agent de nettoyage pâteux dans machines à laver la vaisselle
GB2140450A (en) * 1983-05-24 1984-11-28 Colgate Palmolive Co Thixotropic automatic dishwasher composition with chlorine bleach
FR2568888A1 (fr) * 1984-08-13 1986-02-14 Colgate Palmolive Co Detergent pour machine a laver la vaisselle automatique
EP0264975A1 (fr) * 1986-08-18 1988-04-27 The Procter & Gamble Company Compositions aqueuses épaissisantes pour le lavage de la vaiselle
EP0329419A2 (fr) * 1988-02-17 1989-08-23 Unilever Plc Compositions détergentes contenant des épaississeurs polymériques réticulés et un agent de blanchiment à base d'hypochlorite

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0519603A1 (fr) * 1991-05-20 1992-12-23 Colgate-Palmolive Company Composition détergente exempte de phosphate, sous forme de gel pour le lavage de la vaiselle en machine
EP0517310A1 (fr) * 1991-06-07 1992-12-09 Colgate-Palmolive Company Composition détergente aqueuse liquide contenant un agent d'épaississement polymère
WO1993022412A1 (fr) * 1992-04-30 1993-11-11 Unilever N.V. Produits nettoyants liquides
GR1001212B (el) * 1992-05-29 1993-06-21 Colgate Palmolive Co Συνθεση υδατικου υγρου απορρυπαντικου, εχουσα ενα πολυμερικο πυκνωτικο.
US6268325B1 (en) 1995-09-19 2001-07-31 Reckitt & Colman Sa Cleaning compositions containing thickeners and abrasive materials
WO1997011147A1 (fr) * 1995-09-19 1997-03-27 Reckitt & Colman S.A. Compositions de nettoyage a rheologie amelioree
DE19700799A1 (de) * 1997-01-13 1998-07-16 Henkel Kgaa Wäßrige Bleichmittel
DE19700799C2 (de) * 1997-01-13 1999-02-04 Henkel Kgaa Wäßrige Textilbleichmittel
WO2000011128A1 (fr) * 1998-08-19 2000-03-02 Jeyes Group Limited Compositions liquides de blanchiment
DE19854960A1 (de) * 1998-11-29 2000-05-31 Clariant Gmbh Maschinengeschirrspülmittel
WO2001027236A1 (fr) * 1999-10-08 2001-04-19 Henkel Kommanditgesellschaft Auf Aktien Agent nettoyant aqueux thixotrope
WO2001032820A1 (fr) * 1999-10-30 2001-05-10 Henkel Kommanditgesellschaft Auf Aktien Detergents ou nettoyants
WO2001083662A1 (fr) * 2000-05-04 2001-11-08 Henkel Kommanditgesellschaft Auf Aktien Utilisation de particules nanoscopiques pour faciliter l'enlevement des salissures
EP1162255A2 (fr) * 2000-06-07 2001-12-12 Kao Corporation Composition détergente liquide
EP1162255A3 (fr) * 2000-06-07 2002-01-02 Kao Corporation Composition détergente liquide
US6699831B2 (en) 2000-06-07 2004-03-02 Kao Corporation Liquid detergent composition comprising aluminosilicate or crystalline silicate
WO2007079880A1 (fr) * 2005-12-22 2007-07-19 Henkel Kommanditgesellschaft Auf Aktien Détergent pour laver la vaisselle à la main
WO2008023295A2 (fr) * 2006-08-24 2008-02-28 Kimberly-Clark Worldwide, Inc. Formule nettoyante liquide aux propriétés de suspension et de formation de mousse
WO2008023295A3 (fr) * 2006-08-24 2008-06-05 Kimberly Clark Co Formule nettoyante liquide aux propriétés de suspension et de formation de mousse
US7838477B2 (en) 2006-08-24 2010-11-23 Kimberly-Clark Worldwide, Inc. Liquid cleanser formulation with suspending and foaming capabilities
AU2007287280B2 (en) * 2006-08-24 2012-08-23 Kimberly-Clark Worldwide, Inc. Liquid cleanser formulation with suspending and foaming capabilities
WO2009040728A1 (fr) * 2007-09-24 2009-04-02 The Procter & Gamble Company Procédé de lavage de vaisselle
EP2045315A1 (fr) * 2007-09-24 2009-04-08 The Procter and Gamble Company Procédé pour laver la vaisselle

Also Published As

Publication number Publication date
AU637383B2 (en) 1993-05-27
CA2020647A1 (fr) 1991-01-08
AU5874490A (en) 1991-01-10
JPH0374498A (ja) 1991-03-29
EP0407187A3 (en) 1991-07-17

Similar Documents

Publication Publication Date Title
AU607717B2 (en) Thixotropic clay aqueous suspensions containing polyacrylic acid polymer or copolymer stabilizers
EP0407187A2 (fr) Composition de nettoyage aqueuse thixotropique
EP0295093B1 (fr) Détergent liquide pour machine à laver la vaisselle
EP0323209B1 (fr) Compositions détergentes
EP0446761A1 (fr) Compositions détergentes liquides aqueuses à visco-élasticité linéaire, notamment pour lave-vaisselle automatique, ou à stabilité améliorée à température élevée
GB2140450A (en) Thixotropic automatic dishwasher composition with chlorine bleach
CA1146436A (fr) Agglomeres de zeolite pour detergents
JPS6348399A (ja) ビルダ−としての珪酸ナトリウム並びにコ−ビルダ−及び活性塩素支持剤を含む食器具用洗剤
CA1239562A (fr) Suspensions epaisses detergentes, homogenes, pour la lessive, contenant des stabilisateurs acryliques polymeres
AU616906B2 (en) Thickened aqueous no- or low- phosphate built cleaning composition
EP0502030B1 (fr) Composition nettoyante
EP0479370A2 (fr) Compositions détergentes liquides
EP0314061A2 (fr) Composition détergente liquide aqueuse thixotropique pour le lavage automatique de la vaisselle
US5188752A (en) Linear viscoelastic automatic dishwasher compositions containing a crosslinked methyl vinyl ether/maleic anhydride copolymer
EP0315024A2 (fr) Composition détergente liquide aqueuse thixotropique pour le lavage automatique de la vaiselle
CA1312521C (fr) Compositions detergentes
JPS60262896A (ja) ビルダー入り粒状非イオン性洗剤組成物
EP0519603A1 (fr) Composition détergente exempte de phosphate, sous forme de gel pour le lavage de la vaiselle en machine
NZ242383A (en) Viscoelastic aqueous liquid automatic dishwasher detergent incorporating a fatty acid or benzoic acid derivative which is liquid at room temperature, and a crosslinked polycarboxylate thickening agent
EP0517309A1 (fr) Composition détergente aqueuse liquide, visco-élastique linéaire, spécialement pour le lavage de la vaisselle en machine avec stabilité améliorée à haute température
EP0523826A1 (fr) Composition détergente liquide aqueuse visco-élastique, notamment pour lave-vaisselle automatique, de distribution améliorée
CA2015541A1 (fr) Detergent pour lave-vaisselle en solution aqueuse dote de proprietes anti-taches et anti-depots ameliorees
EP0517310A1 (fr) Composition détergente aqueuse liquide contenant un agent d'épaississement polymère
EP0574236A2 (fr) Composition aqueuse contenant un polymère non-réticulé pour augmenter la viscosité
CA2069835A1 (fr) Composition detergent liquide aqueuse, a epaississant polymere

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): CH DE ES FR GB IT LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): CH DE ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19911025

17Q First examination report despatched

Effective date: 19920403

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER PLC

Owner name: UNILEVER N.V.

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19930503