EP0541204A1 - Linear viscoelastic aqueous liquid automatic dishwasher detergent composition - Google Patents

Linear viscoelastic aqueous liquid automatic dishwasher detergent composition Download PDF

Info

Publication number
EP0541204A1
EP0541204A1 EP92304893A EP92304893A EP0541204A1 EP 0541204 A1 EP0541204 A1 EP 0541204A1 EP 92304893 A EP92304893 A EP 92304893A EP 92304893 A EP92304893 A EP 92304893A EP 0541204 A1 EP0541204 A1 EP 0541204A1
Authority
EP
European Patent Office
Prior art keywords
composition
alkali metal
polymeric
dynes
radians
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Withdrawn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
EP92304893A
Other languages
German (de)
English (en)
French (fr)
Inventor
Amjad Farooq
Ammanuel Mehreteab
Lynne A. Miller
Nagaraj Shripad Dixit
Guy Broze
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.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive Co
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 Colgate Palmolive Co filed Critical Colgate Palmolive Co
Publication of EP0541204A1 publication Critical patent/EP0541204A1/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Withdrawn legal-status Critical Current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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • 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
    • C11D3/16—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

  • Liquid automatic dishwasher detergent compositions both aqueous and nonaqueous, have recently received much attention, and the aqueous products have achieved commercial popularity.
  • Patent 3,684,722 other patents relating to thickened detergent compositions include U.S. Patent 3,985,668; U.K. Patent Applications GB 2,116,199A and GB 2,140,450A; U.S. Patent 4,511,487; U.S. Patent 4,752,409 (Drapier, et al.); U.S. Patent 4,801,395 (Drapier, et al.); U.S. Patent 4,801,395 (Drapier, et al.).
  • Figures 1-13 are rheograms, plotting elastic modules G' and viscous modulus G'' as a function of applied strain, for the compositions of Example 1, Formulations A, C, D, G, J, H, I and K, Example 2, A and B, Example 3, L and M and Comparative Example 1, respectively and Figures 14-30 are rheograms as functions of frequency and applied strain for the compositions of Example V.
  • a novel aqueous liquid automatic dishwasher detergent composition is characterized by its linear viscoelastic behavior, substantially indefinite stability against phase separation or settling of dissolved or suspended particles, low levels of bottle residue, relatively high bulk density, and substantial absence of unbound or free water.
  • compositions are further characterized by a bulk density of at least 1.32 g/cc, such that the density of the polymeric phase and the density of the aqueous (continuous) phase are approximately the same.
  • compositions of this invention are aqueous liquids containing various cleansing active ingredients, detergent adjuvants, structuring and thickening agents and stabilizing components, although some ingredients may serve more than one of these functions.
  • compositions of this invention including physical stability, low bottle residue, high cleaning performance, e.g. low spotting and filming, dirt residue removal, and so on, and superior aesthetics, are believed to be attributed to several interrelated factors such as low solids, i.e. undissolved particulate content, product density and linear viscoelastic rheology.
  • compositional components of the formulations namely, (1) the inclusion of a thickening effective amount of polymeric thickening agent having high water absorption capacity, exemplified by high molecular weight cross-linked polyacrylic acid, (2) inclusion of a physical stabilizing amount of a long chain fatty acid or salt thereof, (3) potassium ion to sodium ion weight ratio K/Na in the range of from 1:2 to 45:1, preferably 1:1 to 45:1, especially from 1:1 to 3:1, and (4) a product bulk density of at least 1.32 g/cc, such that the bulk density and liquid phase density are the same.
  • linear viscoelastic or linear viscoelasticity means that the elastic (storage) moduli (G') and the viscous (loss) moduli (G'') are both substantially independent of strain, at least in an applied strain range of from 0-50%, and preferably over an applied strain range of from 0-80%.
  • a composition is considered to be linear viscoelastic for purposes of this invention, if over the strain range of 0-50% the elastic moduli G' has a minimum value of 100 dynes/sq.cm., preferably at least 250 dynes/sq.cm., and varies less than 500 dynes/sq.cm, preferably less than 300 dynes/sq.cm., especially preferably less than 100 dynes/sq.cm.
  • the minimum value of G' and maximum variation of G' applies over the strain range of 0 to 80%.
  • the variation in loss moduli G'' will be less than that of G'.
  • the ratio of G''/G (tan ⁇ ) is less than 1, preferably less than 0.8, but more than 0.05, preferably more than 0.2, at least over the strain range of 0 to 50%, and preferably over the strain range of 0 to 80%. It should be noted in this regard that % strain is shear strain x100.
  • the elastic (storage) modulus G' is a measure of the energy stored and retrieved when a strain is applied to the composition while viscous (loss) modulus G'' is a measure to the amount of energy dissipated as heat when strain is applied. Therefore, a value of tan ⁇ , 0.05 ⁇ tan ⁇ ⁇ 1, preferably 0.2 ⁇ tan ⁇ ⁇ 0.8 means that the compositions will retain sufficient energy when a stress or strain is applied, at least over the extent expected to be encountered for products of this type, for example, when poured from or shaken in the bottle, or stored in the dishwasher detergent dispenser cup of an automatic dishwashing machine, to return to its previous condition when the stress or strain is removed.
  • compositions with tan ⁇ values in these ranges therefore, will also have a high cohesive property, namely, when a shear or strain is applied to a portion of the composition to cause it to flow, the surrounding portions will follow.
  • the compositions will readily flow uniformly and homogeneously from a bottle when the bottle is tilted, thereby contributing to the physical (phase) stability of the formulation and the low bottle residue (low product loss in the bottle) which characterises the invention compositions.
  • the linear viscoelastic property also contributes to improved physical stability against phase separation of any undissolved suspended particles by providing a resistance to movement of the particles due to the strain exerted by a particle on the surrounding fluid medium.
  • the present invention also relates to polymeric compositions which are thickened aqueous polymeric solutions formed from water and 0.1 to 20 weight %, more preferably 0.5 to 14 weight percent of a polymeric complex which comprises an alkali metal neutralized anionic polymer having a molecular weight of 60,000 to 10,000,000 complexed at a pH of 7-10 with a structuring agent such as an amphoteric metal oxide compound having a particle size of 0.5 to 40 microns, which improves the formation of the polymeric matrix of the anionic polymer, wherein a weight ratio of the alkali metal neutralized anionic polymer to the amphoteric metal oxide compound is 10:1 to 1:10 and the aqueous thickened polymeric solution has a pH of 7 to 10 and a complex viscosity at 10 radians/seconds at room temperature as applied for 30 seconds of 2 to 800 dynes seconds/sq.cm..
  • the aqueous thickened polymeric solution has a G' of at least 80 dynes/sq.cm. at 10 radians/second, a G'' of at least 10 dynes/sq.cm., a ratio of G''/G' of less than 1 and G' is substantially linear over a range of frequency of 0.1 to 50 radians/second and a Brookfield viscosity at RT at 20 rpms with a #6 spindle of 700 to about 27,000 cps.
  • the aqueous thickened polymeric solution has a minimum yield stress of at least 2 dynes/sq.cm., more preferably 2 to 1200 dynes/sq.cm., it is capable of suspending solid particles such as alkali metal silicates and alkali metal detergent builder salts such that they will not settle out of solution.
  • the solid particles to be suspended are not limited to alkali metal compounds, but can be any metal containing compound, organic compound, polymeric compound or even glass beads.
  • the structuring agents such as the amphoteric materials of the instant invention are preferably aluminum oxides having a powdered particle size of 10-20 microns (micrometres), a particle size dispersed in water of 10 to 60 nanometers, a powdered surface area of 180-250 m2/g, and a crystalline size of less than 60 microns (micrometres).
  • An especially preferred aluminum oxide is Dispal T23 sold by Vista Chemicals.
  • suitable structuring agents are mixtures of aluminum oxides and magnesium oxides, zeolites, synthetic clays such as laponite, calcium rich clays such as Promat. Natural clays such as Bentonite, Hectorite and Attapulgite and polymeric aluminum salts sold by Reheis are also useful as a structuring agent.
  • a means for further improving the structuring of the gel formulations of the instant invention in order to obtain improved viscosity as well as G' and G'' values is to form an aqueous polymeric solution of a crosslinked anionic polymer such as a crosslinked polyacrylic acid thickening agent at room temperature with mixing and subsequently with mixing neutralizing the anionic groups such as the carboxylic acid groups by the addition of an excess basic material such as caustic soda to form an alkali metal neutralized crosslinked polyacrylic acid polymer.
  • a crosslinked anionic polymer such as a crosslinked polyacrylic acid thickening agent
  • an excess basic material such as caustic soda
  • the alkali metal crosslinked neutralized polyacrylic acid polymer in combination with the amphoteric compound provides improved G' and G'' values as well as improved increase in viscosity (viscosification) of the aqueous polymeric solution having a pH of 7 to 10 as compared to the use of the alkali metal neutralized crosslinked polyacrylic acid alone as a viscosification agent.
  • the improvement in viscosification results from the association of the amphoteric material and the alkali metal neutralized crosslinked polyacrylic acid polymer in the water, wherein the negative charges of the amphoteric compound and the negatively charged anionic groups of the polyacrylic acid are repulsive to each other thereby causing an uncoiling of the polymeric chain of the alkali metal neutralized crosslinked polyacrylic acid which provides a further building of the polymeric structure within the water.
  • water and amphoteric compound detergent builder salts, silicates, surfactants, foam depressants and bleaching agents can be added without significantly damaging the polymeric structure to form a gel like automatic dishwashing composition.
  • compositions can be formed for a variety of applications such as toothpastes, creams or toothpaste gels, cosmetics, fabric cleaners, shampoos, floor cleaners, cleaning paste, tile cleaners, thickened bleach compositions, ointments, oven cleaners, pharmaceutical suspensions, concentrated coal slurries, oil drilling muds, cleaning prestoppers and aqueous based paints.
  • These compositions can be formulated by adding the appropriate chemicals to the aqueous polymeric solution of alkali metal neutralized polyacrylic acid polymer, caustic soda and the amphoteric compound to form the desired composition.
  • the polymeric aqueous solution of water, caustic soda, alkali metal neutralized polyacrylic acid polymer and the amphoteric compound has a complex viscosity at room temperature at 10 radians/second of 2 to 800 dynes second/sq.cm., more preferably 3 to 600 dynes second/sq.cm.
  • the polymeric solution comprises .05 to 4.0 weight %, more preferably 0.1 to 4.0 weight % of an amphoteric compound, 0.1 to 4.0 weight %, more preferably 0.2 to 3.0 weight % of an alkali metal neutralized crosslinked anionic polymer such as a metal neutralized crosslinked polyacrylic polymer and water, wherein the aqueous polymeric solution has a G' value of at least 80 dynes/sq.cm. at a frequency of 10 radians/second, a G'' value of at least 10 dynes/sq.cm. at a frequency of 10 radians/second, a ratio of G''/G' is less than 1 and G' is substantially constant over a frequency range of 0.01 to 50.0 radians/second.
  • the polymeric solution has a G' value of at least 80 dynes/sq.cm. at a frequency of 10 radians/second and the G'' valve is at least 10 dynes/sq.cm. at a frequency of 10 radians/second, wherein G' is substantially constant over a frequency range of 0.01 to 50 radians/second and a ratio of G''/G' is less than 1 and a yield stress of at least 2 dynes/sq.cm., more preferably 2 to 1200 dynes/sq.cm., the polymeric solution will be a gel which can function as a suspension medium for a plurality of solid particles, immiscible liquid droplets or gaseous bubbles.
  • the solid particles or liquid droplets or gaseous bubbles can be inorganic, organic or polymeric.
  • the solid material liquid droplets or gas bubbles which are not soluble in the water phase, should not decompose in an aqueous solution or react with the anionic groups of the anionic polymer or the carboxylate groups.
  • the concentration of the solid particles, liquid droplets or gaseous bubbles in the suspension medium is 0.1 to 70 weight percent, more preferably 1 to 50 weight %.
  • alkali metal neutralized anionic polymers contemplated within the scope of the instant invention beside polyacrylic and polymers such as the Carbopols are: sulfonated polymers containing a sulfonate functionality as defined in U.S. Patent Nos. 3,642,728; 4,608,425; 4,619,773; 4,626,285; 4,637,882; 4,640,945; 4,647,603; 4,710,555; 5,730,028; 4,963,032; 4,970,260 and 4,975,482, wherein these aforementioned patents are all hereby incorporated by reference as well as polymers and monomers containing a carboxylic acid functionality as defined in U.S. Patent Nos.
  • the thickened aqueous polymeric solutions are made by neutralizing at room temperature with mixing an aqueous solution of the Carbopol resin with caustic soda such that to the resultant aqueous solution of the alkali metal neutralized Carbopol is added at room temperature with mixing an aqueous dispersion of aluminum oxide to form the thickened aqueous polymeric solution.
  • a further enhancement of thickening can be achieved by the further addition of 0.02 to 1.0 weight percent of a fatty acid or a metal salt of a fatty acid.
  • the high potassium to sodium ion ratios in the range of 1:1 to 45:1, preferably 1:1 to 4:1, especially preferably from 1.05:1 to 3:1, for example 1.1:1, 1.2:1, 1.5:1, 2:1, or 2.5:1.
  • the solubility of the solid salt components is substantially increased since the presence of the potassium (K+) ions requires less water of hydration than the sodium (Na+) ions, such that more water is available to dissolve these salt compounds. Therefore, all or nearly all of the normally solid components are present dissolved in the aqueous phase. Since there is none or only a very low percentage, i.e.
  • any undissolved solids tend to be present in extremely small particle sizes, usually colloidal or sub-colloidal, such as 1 micron (micrometre) or less, thereby further reducing the tendency for the undissolved particles to settle.
  • a still further attribute of the invention compositions contributing to the overall product stability and low bottle residue is the high water absorption capacity of the cross-linked polyacrylic acid type thickening agent.
  • This high water absorption capacity virtually all of the aqueous vehicle component is held tightly bound to the polymer matrix. Therefore, there is no or substantially no free water present in the invention compositions.
  • This absence of free water is manifested by the observation that when the composition is poured from a bottle onto a piece of water absorbent filter paper virtually no water is absorbed onto the filter paper and, furthermore, the mass of the linear viscoelastic material poured onto the filter paper will retain its shape and structure until it is again subjected to a stress or strain.
  • the density of the composition should be controlled such that the bulk density of the liquid phase is approximately the same as the bulk density of the entire composition, including the polymeric thickening agent.
  • This control and equalization of the densities is achieved, according to the invention, by providing the composition with a bulk density of at least 1.2a g/cc, preferably at least 1.35 g/cc, up to 1.42 g/cc, preferably up to 1.40 g/cc.
  • it is important to minimize the amount of air incorporated into the composition (a density of 1.42 g/cc is essentially equivalent to zero air content).
  • stabilization of air bubbles which may become incorporated into the compositions during normal processing, such as during various mixing steps, is avoided by post-adding the surface active ingredients, including fatty acid or fatty acid salt stabilizer, to the remainder of the composition, under low shear conditions using mixing devices designed to minimize cavitation and vortex formation.
  • the surface active ingredients present in the composition will include the main detergent surface active cleaning agent, and will also preferably include anti-foaming agent and higher fatty acid or salt thereof as a physical stabilizer.
  • Exemplary of the cross-linked polyacrylic acid-type thickening agents are the products sold by B.F. Goodrich under their Carbopol trademark, especially Carbopol 941, which is the most ion-insensitive of this class of polymers, and Carbopol 940 and Carbopol 934.
  • the Carbopol resins also known as "Carbomer” are hydrophilic high molecular weight, cross-linked acrylic acid polymers having an average equivalent weight of 76, and the general structure illustrated by the following formula: Carbopol 941 has a molecular weight of 1,250,000; Carbopol 940 a molecular weight of approximately 4,000,000 and Carbopol 934 a molecular weight of approximately 3,000,000.
  • the Carbopol resins are cross-linked with polyalkenyl polyether, e.g. 1% of a polyallyl ether of sucrose having an average of 5.8 allyl groups for each molecule of sucrose. Further detailed information on the Carbopol resins is available from B.F. Goodrich, see, for example, the B.F. Goodrich catalog GC-67, Carbopol (Registered Trade Mark) Water Soluble Resins.
  • polyacrylic acid- type refers to water- soluble homopolymers of acrylic acid or methacrylic acid or water-dispersible or water-soluble salts, esters or amides thereof, or water-soluble copolymers of these acids or their salts, esters or amides with each other or with one or more other ethylenically unsaturated monomers, such as, for example, styrene, maleic acid, maleic anhydride, 2-hydroxyethylacrylate, acrylonitrile, vinyl acetate, ethylene, propylene, and the like.
  • the homopolymers or copolymers are characterized by their high molecular weight, in the range of from 500,000 to 10,000,000, preferably 500,000 to 5,000,000, especially from 1,000,000 to 4,000,000, and by their water solubility, generally at least to an extent of up to 5% by weight, or more, in water at 25°C.
  • thickening agents are used in their lightly cross-linked form wherein the cross-linking may be accomplished by means known in the polymer arts, as by irradiation, or, preferably, by the incorporation into the monomer mixture to be polymerized of known chemical cross-linking monomeric agents, typically polyunsaturated (e.g. diethylenically unsaturated) monomers, such as, for example, divinylbenzene, divinylether of diethylene glycol, N, N'-methylene-bisacrylamide, polyalkenylpolyethers (such as described above), and the like.
  • polyunsaturated (e.g. diethylenically unsaturated) monomers such as, for example, divinylbenzene, divinylether of diethylene glycol, N, N'-methylene-bisacrylamide, polyalkenylpolyethers (such as described above), and the like.
  • amounts of cross-linking agent to be incorporated in the final polymer may range from 0.01 to 1.5 percent, preferably from 0.05 to 1.2 percent, and especially, preferably from 0.1 to 0.9 percent, by weight of cross-linking agent to weight of total polymer.
  • degree of cross-linking should be sufficient to impart some coiling of the otherwise generally linear polymeric compound while maintaining the cross-linked polymer at least water dispersible and highly water-swellable in an ionic aqueous medium.
  • the water-swelling of the polymer which provides the desired thickening and viscous properties generally depends on one or two mechanisms, namely, conversion of the acid group containing polymers to the corresponding salts, e.g.
  • the preferred polyacrylic acid-type thickening agents will contain free carboxylic acid (COOH) groups along the polymer backbone.
  • COOH carboxylic acid
  • the amount of the high molecular weight, cross-linked polyacrylic acid or other high molecular weight, hydrophilic cross-linked polyacrylic acid-type thickening agent to impart the desired rheological property of linear viscoelasticity will generally be in the range of from 0.1 to 2%, preferably from 0.2 to 1.4%, by weight, based on the weight of the composition, although the amount will depend on the particular cross-linking agent, ionic strength of the composition, hydroxyl donors and the like.
  • compositions of this invention must include sufficient amount of potassium ions and sodium ions to provide a weight ratio of K/Na of at least 1:1, preferably from 1:1 to 45:1, especially from 1:1 to 3:1, more preferably from 1.05:1 to 3:1, such as 1.5:1, or 2:1.
  • K/Na ratio is less than 1 there is insufficient solubility of the normally solid ingredients whereas when the K/Na ratio is more than 45, especially when it is greater than 3, the product becomes too liquid and phase separation begins to occur.
  • the K/Na ratio is more than 45, especially when it is greater than 3, the product becomes too liquid and phase separation begins to occur.
  • the K/Na ratios become much larger than 45, such as in all or mostly potassium formulation, the polymer thickener loses its absorption capacity and begins to salt out of the aqueous phase.
  • the potassium and sodium ions can be made present in the compositions as the alkali metal cation of the detergent builder salt(s), or alkali metal silicate or alkali metal hydroxide components of the compositions.
  • the alkali metal cation may also be present in the compositions as a component of an ionic detergent, bleach or other ionizable salt compound additive, e.g. alkali metal carbonate. In determining the K/Na weight ratios all of these sources should be taken into consideration.
  • detergent builder salts include the polyphosphates, such as alkali metal pyrophosphate, alkali metal tripolyphosphate, alkali metal metaphosphate, and the like, for example, sodium or potassium tripolyphosphate (hydrated or anhydrous), tetrasodium or tetrapotassium pyrophosphate, sodium or potassium hexa-metaphosphate, trisodium or tripotassium orthophosphate and the like, sodium or potassium carbonate, sodium or potassium citrate, sodium or potassium nitrilotriacetate, and the like.
  • polyphosphates such as alkali metal pyrophosphate, alkali metal tripolyphosphate, alkali metal metaphosphate, and the like
  • sodium or potassium tripolyphosphate hydrated or anhydrous
  • tetrasodium or tetrapotassium pyrophosphate sodium or potassium hexa-metaphosphate
  • trisodium or tripotassium orthophosphate and the like sodium or potassium
  • phosphate builders where not precluded due to local regulations, are preferred and mixtures of tetrapotassium pyrophosphate (TKPP) and sodium tripolyphosphate (NaTPP) (especially the hexahydrate) are especially preferred.
  • Typical ratios of NaTPP to TKPP are from 2:1 to 1:8, especially from 1:1.1 to 1:6.
  • the total amount of detergent builder salts is preferably from 5 to 35% by weight, more preferably from 15 to 35%, especially from 18 to 30% by weight of the composition.
  • Acusol Trade Mark
  • Norasol QR1014 from Norsohaas having a GPC molecular weight of 10,000.
  • the linear viscoelastic compositions of this invention may, and preferably will, contain a small, but stabilizing effective amount of a long chain fatty acid or monovalent or polyvalent salt thereof.
  • a long chain fatty acid or monovalent or polyvalent salt thereof may function as a hydrogen bonding agent or cross-linking agent for the polymeric thickener.
  • the preferred long chain fatty acids are the higher aliphatic fatty acids having from 8 to 22 carbon atoms, more preferably from 10 to 20 carbon atoms, and especially preferably from 12 to 18 carbon atoms, inclusive of the carbon atom of the carboxyl group of the fatty acid.
  • the aliphatic radical may be saturated or unsaturated and may be straight or branched. Straight chain saturated fatty acids are preferred.
  • Mixtures of fatty acids may be used, such as those derived from natural sources, such as tallow fatty acid, coco fatty acid, soya fatty acid, mixtures of these acids, etc.
  • Stearic acid and mixed fatty acids e.g. stearic acid/palmitic acid, are preferred.
  • the free acid form of the fatty acid When used directly it will generally associate with the potassium and sodium ions in the aqueous phase to form the corresponding alkali metal fatty acid soap.
  • the fatty acid salts may be directly added to the composition as sodium salt or potassium salt, or as a polyvalent metal salt, although the alkali metal salts of the fatty acids are preferred fatty acid salts.
  • the preferred polyvalent metals are the di- and trivalent metals of Groups IIA, IIB and IIIB, such as magnesium, calcium, aluminum and zinc, although other polyvalent metals, including those of Groups IIIA, IVA, VA, IB, IVB, VB VIB, VIIB and VIII of the Periodic Table of the Elements can also be used. Specific examples of such other polyvalent metals include Ti, Zr, V, Nb, Mn, Fe, Co, Ni, Cd, Sn, Sb, Bi, etc. Generally, the metals may be present in the divalent to pentavalent state. Preferably the metal salts are used in their higher oxidation states.
  • the metal salt should be selected by taking into consideration the toxicity of the metal.
  • the alkali metal and calcium and magnesium salts are especially higher preferred as generally safe food additives.
  • the amount of the fatty acid or fatty acid salt stabilizer to achieve the desired enhancement of physical stability will depend on such factors as the nature of the fatty acid or its salt, the nature and amount of the thickening agent, detergent active compound, inorganic salts, other ingredients, as well as the anticipated storage and shipping conditions.
  • amounts of the fatty acid or fatty acid salt stabilizing agents in the range of from 0.02 to 2%, preferably 0.04 to 1%, more preferably from 0.06 to 0.8%, especially preferably from 0.08 to 0.4%, provide a long term stability and absence of phase separation upon standing or during transport at both low and elevated temperatures as are required for a commercially acceptable product.
  • fatty acid physical stabilizers and polyacrylic acid-type thickening agents Depending on the amounts, proportions and types of fatty acid physical stabilizers and polyacrylic acid-type thickening agents, the addition of the fatty acid or salt not only increases physical stability but also provides a simultaneous increase in apparent viscosity. Amounts of fatty acid or salt to polymeric thickening agent in the range of from 0.08-0.4 weight percent fatty acid salt and from 0.4-1.5 weight percent polymeric thickening agent are usually sufficient to provide these simultaneous benefits and, therefore, the use of these ingredients in these amounts is most preferred.
  • the fatty acid or salt stabilizer should be post-added to the formulation, preferably together with the other surface active ingredients, including detergent active compound and anti-foaming agent, when present.
  • These surface active ingredients are preferably added as an emulsion in water wherein the emulsified oily or fatty materials are finely and homogeneously dispersed throughout the aqueous phase.
  • the emulsion or preheat the water
  • an elevated temperature near the melting temperature of the fatty acid or its salt.
  • a temperature in the range of between 50°C and 70°C will be used.
  • an elevated temperature of 35°C to 50°C can be used.
  • the fatty acid or salt and other surface active ingredients can be more readily and uniformly dispersed (emulsified) in the form of fine droplets throughout the composition.
  • the composition is not linear viscoelastic as defined above and the stability of the composition is clearly inferior.
  • Foam inhibition is important to increase dishwasher machine efficiency and minimize destabilizing effects which might occur due to the presence of excess foam within the washer during use. Foam may be reduced by suitable selection of the type and/or amount of detergent active material, the main foam-producing component.
  • the degree of foam is also somewhat dependent on the hardness of the wash water in the machine whereby suitable adjustment of the proportions of the builder salts such as NaTPP which has a water softening effect, may aid in providing a degree of foam inhibition.
  • each type of ester may represent independently a C12-C20 alkyl or ethoxylated alkyl group.
  • the ethoxylated derivatives of each type of ester for example, the condensation products of one mole of ester with from 1 to 10 moles, preferably 2 to 6 moles, more preferably 3 or 4 moles, ethylene oxide can also be used.
  • Some examples of the foregoing are commercially available, such as the products SAP from Hooker and LPKN-158 from Knapsack.
  • Mixtures of the two types, or any other chlorine bleach stable types, or mixtures of mono- and di-esters of the same type, may be employed.
  • a mixture of mono- and di-C16-C18 alkyl acid phosphate esters such as monostearyl/distearyl acid phosphates 1.2/1, and the 3 to 4 mole ethylene oxide condensates thereof.
  • proportions of 0.05 to 1.5 weight percent, preferably 0.1 to 0.5 weight percent, of foam depressant in the composition is typical, the weight ratio of detergent active component (d) to foam depressant (e) generally ranging from 10:1 to 1:1 and preferably 5:1 to 1:1.
  • defoamers which may be used include, for example, the known silicones, such as available from Dow Chemicals.
  • the stabilizing salts such as the stearate salts, for example, aluminum stearate, when included, are also effective as foam killers.
  • any chlorine bleach compound may be employed in the compositions of this invention, such as dichloro-isocyanurate, dichloro-dimethyl hydantoin, or chlorinated TSP, alkali metal or alkaline earth metal, e.g. potassium, lithium, magnesium and especially sodium, hypochlorite is preferred.
  • the composition should contain sufficient amount of chlorine bleach compound to provide 0.2 to 4.0% by weight of available chlorine, as determined, for example by acidification of 100 parts of the composition with excess hydrochloric acid.
  • a solution containing 0.2 to 4.0% by weight of sodium hypochlorite contains or provides roughly the same percentage of available chlorine. 0.8 to 1.6% by weight of available chlorine is especially preferred.
  • sodium hypochlorite (NaOCL) solution of from 11 to 13% available chlorine in amounts of 3 to 20%, preferably 7 to 12%, can be advantageously used.
  • Detergent active material useful herein should be stable in the presence of chlorine bleach, especially hypochlorite bleach, and for this purpose those of the organic anionic, amine oxide, phosphine oxide, sulphoxide or betaine water dispersible surfactant types are preferred, the first mentioned anionics being most preferred.
  • Particularly preferred surfactants herein are the linear or branched alkali metal mono- and/or di-(C8-C14) alkyl diphenyl oxide mono-and/or di-sulphates, commercially available for example as DOWFAX (Registered Trademark) 3B-2 and DOWFAX 2A-1.
  • the surfactant should be compatible with the other ingredients of the composition.
  • organic anionic, non-soap surfactants include the primary alkylsulphates, alkylsulphonates, alkylarylsulphonates and sec.- alkylsulphates.
  • Examples include sodium C10-C18 alkylsulphates such as sodium dodecylsulphate and sodium tallow alcoholsulphate; sodium C10-C18 alkanesulphonates such as sodium hexadecyl-1-sulphonate and sodium C12-C18 alkylbenzene sulphonates such as sodium dodecylbenzenesulphonates.
  • the corresponding potassium salts may also be employed.
  • the amine oxide surfactants are typically of the structure R2R1NO, in which each R represents a lower alkyl group, for instance, methyl, and R1 represents a long chain alkyl group having from 8 to 22 carbon atoms, for instance a lauryl, myristyl, palmityl or cetyl group.
  • R2R1NO a corresponding surfactant phosphine oxide R2R1PO or sulphoxide RR1SO can be employed.
  • Betaine surfactants are typically of the structure R2R1N+R''COO-, in which each R represents a lower alkylene group having from 1 to 5 carbon atoms, R1 being as defined above in respect of the amine oxide surfactants.
  • Specific examples of these surfactants include lauryl-dimethylamine oxide, myristyl-dimethylamine oxide, the corresponding phosphine oxides and sulphoxides, and the corresponding betaines, including dodecyldimethylammonium acetate, tetradecyldiethylammonium pentanoate, hexadecyldimethylammonium hexanoate and the like.
  • the alkyl groups in these surfactants should be linear, and such compounds are preferred.
  • the chlorine bleach stable, water dispersible organic detergent-active material will normally be present in the composition in minor amounts, generally 1% by weight of the composition, although smaller or larger amounts, such as up to 5%, such as from 0.1 to 5%, preferably from 0.3 or 0.4 to 2% by weight of the composition, may be used.
  • Alkali metal (e.g. potassium or sodium) silicate which provides alkalinity and protection of hard surfaces, such as fine china glaze and pattern, is generally employed in an amount ranging from 5 to 20 weight percent, preferably 5 to 15 weight percent, more preferably 8 to 12% in the composition.
  • the sodium or potassium silicate is generally added in the form of an aqueous solution, preferably having Na2O:SiO2 or K2O:SiO2 ratio of 1:1.3 to 1:2.8, especially preferably 1:2.0 to 1:2.6.
  • alkali metal hydroxide and bleach are also often added in the form of a preliminary prepared aqueous dispersion or solution.
  • the effectiveness of the liquid automatic dishwasher detergent compositions is related to the alkalinity, and particularly to moderate to high alkalinity levels. Accordingly, the compositions of this invention will have pH values of at least 9.5, preferably at least 11 to as high as 14, generally up to 13 or more, and, when added to the aqueous wash bath at a typical concentration level of 10 grams per liter, will provide a pH in the wash bath of at least 9, preferably at least 10, such as 10.5, 11, 11.5 or 12 or more.
  • the alkalinity will be achieved, in part by the alkali metal ions contributed by the alkali metal detergent builder salts, e.g. sodium tripolyphosphate, tetrapotassium pyrophosphate, and alkali metal silicate, however, it is usually necessary to include alkali metal hydroxide, e.g. NaOH or KOH, to achieve the desired high alkalinity.
  • alkali metal hydroxide e.g. NaOH or KOH
  • Amounts of alkali metal hydroxide in the range of (on an active basis) of from 0.5 to 8%, preferably from 1 to 6%, more preferably from 1.2 to 4%, by weight of the composition will be sufficient to achieve the desired pH level and/or to adjust the K/Na weight ratio.
  • alkali metal salts such as alkali metal carbonate may also be present in the compositions in minor amounts, for example from 0 to 4%, preferably 0 to 2%, by weight of the composition.
  • compositions may be included in small amounts, generally less than 3 weight percent, such as perfume, hydrotropic agents such as the sodium benzene, toluene, xylene and cumene sulphonates, preservatives, dyestuffs and pigments and the like, all of course being stable to chlorine bleach compound and high alkalinity.
  • hydrotropic agents such as the sodium benzene, toluene, xylene and cumene sulphonates
  • preservatives dyestuffs and pigments and the like
  • dyestuffs and pigments and the like all of course being stable to chlorine bleach compound and high alkalinity.
  • Especially preferred for coloring are the chlorinated phthalocyanines and polysulphides of aluminosilicate which provide, respectively, pleasing green and blue tints.
  • TiO2 may be employed for whitening or neutralizing off-shades.
  • incorporation of small amounts of finely divided air bubbles can be incorporated to adjust the bulk density to approximate liquid phase density.
  • the incorporated air bubbles should be finely divided, such as up to 100 microns in diameter, preferably from 20 to 40 microns in diameter, to assure maximum stability.
  • air is the preferred gaseous medium for adjusting densities to improve physical stability of the composition
  • inert gases can also be used, such as nitrogen, carbon dioxide, helium, oxygen, etc.
  • the amount of water contained in these compositions should, of course, be neither so high as to produce unduly low viscosity and fluidity, nor so low as to produce unduly high viscosity and low flowability, linear viscoelastic properties in either case being diminished or destroyed by increasing tan ⁇ . Such amount is readily determined by routine experimentation in any particular instance, generally ranging from 30 to 75 weight percent, preferably 35 to 65 weight percent.
  • the water should also be preferably deionized or softened.
  • the manner of formulating the invention compositions is also important. As discussed above, the order of mixing the ingredients as well as the manner in which the mixing is performed will generally have a significant effect on the properties of the composition, and in particular on product density (by incorporation and stabilization of more or less air) and physical stability (e.g. phase separation).
  • compositions are prepared by first forming a dispersion of the polyacrylic acid-type thickener in water under moderate to high shear conditions, neutralizing the dissolved polymer to cause gelation, and then introducing, while continuing mixing, the detergent builder salts, alkali metal silicates, chlorine bleach compound and remaining detergent additives, including any previously unused alkali metal hydroxide, if any, other than the surface-active compounds.
  • All of the additional ingredients can be added simultaneously or sequentially.
  • the ingredients are added sequentially, although it is not necessary to complete the addition of one ingredient before beginning to add the next ingredient.
  • one or more of these ingredients can be divided into portions and added at different times.
  • mixing steps should also be performed under moderate to high shear rates to achieve complete and uniform mixing. These mixing steps may be carried out at room temperature, although the polymer thickener neutralization (gelation) is usually exothermic.
  • the composition may be allowed to age, if necessary, to cause dissolved or dispersed air to dissipate out of the composition.
  • the remaining surface active ingredients including the anti-foaming agent, organic detergent compound, and fatty acid or fatty acid salt stabilizer is post-added to the previously formed mixture in the form of an aqueous emulsion (using from 1 to 10%, preferably from 2 to 4% of the total water added to the composition other than water added as carrier for other ingredients or water of hydration) which is pre-heated to a temperature in the range of from Tm+5 to Tm-20, preferably from Tm to Tm-10, where Tm is the melting point temperature of the fatty acid or fatty acid salt.
  • the heating temperature is in the range of 50°C to 70°C.
  • the order of addition of the surface active ingredients should be less important.
  • the thickened linear viscoelastic aqueous automatic dishwasher detergent composition of this invention includes, on a weight basis:
  • compositions will be supplied to the consumer in suitable dispenser containers preferably formed of molded plastic, especially polyolefin plastic, and most preferably polyethylene, for which the invention compositions appear to have particularly favorable slip characteristics.
  • suitable dispenser containers preferably formed of molded plastic, especially polyolefin plastic, and most preferably polyethylene, for which the invention compositions appear to have particularly favorable slip characteristics.
  • the compositions of this invention may also be characterized as pseudoplastic gels (non-thixotropic) which are typically near the borderline between liquid and solid viscoelastic gel, depending, for example, on the amount of the polymeric thickener.
  • pseudoplastic gels non-thixotropic
  • the invention compositions can be readily poured from their containers without any shaking or squeezing, although squeezable containers are often convenient and accepted by the consumer for gel-like products.
  • liquid aqueous linear viscoelastic automatic dishwasher compositions of this invention are readily employed in known manner for washing dishes, other kitchen utensils and the like in an automatic dishwasher, provided with a suitable detergent dispenser, in an aqueous wash bath containing an effective amount of the composition, generally sufficient to fill or partially fill the automatic dispenser cup of the particular machine being used.
  • the invention also provides a method for cleaning dishware in an automatic dishwashing machine with an aqueous wash bath containing an effective amount of the liquid linear viscoelastic automatic dishwasher detergent composition as described above.
  • the composition can be readily poured from the polyethylene container with little or no squeezing or shaking into the dispensing cup of the automatic dishwashing machine and will be sufficiently viscous and cohesive to remain securely within the dispensing cup until shear forces are again applied thereto, such as by the water spray from the dishwashing machine.
  • Formulations A, B, C, D, E, G, J, and K are prepared by first forming a uniform dispersion of the Carbopol 941 or 940 thickener in 97% of the water (balance).
  • the Carbopol is slowly added to deionized water at room temperature using a mixer equipped with a premier blade, with agitation set at a medium shear rate, as recommended by the manufacturer.
  • the dispersion is then neutralized by addition, under mixing, of the caustic soda (50% NaOH or KOH) component to form a thickened product of gel-like consistency.
  • TKPP tetrapotassium pyrophosphate
  • TP(TPP, Na) and bleach are added sequentially, in the order stated, with the mixing continued at medium shear.
  • an emulsion of the phosphate anti-foaming agent (LPKN), stearic acid/palmitic acid mixture and detergent (Dowfax 3B2) is prepared by adding these ingredients to the remaining 3% of water (balance) and heating the resulting mixture to a temperature in the range of 50°C to 70°C.
  • This heated emulsion is then added to the previously prepared gelled dispersion under low shear conditions, such that a vortex is not formed.
  • formulations F, H and I are prepared in essentially the same manner as described above except that the heated emulsion of LPKN, stearic acid and Dowfax 3B2 is directly added to the neutralized Carbopol dispersion prior to the addition of the remaining ingredients.
  • formulations F, H and I have higher levels of incorporated air and densities below 1.30 g/cc.
  • rheograms for the formulations A, C, D, G and J are shown in figures 1-5, respectively, and rheograms for formulations H, I and K are shown in figures 6, 7 and 8 respectively.
  • composition formulations A, B, C, D, G and J which include Carbopol 941 and stearic acid exhibit linear viscoelasticity as seen from the rheograms of figure 1-5.
  • Formulation E which includes Carbopol 941 but not stearic acid showed no phase separation at either room temperature or 100°F (38°C) after 3 weeks, but exhibited 10% phase separation after 8 weeks at room temperature and after only 6 weeks at 100°F (38°C).
  • Formulation K containing Carbopol 940 in place of Carbopol 941, as seen from the rheogram in Figure 8, exhibits substantial linearity over the strain range of from 2% to 50% (G' at 1% strain-G' at 50% strain > 500 dynes/sq.cm.) although tan ⁇ > 1 at a strain above 50%.
  • the Carbopol 941 is dispersed, under medium shear rate, using a premier blade mixer, in deionized water at ambient temperature.
  • the NaOH is added, under mixing, to neutralize and gel the Carbopol 941 dispersion.
  • To the thickened mixture the following ingredients are added sequentially while the stirring is continued: sodium silicate, TKPP, TPP, and bleach.
  • an emulsion is prepared by adding the Dowfax 3B2, stearic acid and LPKN to water while mixing at moderate shear and heating the mixture to 65°C to finely disperse the emulsified surface active ingredients in the water phase.
  • This emulsion premix is then slowly added to the Carbopol dispersion while mixing under low shear conditions without forming a vortex. The results are shown below in Table 3.
  • Method A is repeated except that the heated emulsion premix is added to the neutralized Carbopol 941 dispersion before the sodium stearate; TKPP, TPP, and bleach. The results are also shown below.
  • Method B Density (g/cc) 1.38 1.30 Stability (RT-8 weeks) 0.00% 7.00% Rheogram Fig. 9 Fig. 10
  • This example shows the importance of the temperature at which the premixed surfactant emulsion is prepared.
  • Two formulations, L and M, having the same composition as in Example 2 except that the amount of stearic acid was increased from 0.1% to 0. 2% are prepared as shown in Method A for formulation L and by the following Method C for formulation M.
  • Method A The procedure of Method A is repeated in all details except that emulsion premix of the surface active ingredients is prepared at room temperature and is not heated before being post-added to the thickened Carbopol dispersion containing silicate, builders and bleach.
  • the rheograms for formulations L and M are shown in Figures 11 and 12, respectively. From these rheograms it is seen that formulation L is linear viscoelastic in both G' and G'' whereas formulation M is nonlinear viscoelastic particularly for elastic modulus G' (G' at 1% strain-G' at 30% strain > 500 dynes/cm2) and also for G'' (G'' at 1% strain-G'' at 30% strain > 300 dynes/cm2).
  • Formulation L remains stable after storage at RT and 100°F (38°C) for at least 6 weeks whereas formulation M undergoes phase separation.
  • Formulations A, B, C, D and K according to this invention and comparative formulations F as shown in Table 1 and a commercial liquid automatic dishwasher detergent product above were subject to a bottle residue test using a standard polyethylene 28 ounce bottle as used for current commercial liquid dishwasher detergent bottle.
  • the following formulas (A - K ) were prepared according to the following procedure: The Carbopol polymer was added to water at 75°-80°C with mixing. To the solution of the Carbopol polymer and water was added with mixing the sodium hydroxide to neutralize the Carbopol polymer so that the solution has a pH of 7 to 10. The dispersion of the alumina (Dispal T23) was added with mixing to the solution of water and neutralized Carbopol polymer to form formulas (A - K). The polymer solutions were tested on the System 4 Rheometer as in Example 1. The Brookfield viscosities were run at room temperature using a #4 spindle at 20 rpms. Rheograms ( Figure 14-34) depict the G' and G'' for formulas A-K, wherein for each formula a plot of G' and G'' is illustrated.

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)
EP92304893A 1991-11-08 1992-05-29 Linear viscoelastic aqueous liquid automatic dishwasher detergent composition Withdrawn EP0541204A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US78957491A 1991-11-08 1991-11-08
US789574 1991-11-08

Publications (1)

Publication Number Publication Date
EP0541204A1 true EP0541204A1 (en) 1993-05-12

Family

ID=25148037

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92304893A Withdrawn EP0541204A1 (en) 1991-11-08 1992-05-29 Linear viscoelastic aqueous liquid automatic dishwasher detergent composition

Country Status (7)

Country Link
EP (1) EP0541204A1 (fi)
AU (1) AU662904B2 (fi)
CA (1) CA2069845A1 (fi)
FI (1) FI922510A (fi)
NO (1) NO922066L (fi)
NZ (1) NZ242845A (fi)
PT (1) PT100544A (fi)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0574236A2 (en) * 1992-06-08 1993-12-15 Colgate-Palmolive Company Aqueous composition containing a non-crosslinked polymer for augmenting viscosity
US8093200B2 (en) 2007-02-15 2012-01-10 Ecolab Usa Inc. Fast dissolving solid detergent

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2134695A1 (de) * 1971-07-12 1973-01-25 Henkel & Cie Gmbh Streufaehige, als komplexbildner geeignete stoffgemische und diese enthaltende wasch-, waschhilfs-, bleich- und reinigungsmittel
EP0208836A2 (de) * 1985-06-20 1987-01-21 Degussa Aktiengesellschaft Waschmittelcobuildermischung
EP0295093A1 (en) * 1987-06-12 1988-12-14 Unilever Plc Liquid machine dishwashing composition
EP0323209A2 (en) * 1987-12-30 1989-07-05 Unilever Plc Detergent compositions

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5232621A (en) * 1987-09-29 1993-08-03 Colgate-Palmolive Company Linear viscoelastic gel compositions
US4970016A (en) * 1987-09-29 1990-11-13 Colgate-Palmolive Co. Thixotropic aqueous liquid automatic dishwashing detergent composition
US5219486A (en) * 1987-09-29 1993-06-15 Colgate Palmolive Company Linear visoelastic aqueous liquid automatic dishwasher detergent composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2134695A1 (de) * 1971-07-12 1973-01-25 Henkel & Cie Gmbh Streufaehige, als komplexbildner geeignete stoffgemische und diese enthaltende wasch-, waschhilfs-, bleich- und reinigungsmittel
EP0208836A2 (de) * 1985-06-20 1987-01-21 Degussa Aktiengesellschaft Waschmittelcobuildermischung
EP0295093A1 (en) * 1987-06-12 1988-12-14 Unilever Plc Liquid machine dishwashing composition
EP0323209A2 (en) * 1987-12-30 1989-07-05 Unilever Plc Detergent compositions

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPIL Week 8425, Derwent Publications Ltd., London, GB; AN 84-154809 & JP-A-59 080 459 (ARAKAWA KAGAKU KOGYO) 9 May 1984 *
DATABASE WPIL Week 8538, Derwent Publications Ltd., London, GB; AN 85-233850 & JP-A-60 152 551 (NITTO ELECTRIC IND KK) 10 August 1985 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0574236A2 (en) * 1992-06-08 1993-12-15 Colgate-Palmolive Company Aqueous composition containing a non-crosslinked polymer for augmenting viscosity
EP0574236A3 (fi) * 1992-06-08 1994-08-31 Colgate Palmolive Co
US8093200B2 (en) 2007-02-15 2012-01-10 Ecolab Usa Inc. Fast dissolving solid detergent
US8309509B2 (en) 2007-02-15 2012-11-13 Ecolab Usa Inc. Fast dissolving solid detergent
US8697625B2 (en) 2007-02-15 2014-04-15 Ecolab Usa Inc. Fast dissolving solid detergent
US9267097B2 (en) 2007-02-15 2016-02-23 Ecolab Usa Inc. Fast dissolving solid detergent
US10005986B2 (en) 2007-02-15 2018-06-26 Ecolab Usa Inc. Fast dissolving solid detergent
US10577565B2 (en) 2007-02-15 2020-03-03 Ecolab Usa Inc. Fast dissolving solid detergent
US11261406B2 (en) 2007-02-15 2022-03-01 Ecolab Usa Inc. Fast dissolving solid detergent

Also Published As

Publication number Publication date
NO922066L (no) 1993-05-10
NO922066D0 (no) 1992-05-25
FI922510A (fi) 1993-05-14
AU662904B2 (en) 1995-09-21
CA2069845A1 (en) 1993-05-09
NZ242845A (en) 1993-07-27
PT100544A (pt) 1993-10-29
FI922510A0 (fi) 1992-05-29
AU1625692A (en) 1993-05-13

Similar Documents

Publication Publication Date Title
EP0398021B1 (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
US5053158A (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
US5209863A (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition having improved anti-filming properties
AU663496B2 (en) Polymeric solutions and viscoelastic gels
US5225096A (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition having improved chlorine stability
US5395547A (en) Process of making an aqueous viscoelastic automatic dishwash detergent containing a silicate-neutralized crosslinked polyacrylate
AU656580B2 (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
US5368766A (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
US5202046A (en) Process for preparing a linear viscoelastic aqueous liquid automatic dishwasher deteregent composition
EP0560615A1 (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
EP0541204A1 (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
EP0517314A1 (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
AU650121B2 (en) Process for preparing a linear viscoelastic aqueous liquid automatic dishwasher detergent composition
AU653809B2 (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
EP0517313A1 (en) Linear viscoelastic aqueous liquid detergent composition, especially for automatic dishwashers, of improved high temperature stability
EP0517311A1 (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
EP0517308A1 (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
IE921742A1 (en) Linear viscoelastic aqueous liquid automatic dishwasher¹detergent composition
IE921759A1 (en) Linear viscoelastic aqueous liquid automatic dishwasher¹detergent composition
CA2070093A1 (en) Linear viscoelastic aqueous liquid detergent composition, especially for automatic dishwashers, of improved high temperature stability
NZ242837A (en) Linear viscoelastic aqueous automatic dishwashing detergent containing alkali metal builder salt, alkali metal silicate, bleach, cross-linked polyacrylic acid thickener and non-cross-linked polyacrylate
NZ242833A (en) Linear viscoelastic aqueous automatic dishwasher detergent containing alkali metal builder salt, alkali metal silicate, bleach, organic detergent, cross-linked polyacrylic acid thickener, c8-c50 fatty acid and a polymeric chelating agent
IE921747A1 (en) Linear viscoelastic aqueous liquid automatic dishwasher¹detergent composition
IE921748A1 (en) Linear viscoelastic aqueous liquid automatic dishwasher¹detergent composition
NZ242832A (en) Linear viscoelastic aqueous automatic dishwasher detergent containing alkali metal builder salt, bleach, cross-linked polyacrylate thickener and sodium and potassium ions

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

17P Request for examination filed

Effective date: 19920615

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

17Q First examination report despatched

Effective date: 19970401

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

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19970812