EP0446761A1 - Lineare viskoelastische wässerig-flüssige Detergenszusammensetzungen, insbesondere für Geschirrspülautomaten, oder mit verbesserter Stabilität bei erhöhter Temperatur - Google Patents

Lineare viskoelastische wässerig-flüssige Detergenszusammensetzungen, insbesondere für Geschirrspülautomaten, oder mit verbesserter Stabilität bei erhöhter Temperatur Download PDF

Info

Publication number
EP0446761A1
EP0446761A1 EP91103284A EP91103284A EP0446761A1 EP 0446761 A1 EP0446761 A1 EP 0446761A1 EP 91103284 A EP91103284 A EP 91103284A EP 91103284 A EP91103284 A EP 91103284A EP 0446761 A1 EP0446761 A1 EP 0446761A1
Authority
EP
European Patent Office
Prior art keywords
composition
weight
acid
water
detergent
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Withdrawn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
EP91103284A
Other languages
English (en)
French (fr)
Inventor
Nagaraj S. Dixit
Divaker Kenkare
Makaran Shevade
Patricia Phillips
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 EP0446761A1 publication Critical patent/EP0446761A1/de
Withdrawn legal-status Critical Current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
    • C11D3/16—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
    • 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
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions

Definitions

  • the invention relates to aqueous linear viscoelastic (gel-like) liquid compositions which are especially useful as automatic dishwasher detergent compositions.
  • Liquid automatic dishwasher detergent compositions both aqueous and nonaqueous, have recently received much attention, and the aqueous products have achieved commercial popularity.
  • Potassium pyrophosphate is disclosed as the preferred potassium salt for its sequestering and solubilizing activity and also because "it effectively stabilizes the tripolyphosphate agent hydrolysis in aqueous solution into sodium pyrophosphate and sodium orthophosphate.”
  • the patent also states that, "[t]he content [of TKPP] should not ... be too great so as to undergo a double-decomposition reaction with TPP to form sodium pyrophosphate, which is well known, has a very low solubility in water and, therefore, tends to separate out as a precipitate.
  • the applicants investigations have shown that the optimum proportion of potassium pyrophosphate incorporated in the liquid detergent compositions ... is between 5 and 25 percent based on the TPP present in the compositions.”
  • U.S. Patent 4,836,948 discloses a viscoelastic gel detergent composition characterized by its viscosity under low and high shear conditions, pH, and steady state viscoelastic deformation compliance.
  • the composition requires the presence of a polycarboxylate polymeric thickener, preferably a cross-linked polyacrylic acid.
  • the compositions of this patent also, however, require a trivalent metal containing material, especially an aluminum containing material such as alumina.
  • the compositions may further include a structuring chelant which may be a salt of carbonate, pyrophosphate or mixture thereof, and preferably the potassium salts.
  • the recently issued U.S. Patent 4,859,358 discloses the incorporation of metal salts of long chain hydroxy fatty acids, as anti-tarnishing agents, in thickened aqueous automatic dishwashing detergent compositions.
  • the thickeners for these compositions may be a high molecular weight polycarboxylate polymer, such as those sold under the Carbopol trade name, and specific 600 and 900 series resins are mentioned. It is also disclosed that the compositions may include entrained gas, e.g. air, bubbles to further ensure stability.
  • Amounts of air in the range of from about 1% to about 20%, preferably from about 5 to 15% by volume will lower the specific gravity of the overall composition to within from about 5% more than to about 10% less than, preferably from 1% more than to 5% less than, the specific gravity of the aqueous phase.
  • the specific gravity of the composition was stated as 1.32 g/cm3.
  • the compositions are not described as being linear viscoelastic and as exemplified do not include any potassium salts.
  • compositions disclosed in our prior application Serial No. 353,712 provided a satisfactory solution to the problems of phase instability and bottle residue, as well as cup leakage, it has now been found that under some storage/handling conditions and/or processing conditions, additional improvements would be desirable. Specifically, if the viscoelastic composition is subjected to repeated heating and cooling cycles, growth of crystals and product thinning and/or precipitate formation has been observed. Chemical analysis of the precipitated crystals has shown that these crystals are comprised predominantly of sodium pyrophosphate. In addition, it appears that the crystals tend to become entangled with the polymeric thickener which tendency is presumed to account for the thinning out or aqueous phase separation which has been observed in conjunction with crystal formation and precipitation.
  • the finished product not only may be perceived as unaesthetic but, more importantly, the product viscosity is often lowered which in turn may lead to cup leakage and corresponding degradation in cleaning performance.
  • the present invention provides ingredient and processing modifications to our previously developed compositions which help to alleviate and overcome the above problems.
  • Figures 1-6 are rheograms, plotting elastic modulus G' and viscous modulus G'' as a function of applied strain, for the compositions of Example 1, Formulations A, B, C, D, E and F, respectively.
  • an improved aqueous liquid automatic dishwasher detergent composition is characterized not only by its linear viscoelastic behavior, substantially indefinite stability against phase separation or settling of dissolved or suspended particles under high and low temperature conditions, low levels of bottle residue, relatively high bulk density, and substantial absence of loosely bound water,but also by its overall product consistency from batch to batch and run to run and over a wide range of storage and aging conditions, including superior aesthetics, freedom from fish-eyes, absence of crystal formation and growth, and resistance to cup leakage.
  • the present invention was accomplished based, in part, on the discovery that by replacing part or all of the tetrapotassium pyrophosphate (TKPP) with potassium tripolyphosphate (KTPP), crystal growth can be inhibited and product consistency can be improved and the linear viscoelastic properties can be extended beyond that previously achieved. Further improvements are obtained by utilizing more highly cross-linked and branched, temperature stable and bleach and salt compatible polymeric thickening agents. Furthermore, by controlling the conditions of mixing the ingredients of the compositions, and particularly the pH and temperature of the aqueous phase used to form the aqueous solution of the polymeric thickener, formation of fish-eyes and elimination of viscosity reductions with time can be achieved.
  • TKPP tetrapotassium pyrophosphate
  • KTPP potassium tripolyphosphate
  • the present invention provides an improved linear viscoelastic aqueous liquid automatic dishwasher detergent composition
  • water up to about 2% by weight of long chain fatty acid or salt thereof, from about 0.1 to 5% by weight of low-foaming chlorine bleach stable, water dispersible automatic dishwasher non-soap organic detergent, from about 10 to 35% by weight of alkali metal detergent builder salt, at least 50% by weight of which is potassium tripolyphosphate and at least about 5% by weight of which is sodium tripolyphosphate, from about 3 to 20% by weight of a chlorine bleach compound, and a cross-linked polycarboxylate thickening agent having a molecular weight of at least about 500,000, wherein the aqueous phase includes both sodium and potassium ions at a K/Na weight ratio of from about 1/1 to about 45/1.
  • the compositions preferably have a bulk density of from about 1.28 g/cm3 to about 1.42 g/cm3.
  • the linear viscoelastic aqueous liquid automatic dishwasher detergent comprises, approximately, by weight,
  • a method for preparing the aqueous linear viscoelastic composition comprises the steps of
  • the pH of the aqueous slurry of the cross-linked polycarboxylate thickener after the neutralization in step (b) and in each succeeding step is maintained at a value of at least 11.
  • compositions of this invention are thickened aqueous liquids containing various cleansing active ingredients, detergent builder salts and other detergent adjuvants, structuring and thickening agents and stabilizing components, although some ingredients may serve more than one of these functions.
  • compositions of this invention include physical stability, as manifested by little or no phase separation, solid settling or viscosity changes over time or resulting from exposure to low or high temperatures, low bottle residue, low cup leakage, high cleaning performance, e.g. low spotting and filming, dirt residue removal, and consistency in product characteristics and performance, and superior aesthetics. These characteristics 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 and processing conditions of the formulations namely, (1) the inclusion of a thickening effective amount of a temperature, bleach and salt stable cross-linked polymeric thickening agent having high water absorption capacity, exemplified by cross-linked polyacrylic acid, (2) inclusion of a physical stabilizing amount of a long chain fatty acid or salt thereof, and (3) potassium ion to sodium ion weight ratio K/Na in the range of from about 1:1 to 45:1, especially from 1:1 to 3:1, and preferably also (4)-(6): (4) a product bulk density of at least about 1.28 g/cc, especially at least 1.32 g/cc, (5) hydrating the cross-linked polymeric thickener with heated water, and (6) maintaining the pH of the neutralized polymeric thickener at a pH of at least 11, preferably at least 11.5.
  • linear viscoelastic aqueous liquid automatic dishwasher detergent compositions of this invention will, at least in the preferred embodiments, satisfy each of the following stability criteria over the aging temperature-time schedule shown by the following Table A: More specifically, the compositions are considered stable if each of the following stability criteria is satisfied for at least the minimum number of weeks for each aging temperature shown in Table A:
  • 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 to 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 about 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 of 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 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.
  • Linear viscoelasticity also contributes to the elimination of dripping of the contents when the product is poured from a bottle and hence reduction of formation of drops around the container mouth at the conclusion of pouring the product from a container.
  • 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 or less, thereby further reducing the tendency for the undissolved particles to settle. Since there are substantially no undissolved solid particles of size in excess of 1 micron, the invention products tend to be transparent or at least translucent, depending, in part, on air bubble content.
  • 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 appears to be held tightly bound to the polymer matrix. Therefore, there appears to be no or substantially no free water present in the invention compositions.
  • This apparent 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 over a period of at least several hours or longer and, furthermore, the mass of the linear viscoelastic material poured onto the filter paper will retain its shape and structure.
  • 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 was achieved, according to our earlier invention, by providing the composition with a bulk density of at least 1.32 g/cc. A density of about 1.42 g/cc is essentially equivalent to zero air content.
  • the bulk density of the product can be adjusted by controlling the degree of aeration, as well as total solid content. Further, the dispersed air bubbles also contribute to the viscoelastic property of the product.
  • the product density is preferably selected in the range of 1.28 to 1.42 g/cc, especially 1.32 to 1.40 g/cc, and most preferably from 1.35 to 1.40 g/cc. Within these ranges air bubble incorporation is determined to achieve the desired product aesthetic appearance and flow characteristics.
  • 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 (e.g. phosphate ester) and higher fatty acid or salt thereof as a physical stabilizer.
  • anti-foaming agent e.g. phosphate ester
  • higher fatty acid or salt thereof e.g. phosphate ester
  • polycarboxylate type thickening agents are cross-linked polyacrylic acid-type thickening agents sold by B.F. Goodrich under their Carbopol trademark, including both the 900 series resins, especially Carbopol 941, which is the most ion-insensitive of this class of polymers, and Carbopol 940 and Carbopol 934, and the 600 series resins, especially Carbopol 614.
  • the Carbopol 900 series resins are hydrophilic high molecular weight, cross-linked linear 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 about 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 900 series resins are cross-linked with polyalkenyl polyether, e.g. about 1% of a polyallyl ether of sucrose having an average of about 5.8 allyl groups for each molecule of sucrose. The preparation of this class of cross-linked carboxylic polymers is described in U.S.
  • Patent 2,798,053 the disclosure of which is incorporated by reference. Further detailed information on the Carbopol 900 series resins is available from B.F. Goodrich, see, for example, the B.F. Goodrich catalog GC-67, Carbopol® Water Soluble Resins.
  • these thickening resins are preferably copolymers of a water dispersible copolymer of an alpha-beta monoethylenically unsaturated lower aliphatic carboxylic acid cross-linked with a polyether of a polyol selected from oligo saccharides, reduced derivatives thereof in which the carbonyl group is converted to an alcohol group and pentaerythritol, the hydroxyl groups of the polyol which are modified being etherified with allyl groups, there being preferably at least two such allyl groups per molecule.
  • Carbopol 614 which is the most chlorine bleach stable of this class of thickening resins.
  • Carbopol 614 is also highly stable in the high alkalinity environment of the preferred liquid automatic dishwasher detergent compositions and is also highly stable to any anticipated storage temperature conditions from below freezing to elevated temperatures as high as 120°F, preferably 140°F, and especially 160°F, for periods of as long as several days to several weeks or months or longer.
  • polycarboxylate-type refers to water-soluble carboxyvinyl polymers of alpha,beta monoethylenically unsaturated lower aliphatic carboxylic acids, which may be linear or non-linear, and are exemplified by 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
  • homopolymers or copolymers are characterized by their high molecular weight, in the range of from about 500,000 to 10,000,000, preferably 750,000 to 5,000,000, especially from about 1,000,000 to 4,000,000, and by their water solubility, generally at least to an extent of up to about 5% by weight, or more, in water at 25°C.
  • thickening agents are used in their 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 about 0.01 to about 5 percent, preferably from about 0.05 to about 2 percent, and especially, preferably from about 0.1 to about 1.5 percent, by weight of cross-linking agent to weight of total polymer.
  • degrees of cross-linking should be sufficient to impart some coiling of the otherwise generally linear or non-linear polymeric compound while maintaining the cross-linked polymer at least water dispersible and highly water-swellable in an ionic aqueous medium.
  • the amount of the high molecular weight, cross-linked polyacrylic acid or other high molecular weight, hydrophilic cross-linked polycarboxylate thickening agent to impart the desired rheological property of linear viscoelasticity will generally be in the range of from about 0.1 to 2%, preferably from about 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 about 1:1 to 4:1, more preferably from 1.05:1 to 3:1, such as 1.1:1, 1.2:1, 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 about 3 or 4, the product becomes too liquid and phase separation begins to occur.
  • the K/Na ratios become much larger than 45, such as in an all or mostly potassium formulation, the polycarboxylate thickener loses it absorption capacity and begins to salt out of the aqueous phase.
  • the potassium and sodium ions will be made present in the compositions as the alkali metal cation of the detergent builder salt(s), as well as 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 anionic 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
  • the detergent builder salts will be comprised of mixtures of at least potassium tripolyphosphate (KTPP) and sodium tripolyphosphate (NaTPP) (especially hexahydrate). Typical ratios of KTPP to NaTPP are from about 1.4:1 to 10:1, especially from about 2:1 to 8:1.
  • the total amount of detergent builder salts is preferably from about 10 to 35% by weight, more preferably from about 15 to 35%, especially from about 18 to 30% by weight of the composition. Of this total amount of the detergent builders at least 50% by weight (preferably at least about 8% by weight of the composition) will be KTPP and preferably at least 5% by weight (preferably at least 2% by weight of the composition) will be NaTPP.
  • the alkali metal detergent builder salt will be comprised of from about 65 to 95% of KTPP, especially 75 to 90% of KTPP and from about 5 to 35%, especially 10 to 25% of NaTPP.
  • the amount of KTPP will be in the range of from about 8 to 25%, preferably 15 to 22% by weight, and the amount of NaTPP will be in the range of from about 2 to 10%, preferably 3 to 8% by weight.
  • alkali metal detergent builder salts When other alkali metal detergent builder salts are present in the formulation, they will usually be present in amounts less than 5% by weight based on the total composition and, in any case, in amounts to maintain the K/Na ratios to within the above described range, preferably from 1:1.1 to 1:3.
  • 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 about 10 to 50 carbon atoms, more preferably from about 12 to 40 carbon atoms, and especially preferably from about 14 to 40 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, etc., or from synthetic sources available from industrial manufacturing processes.
  • examples of the fatty acids include, for example, decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, behenic acid, oleic acid, eicosanoic acid, 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 about 0.02 to 2%, preferably 0.04 to 1%, more preferably from about 0.06 to 0.8%, especially preferably from about 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 polycarboxylate thickening agents Depending on the amounts, proportions and types of fatty acid physical stabilizers and polycarboxylate 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 about 0.08-0.4 weight percent fatty acid salt and from about 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 is preferably 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.
  • stearic acid having a melting point of 68°-69°C a temperature in the range of between 50°C and 70°C will be used.
  • an elevated temperature of about 35° 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.
  • 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 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 diesters 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 about 10:1 to 1:1 and preferably about 5:1 to 1:1.
  • Other 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 about 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 about 0.2 to 4.0% by weight of sodium hypochlorite contains or provides roughly the same percentage of available chlorine. About 0.8 to 1.6% by weight of available chlorine is especially preferred.
  • sodium hypochlorite (NaOCl) solution of from about 11 to about 13% available chlorine in amounts of about 3 to 20%, preferably about 7 to 12%, can be advantageously used.
  • Another surprising and unexpected benefit and advantage of the preferred Carbopol thickened compositions of this invention is the essentially total masking of any chlorine bleach odor which is characteristic of, for example, the prior known clay thickened products.
  • the subject compositions can be blended with substantially lower amounts of fragrance, e.g. lemon oil fragrance, to achieve the same or superior olfactory sensation for the consumer. For instance, as little as 0.05% of lemon fragrance will have the same effect as about 0.12% in clay thickened products.
  • fragrance does not adversely affect the stability criteria, as previously defined, such as viscosity or phase stability, of the compositions.
  • Detergent active material useful herein should be low-foaming and stable in the presence of chlorine bleach, when present, especially hypochlorite bleach, and for this purpose those of the organic anionic, nonionic, 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 alkylbenzenesulphonates 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.
  • R1 represents a long chain alkyl group having from 8 to 22 carbon atoms, for instance a lauryl, myristyl, palmityl or cetyl group.
  • 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.
  • 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 about 1% by weight of the composition, although smaller or larger amounts, such as up to about 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 about 5 to 20 weight percent, preferably about 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 about 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 reference is to an active ingredient basis, i.e. does not include the aqueous carrier.
  • 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 about 9.5, preferably at least about 11 to as high as 14, generally up to about 13 or more, and, when added to the aqueous wash bath at a typical concentration level of about 10 grams per liter, will provide a pH in the wash bath of at least about 9, preferably at least about 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, potassium tripolyphosphate, 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 from about 0.5 to 8%, preferably from 1 to 6%, more preferably from about 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.
  • the pH of the composition during processing is highly important for product stability, e.g. viscosity, and bleach stability and phase stability.
  • the amount of basic neutralizing agent preferably NaOH
  • these high alkalinity levels should be maintained throughout the product formulation steps, namely, the pH value of at least 11, preferably at least 11.5, should be maintained during the successive additions of the other ingredients of the composition.
  • 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.
  • the low m.w. polyacrylic acids can provide additional thickening characteristics but are primarily introduced for their ability to function as a builder or chelating agent. In this capacity, the low m.w. polyacrylic acids can contribute to reduced spotting or streaking and reduced filming on dishes, glassware, pots, pans, and other utensils and appliances.
  • a suitable molecular weight ranges for the non-crosslinked polyacrylic acid is from about 800 to 200,000, preferably 1000 to 150,000, especially from about 2,000 to 100,000.
  • the non-crosslinked polyacrylic acid can be used in amounts up to about 10% by weight, preferably from about 1 to 8% by weight, especially 2 to 6% by weight of the composition.
  • compositions may be included in small amounts, generally less than about 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.
  • chlorinated phthalocyanines and polysulphides of aluminosilicate which provide, respectively, pleasing green and blue tints.
  • the bleach stable mixed dyes C.I. Direct Yellow 28 (C.I. 19555) or C.I. Direct Yellow 29 (C.I. 19556) can be added to the compositions. These colors meet stability criteria described in Table A
  • incorporation of small amounts of finely divided air bubbles can be incorporated to adjust the visual appearance, product density and flowability.
  • the incorporated air bubbles should be finely divided, such as up to about 100 microns in diameter, preferably from about 20 to about 40 microns in diameter.
  • Other 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 1.
  • Such amount is readily determined by routine experimentation in any particular instance, and generally will range from 30 to 75 weight percent, preferably about 35 to 65 weight percent.
  • the water should also be deionized or softened.
  • compositions are prepared by forming a dispersion of the polycarboxylate type thickener in heated water, e.g.
  • the ingredients are added sequentially, with mixing continued for from 2 to 10 minutes for each ingredient, 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.
  • These mixing steps should also be performed under moderate to high shear rates to achieve complete and uniform mixing.
  • These additional ingredient mixing steps may be carried out at room temperature, but preferably the elevated temperature of the thickener slurry is maintained.
  • 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 about 1 to 10%, preferably from about 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 about Tm-5 to Tm+20, preferably from about 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 150° to 170°F (65° to 77°C).
  • 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 opaque or translucent 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, i.e. have a sufficiently low yield stress value to flow under their own weight (gravity), 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 and F are prepared by first forming a uniform dispersion of the Carbopol 614 or 940 thickener in about 97% of the water of the total formula water.
  • the Carbopol is slowly added by sprinkling it into the vortex of previously colored deionized water preheated to a temperature of 105°F using a mixer equipped with a premier blade, with agitation set at a medium shear rate, as recommended by the manufacturer. After mixing for about 15 minutes, the dispersion is then neutralized by addition, under the same mixing, of the caustic soda (50% NaOH) component until a thickened product of gel-like consistency is formed (about 10 minutes).
  • the caustic soda 50% NaOH
  • the silicate sodium tripolyphosphate (NaTPP), tetrapotassium pyrophosphate (TKPP), or potassium tripolyphosphate (KTPP), the surfactant emulsion (described below) and bleach and color, are added sequentially, in the order stated, with the mixing continued at medium shear for several minutes before adding the next ingredient.
  • the surfactant emulsion at 160°F
  • the mixture is cooled to from 90°-95°F before the bleach is added.
  • the surfactant emulsion of the phosphate anti-foaming agent (LPKN), stearic acid or fatty acid mixture and detergent (Dowfax 3B2) is prepared by adding these ingredients to the remaining 3% of water and heating the resulting mixture to a temperature in the range of 160°F (71°C).
  • the Acrysol LMW 45-N may be added at this stage.
  • composition formulations C, D and F exhibit linear viscoelasticity as seen from the rheograms of figure 2-6. No phase separation at from ambient temperature to 140°F were observed for any of the formulations for at least the minimum number of weeks required to satisfy the criteria stability as shown in Table A above. Formulations E and F were still being tested when this application was filed.
  • formulations A and B maintained at 100°F, the TKPP crystallized in the aqueous phase and eventually formed sufficiently large size crystals which separated to the bottom of the composition.
  • formulations A and B are not linear viscoelastic, at least within the preferred criteria as previously described.
  • Formulations C, D, E and F, according to the invention did not undergo any crystal growth.
  • each formulation is allowed to age for about 1 week at ambient temperature in a standard 32 ounce small necked polyethylene bottle.
  • An amount of product is poured from the bottle to fill a standard sized dispenser cup of an automatic dishwasher.
  • the bottle is then replaced in an upright position and is retained in the upright position for at least 15 minutes. This procedure of filling the dispenser cup, placing the container in the upright position and waiting at least 15 minutes is repeated until no more product flows from the bottle. At this time, the weight of the bottle is measured.
  • Bottle residue is calculated as Wo is the initial weight of the filled bottle and Wf is the final weight of the filled bottle.
  • the bottle residue for each formulation A-F is about 4 to 5%.
  • Formulations C-F have viscosities of from 10,000 to 20,000 measured with a Brookfield LVT viscometer, #4 spindle at 20 rpm measured at 80°F. all of these products are easily pourable from the polyethylene bottle.
  • a Carbopol 614 slurry is formed as described in Example 1 except that the coloring agent is first added to the deionized water (about 92% of the total added water) and the amounts of the ingredients are changed as shown below.
  • the premix (surfactant emulsion) of the surface active ingredients is also formed as in Example 1 using stearic acid as the fatty acid stabilizer and the remaining 8% of the total added water.
  • the ingredients are then mixed together with the Carbopol 614 slurry in the following order: alkali metal silicate, NaTPP (powder), KTPP (powder), surfactant emulsion, bleach and perfume.
  • the resulting composition is obtained with the following ingredients in the following amounts:
  • the composition has a pH of 11.3 + 0.2 and density (sp.gr.) of 1.39 + 0.03.
  • the viscosity at 80°F measured with a Brookfield LVT viscometer at 20 rpm with a #4 spindle is 12,000 + 2,000.

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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP91103284A 1990-03-13 1991-03-05 Lineare viskoelastische wässerig-flüssige Detergenszusammensetzungen, insbesondere für Geschirrspülautomaten, oder mit verbesserter Stabilität bei erhöhter Temperatur Withdrawn EP0446761A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US49300390A 1990-03-13 1990-03-13
US493003 1990-03-13

Publications (1)

Publication Number Publication Date
EP0446761A1 true EP0446761A1 (de) 1991-09-18

Family

ID=23958489

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91103284A Withdrawn EP0446761A1 (de) 1990-03-13 1991-03-05 Lineare viskoelastische wässerig-flüssige Detergenszusammensetzungen, insbesondere für Geschirrspülautomaten, oder mit verbesserter Stabilität bei erhöhter Temperatur

Country Status (11)

Country Link
EP (1) EP0446761A1 (de)
AU (1) AU632221B2 (de)
CA (1) CA2038023A1 (de)
GR (1) GR1000851B (de)
IE (1) IE910817A1 (de)
IL (1) IL97427A0 (de)
MY (1) MY109088A (de)
NO (1) NO910964L (de)
NZ (1) NZ237301A (de)
PL (1) PL289391A1 (de)
PT (1) PT96998A (de)

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0469847A2 (de) * 1990-08-01 1992-02-05 Diversey Corporation Waschmittelzusammensetzung für Geschirrspülmaschinen
EP0510944A2 (de) * 1991-04-22 1992-10-28 Colgate-Palmolive Company Lineare viskoelastische Zusammensetzungen für Geschirrspülautomaten
EP0510945A2 (de) * 1991-04-22 1992-10-28 Colgate-Palmolive Company Lineare, viskoelastische, wässerig-flüssige Detergenszusammensetzungen, insbesondere für Geschirrspülautomaten
EP0517309A1 (de) * 1991-06-07 1992-12-09 Colgate-Palmolive Company Lineares viscoelastisches wässriges flüssiges Waschmittel, insbesondere für Geschirrspülautomaten mit verbesserter Temperaturstabilität
EP0517314A1 (de) * 1991-06-07 1992-12-09 Colgate-Palmolive Company Lineares, viskoelastisches, wässriges flüssiges Waschmittel für Geschirrspülautomaten
EP0517313A1 (de) * 1991-06-07 1992-12-09 Colgate-Palmolive Company Linares viskoseelastisches wässeriges Flüssigwaschmittel, insbesondere für Geschirrspülmaschinen mit verbesserter Temperaturbeständigkeit
EP0522604A2 (de) * 1991-04-19 1993-01-13 Colgate-Palmolive Company Verfahren zur Herstellung von einer linearen viskoelastischen wässrig-flüssigen Detergenzusammensetzung für Geschirrspülautomat
EP0523826A1 (de) * 1991-07-11 1993-01-20 Colgate-Palmolive Company Viskoelastische wässrig-flüssige Detergenszusammensetzung, insbesondere für Geschirrspülautomaten, mit verbesserter Verteilbarkeit
EP0541202A1 (de) * 1991-11-08 1993-05-12 Colgate-Palmolive Company Lineares, viskoelastisches, wässriges flüssiges Waschmittel für Geschirrspülautomaten mit verbesserten nichtfilmbildenden Eigenschaften
EP0541201A1 (de) * 1991-11-08 1993-05-12 Colgate-Palmolive Company Lineares, viskoelastisches, wässriges flüssiges Waschmittel für Geschirrspülautomaten mit verbesserter Beständigkeit des Chlors
EP0541200A1 (de) * 1991-11-08 1993-05-12 Colgate-Palmolive Company Lineares, viskoelastisches, wässriges flüssiges Waschmittel für Geschirrspülautomaten
EP0541203A1 (de) * 1991-11-08 1993-05-12 Colgate-Palmolive Company Lineare viskoelastische wässrig flüssige Detergenzzusammensetzung für Geschirrspülautomaten
EP0491553A3 (en) * 1990-12-18 1993-06-30 Cussons (International) Limited Detergent composition
EP0560615A1 (de) * 1992-03-11 1993-09-15 Colgate-Palmolive Company Lineares, viskoelastisches, wässriges, flüssiges Waschmittel für Geschirrspülautomaten
GR1001379B (el) * 1992-05-29 1993-10-29 Colgate Palmolive Co Γραμμική ιξωδοελαστική σύν?εση υδατικού υγρού απορρυπαντικού αυτομάτου πλυντηρίου πιάτων.
TR26143A (tr) * 1991-06-07 1995-02-15 Colgate Palmolive Co OTOMATIK BULASIK MAKINELERI ICIN ARTTIRILMIS YüKSEK SICAKLIK DENGESINE SAHIP DOGRUSAL VISKOELASTIK SULU SIVI DETERJAN BILESIMI
US5470499A (en) * 1993-09-23 1995-11-28 The Clorox Company Thickened aqueous abrasive cleanser with improved rinsability
US5529711A (en) * 1993-09-23 1996-06-25 The Clorox Company Phase stable, thickened aqueous abrasive bleaching cleanser
US5650017A (en) * 1994-07-04 1997-07-22 Lever Brothers Company, Division Of Conopco, Inc. Washing process and composition
WO2002016541A1 (en) * 2000-08-25 2002-02-28 Reckitt Benckiser N.V. Water-soluble packages containing liquid compositions
US7041628B2 (en) 2001-07-07 2006-05-09 Henkel Kommanditgesellschaft Auf Aktien Aqueous 3 in 1 dishwasher products
US7153816B2 (en) 2001-08-17 2006-12-26 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Dishwasher detergent with improved protection against glass corrosion
US7192911B2 (en) 2001-07-07 2007-03-20 Henkel Kgaa Nonaqueous 3 in 1 dishwasher products
US8021610B2 (en) 2006-09-07 2011-09-20 Biolargo Life Technologies, Inc. Systems providing antimicrobial activity to an environment
US8226964B2 (en) 2006-09-07 2012-07-24 Biolargo Life Technologies, Inc. Systems and methods for cleaning liquid carriers related applications data
US9127235B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US9414601B2 (en) 2006-09-07 2016-08-16 Biolargo Life Technologies, Incorporated Material having antimicrobial activity when wet
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5064553A (en) * 1989-05-18 1991-11-12 Colgate-Palmolive Co. Linear-viscoelastic aqueous liquid automatic dishwasher detergent composition
US5188752A (en) * 1991-04-22 1993-02-23 Colgate-Palmolive Company Linear viscoelastic automatic dishwasher compositions containing a crosslinked methyl vinyl ether/maleic anhydride copolymer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0165676A2 (de) * 1984-06-19 1985-12-27 Chemed Corporation Stabilisiertes aktives Halogen enthaltende Detergenszusammensetzungen und Verfahren
EP0264975A1 (de) * 1986-08-18 1988-04-27 The Procter & Gamble Company Verdickte wässrige Geschirrwaschmittel-Zusammensetzungen
US4836948A (en) * 1987-12-30 1989-06-06 Lever Brothers Company Viscoelastic gel detergent compositions
US4859358A (en) * 1988-06-09 1989-08-22 The Procter & Gamble Company Liquid automatic dishwashing compositions containing metal salts of hydroxy fatty acids providing silver protection
EP0362178A2 (de) * 1988-08-10 1990-04-04 Monsanto Company Geschirrwaschmittel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0165676A2 (de) * 1984-06-19 1985-12-27 Chemed Corporation Stabilisiertes aktives Halogen enthaltende Detergenszusammensetzungen und Verfahren
EP0264975A1 (de) * 1986-08-18 1988-04-27 The Procter & Gamble Company Verdickte wässrige Geschirrwaschmittel-Zusammensetzungen
US4836948A (en) * 1987-12-30 1989-06-06 Lever Brothers Company Viscoelastic gel detergent compositions
US4859358A (en) * 1988-06-09 1989-08-22 The Procter & Gamble Company Liquid automatic dishwashing compositions containing metal salts of hydroxy fatty acids providing silver protection
EP0362178A2 (de) * 1988-08-10 1990-04-04 Monsanto Company Geschirrwaschmittel

Cited By (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0469847A3 (en) * 1990-08-01 1993-01-20 Diversey Corporation Dishwasher detergent composition
EP0469847A2 (de) * 1990-08-01 1992-02-05 Diversey Corporation Waschmittelzusammensetzung für Geschirrspülmaschinen
EP0491553A3 (en) * 1990-12-18 1993-06-30 Cussons (International) Limited Detergent composition
EP0522604A3 (en) * 1991-04-19 1993-07-14 Colgate Palmolive Co Process for preparing a linear viscoelastic aqueous liquid automatic dishwasher detergent composition
EP0522604A2 (de) * 1991-04-19 1993-01-13 Colgate-Palmolive Company Verfahren zur Herstellung von einer linearen viskoelastischen wässrig-flüssigen Detergenzusammensetzung für Geschirrspülautomat
TR26648A (tr) * 1991-04-22 1995-03-15 Colgate Palmolive Co Otomatik bulasik makineleri icin dogrusal,visko- elastik, sulu sivi deterjan bilesimi
EP0510944A2 (de) * 1991-04-22 1992-10-28 Colgate-Palmolive Company Lineare viskoelastische Zusammensetzungen für Geschirrspülautomaten
EP0510945A2 (de) * 1991-04-22 1992-10-28 Colgate-Palmolive Company Lineare, viskoelastische, wässerig-flüssige Detergenszusammensetzungen, insbesondere für Geschirrspülautomaten
GR1001211B (el) * 1991-04-22 1993-06-21 Colgate Palmolive Co Συνθεση γραμμικου ιξωδοελαστικου υδατικου υγρου απορρυπαντικου, ειδικα για αυτοματα πλυντηρια πιατων.
EP0510944A3 (en) * 1991-04-22 1993-03-10 Colgate-Palmolive Company Linear viscoelastic automatic dishwasher compositions
EP0510945A3 (en) * 1991-04-22 1993-03-17 Colgate-Palmolive Company Linear viscoelastic aqueous liquid detergent composition, especially for automatic dishwashers
EP0517314A1 (de) * 1991-06-07 1992-12-09 Colgate-Palmolive Company Lineares, viskoelastisches, wässriges flüssiges Waschmittel für Geschirrspülautomaten
TR26143A (tr) * 1991-06-07 1995-02-15 Colgate Palmolive Co OTOMATIK BULASIK MAKINELERI ICIN ARTTIRILMIS YüKSEK SICAKLIK DENGESINE SAHIP DOGRUSAL VISKOELASTIK SULU SIVI DETERJAN BILESIMI
TR26584A (tr) * 1991-06-07 1995-03-15 Colgate Palmolive Co CAPRAZ BAGLI,YüKSEK MOLEKüLER AGIRLIKLI POLIKAR- BOKSILAT ASIT TIPI BIR KOYULASTIRICI ICEREN OTOMATIK BULASIK MAKINESI DETERJAN BILESIMI
EP0517313A1 (de) * 1991-06-07 1992-12-09 Colgate-Palmolive Company Linares viskoseelastisches wässeriges Flüssigwaschmittel, insbesondere für Geschirrspülmaschinen mit verbesserter Temperaturbeständigkeit
EP0517309A1 (de) * 1991-06-07 1992-12-09 Colgate-Palmolive Company Lineares viscoelastisches wässriges flüssiges Waschmittel, insbesondere für Geschirrspülautomaten mit verbesserter Temperaturstabilität
EP0523826A1 (de) * 1991-07-11 1993-01-20 Colgate-Palmolive Company Viskoelastische wässrig-flüssige Detergenszusammensetzung, insbesondere für Geschirrspülautomaten, mit verbesserter Verteilbarkeit
GR1001216B (el) * 1991-07-11 1993-06-21 Colgate Palmolive Co Συνθεση ιξωδοελαστικου υδατικου υγρου απορρυπαντικου, ειδικα για αυτοματα πλυντηρια πιατων, βελτιωμενης ικανοτητας διανομης.
EP0541203A1 (de) * 1991-11-08 1993-05-12 Colgate-Palmolive Company Lineare viskoelastische wässrig flüssige Detergenzzusammensetzung für Geschirrspülautomaten
GR1001240B (el) * 1991-11-08 1993-06-30 Colgate Palmolive Co Γραμμικη ιξωδοελαστικη συνθεση υδατικου υγρου απορρυπαντικου αυτοματου πλυντηριου πιατων.
GR1001250B (el) * 1991-11-08 1993-06-30 Colgate Palmolive Co Γραμμικη ιξωδοελαστικη υδατικη υγρη συνθεση απορρυπαντικου για αυτοματο πλυντηριο πιατων,εχουσα βελτιωμενες ιδιοτητες κατα του σχηματισμου φιλμ.
GR1001335B (el) * 1991-11-08 1993-08-31 Colgate Palmolive Co Γραμμικη ιξωδοελαστικη συνθεση υδατικου υγρου απορρυπαντικου αυτοματου πλυντηριου πιατων εχουσα βελτιωμενη σταθεροτητα χλωριου.
EP0541200A1 (de) * 1991-11-08 1993-05-12 Colgate-Palmolive Company Lineares, viskoelastisches, wässriges flüssiges Waschmittel für Geschirrspülautomaten
GR1001365B (el) * 1991-11-08 1993-10-29 Colgate Palmolive Co Γραμμική ιξωδοελαστική σύν?εση υδατικού υγρού απορρυπαντικού αυτομάτου πλυντηρίου πιάτων.
EP0541201A1 (de) * 1991-11-08 1993-05-12 Colgate-Palmolive Company Lineares, viskoelastisches, wässriges flüssiges Waschmittel für Geschirrspülautomaten mit verbesserter Beständigkeit des Chlors
TR26040A (tr) * 1991-11-08 1993-11-01 Colgate Palmolive Co Filmlesmeye-karsi gelistirilmis özelliklere sahip olan,lineer viskoelastik,sulu,sivi otomatik bulasik makinesi deterjani bilesimi.
TR26089A (tr) * 1991-11-08 1994-12-15 Colgate Palmolive Co Gelistirilmis klor stabilitesine sahip,lineer viskoelastik sulu sivi otomatik bulasik makinesi deterjan bilesimi.
EP0541202A1 (de) * 1991-11-08 1993-05-12 Colgate-Palmolive Company Lineares, viskoelastisches, wässriges flüssiges Waschmittel für Geschirrspülautomaten mit verbesserten nichtfilmbildenden Eigenschaften
EP0560615A1 (de) * 1992-03-11 1993-09-15 Colgate-Palmolive Company Lineares, viskoelastisches, wässriges, flüssiges Waschmittel für Geschirrspülautomaten
GR1001379B (el) * 1992-05-29 1993-10-29 Colgate Palmolive Co Γραμμική ιξωδοελαστική σύν?εση υδατικού υγρού απορρυπαντικού αυτομάτου πλυντηρίου πιάτων.
US5470499A (en) * 1993-09-23 1995-11-28 The Clorox Company Thickened aqueous abrasive cleanser with improved rinsability
US5529711A (en) * 1993-09-23 1996-06-25 The Clorox Company Phase stable, thickened aqueous abrasive bleaching cleanser
US5650017A (en) * 1994-07-04 1997-07-22 Lever Brothers Company, Division Of Conopco, Inc. Washing process and composition
WO2002016541A1 (en) * 2000-08-25 2002-02-28 Reckitt Benckiser N.V. Water-soluble packages containing liquid compositions
US7271141B2 (en) 2000-08-25 2007-09-18 Reckitt Benckiser N.V. & Reckitt Benckiser (Uk) Limited Water soluble packages containing liquid compositions
AU2001282341B2 (en) * 2000-08-25 2006-10-12 Reckitt Benckiser (Uk) Limited Water-soluble packages containing liquid compositions
US7192911B2 (en) 2001-07-07 2007-03-20 Henkel Kgaa Nonaqueous 3 in 1 dishwasher products
US7041628B2 (en) 2001-07-07 2006-05-09 Henkel Kommanditgesellschaft Auf Aktien Aqueous 3 in 1 dishwasher products
US7153816B2 (en) 2001-08-17 2006-12-26 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Dishwasher detergent with improved protection against glass corrosion
US8021610B2 (en) 2006-09-07 2011-09-20 Biolargo Life Technologies, Inc. Systems providing antimicrobial activity to an environment
US8226964B2 (en) 2006-09-07 2012-07-24 Biolargo Life Technologies, Inc. Systems and methods for cleaning liquid carriers related applications data
US9414601B2 (en) 2006-09-07 2016-08-16 Biolargo Life Technologies, Incorporated Material having antimicrobial activity when wet
US9127235B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer
US9840683B2 (en) 2013-10-09 2017-12-12 Basf Se Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US10364409B2 (en) 2013-10-09 2019-07-30 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer

Also Published As

Publication number Publication date
NO910964D0 (no) 1991-03-12
CA2038023A1 (en) 1991-09-14
NZ237301A (en) 1992-09-25
AU7291291A (en) 1991-09-19
NO910964L (no) 1991-09-16
GR910100120A (en) 1992-06-30
IE910817A1 (en) 1991-10-09
GR1000851B (el) 1993-02-17
PL289391A1 (en) 1991-12-02
AU632221B2 (en) 1992-12-17
MY109088A (en) 1996-11-30
IL97427A0 (en) 1992-06-21
PT96998A (pt) 1991-10-31

Similar Documents

Publication Publication Date Title
EP0446761A1 (de) Lineare viskoelastische wässerig-flüssige Detergenszusammensetzungen, insbesondere für Geschirrspülautomaten, oder mit verbesserter Stabilität bei erhöhter Temperatur
EP0398021B1 (de) Lineares, viscoelastisches wässriges, flüssiges Waschmittel für Geschirrspülmaschinen
US5053158A (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
US5225096A (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition having improved chlorine stability
EP0541200A1 (de) Lineares, viskoelastisches, wässriges flüssiges Waschmittel für Geschirrspülautomaten
US5395547A (en) Process of making an aqueous viscoelastic automatic dishwash detergent containing a silicate-neutralized crosslinked polyacrylate
US5298180A (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
AU656580B2 (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
US5368766A (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
US5246615A (en) Aqueous polymeric solution of a neutralized crosslinked polymeric acid
US5202046A (en) Process for preparing a linear viscoelastic aqueous liquid automatic dishwasher deteregent composition
EP0517309A1 (de) Lineares viscoelastisches wässriges flüssiges Waschmittel, insbesondere für Geschirrspülautomaten mit verbesserter Temperaturstabilität
EP0510945A2 (de) Lineare, viskoelastische, wässerig-flüssige Detergenszusammensetzungen, insbesondere für Geschirrspülautomaten
EP0560615A1 (de) Lineares, viskoelastisches, wässriges, flüssiges Waschmittel für Geschirrspülautomaten
EP0517310A1 (de) Wässriges flüssiges Waschmittel mit polymerem Verdichtungsmittel
EP0517314A1 (de) Lineares, viskoelastisches, wässriges flüssiges Waschmittel für Geschirrspülautomaten
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 (de) Linares viskoseelastisches wässeriges Flüssigwaschmittel, insbesondere für Geschirrspülmaschinen mit verbesserter Temperaturbeständigkeit
EP0541204A1 (de) Lineares, viskoelastisches, wässriges flüssiges Waschmittel für Geschirrspülautomaten
IE921755A1 (en) Aqueous Liquid Detergent Composition, Having a Polymeric¹Thickener
EP0517308A1 (de) Lineares, viscoelastisches, wässriges, flüssiges Waschmittel für Geschirrspülautomaten
AU654008B2 (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition
EP0523826A1 (de) Viskoelastische wässrig-flüssige Detergenszusammensetzung, insbesondere für Geschirrspülautomaten, mit verbesserter Verteilbarkeit
NZ242825A (en) Viscoelastic automatic dishwashing compositions containing an alkali metal compound, sodium and potassium ions and c10-c50 fatty acid; the composition does not wet or adhere to a polyolefinic bottle

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: 19910727

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

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: 19941001