EP0517309A1 - Lineares viscoelastisches wässriges flüssiges Waschmittel, insbesondere für Geschirrspülautomaten mit verbesserter Temperaturstabilität - Google Patents

Lineares viscoelastisches wässriges flüssiges Waschmittel, insbesondere für Geschirrspülautomaten mit verbesserter Temperaturstabilität Download PDF

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Publication number
EP0517309A1
EP0517309A1 EP92201527A EP92201527A EP0517309A1 EP 0517309 A1 EP0517309 A1 EP 0517309A1 EP 92201527 A EP92201527 A EP 92201527A EP 92201527 A EP92201527 A EP 92201527A EP 0517309 A1 EP0517309 A1 EP 0517309A1
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Prior art keywords
composition
alkali metal
weight
potassium
salt
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EP92201527A
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English (en)
French (fr)
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Makarand Shevade
Nagaraj Shripad Dixit
Rhyta Rounds
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Colgate Palmolive Co
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Colgate Palmolive Co
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Publication of EP0517309A1 publication Critical patent/EP0517309A1/de
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    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3958—Bleaching agents combined with phosphates

Definitions

  • Liquid automatic dishwasher detergent compositions both aqueous and nonaqueous have recently received much attention, and the aqueous products have achieved commercial popularity.
  • U.S. Patent 3,720,621 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.
  • compositions may further include a structuring chelant which may be a salt of carbonate, pyrophosphate or mixture thereof, and preferably the potassium salts.
  • 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.
  • 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 viscoelastic aqueous liquid automatic dishwasher detergent composition according to the present invention comprises water, 0.01 to 2% by weight of a long chain fatty acid or salt thereof from 5 to 20% by weight of an alkali metal metal silicate, from 5 to 40% by weight of at least one alkali metal detergent builder salt, a sufficient amount of a chlorine bleach compound to provide 0.2 to 4% by weight of available chlorine 1 to 8 wt.
  • aqueous phase includes both sodium and potassium ions at a K/Na weight ratio of from 1/1 to 45/1.
  • the present invention provides an improved linear viscoelastic aqueous liquid automatic dishwasher detergent composition
  • water 0.01-2 % by weight of long chain fatty acid or salt thereof, optionally, from 0.1 to 5% by weight of low-foaming chlorine bleach stable, water dispersible automatic dishwasher non-soap organic detergent, from 10 to 35% by weight of alkali metal detergent builder salt, at least 50% by weight of which is potassium tripolyphosphate or potassium pyrophosphate and at least 5% by weight of which is sodium tripolyphosphate, from 3 to 20% by weight of a chlorine bleach compound, and at least one cross-linked polycarboxylate thickening agent having a molecular weight of at least 500,000, wherein the aqueous phase includes both sodium and potassium ions at a K/Na weight ratio of from 1/1 to 45/1.
  • the compositions preferably have a bulk density of from 1.28 g/cm3 to 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, (a) 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 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 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.
  • the 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: TABLE A Aging Temperature (°F) Duration (Weeks) Minimum Preferred 140 > 1 > 2 120 > 6 > 8 100 > 13 > 16 Ambient > 24 > 24 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 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 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 include anti-foaming agent (e.g. phosphate ester) and higher fatty acid or salt thereof as a physical stabilizer and optionally a detergent surface active cleaning agent.
  • anti-foaming agent e.g. phosphate ester
  • higher fatty acid or salt thereof as a physical stabilizer
  • optionally a detergent surface active cleaning agent 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 1,250,000; Carbopol 940 a molecular weight of 4,000,000 and Carbopol 934 a molecular weight of 3,000,000.
  • the Carbopol 900 series 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.
  • the preparation of this class of cross-linked carboxylic polymers is described in U.S. Patent 2,798,053. 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 high 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 500,000 to 10,000,000, preferably 750,000 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 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 5 percent, preferably from 0.05 to 2 percent, and especially, preferably from 0.1 to 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 be in the range of from 0.2 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 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 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 its 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) or potassium pyrophosphate and sodium tripolyphosphate (NaTPP) (especially hexahydrate).
  • KTPP potassium tripolyphosphate
  • NaTPP sodium tripolyphosphate
  • Typical ratios of KTPP to NaTPP are from 1.4:1 to 10:1, especially from 2:1 to 8:1.
  • the total amount of detergent builder salts is preferably from 10 to 35% by weight, more preferably from 15 to 35%, especially from 18 to 30% by weight of the composition.
  • the alkali metal detergent builder salt will be comprised of from 65 to 95% of KTPP, especially 75 to 90% of KTPP and from 5 to 35%, especially 10 to 25% of NaTPP.
  • the amount of KTPP will be in the range of from 8 to 25%, preferably 15 to 22% by weight, and the amount of NaTPP will be in the range of from 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 10 to 50 carbon atoms, more preferably from 12 to 40 carbon atoms, and especially preferably from 14 to 40 carbon atoms, and most preferably 20 to 40, 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 di- and trivalent metals of Groups IIA, IIB and IIIB, such as magnesium, calcium, aluminium and zinc, although other polyvalent metals, including those of Groups IIIA, IVA, VA, IB, IVB, VB, 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.
  • the metals may be present in the divalent to pentavelent state.
  • 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.
  • 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 and salt 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 more 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.
  • 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 35° to 50°C can be used.
  • 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 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 about 10:1 to 1:1 and preferably 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 dichloroisocyanurate, 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 contains 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 (NaOC1) solution of from 11 to 13% available chlorine in amounts of 3 to 20%, preferably 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 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 which are optionally 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.
  • surfactant should be compatible with the other ingredients of the composition.
  • suitable 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 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 3% 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 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 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.
  • the composition 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 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 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.
  • 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 should be sufficient to provide the neutralized thickening agent with a pH of at least 11, preferably at least 11.5.
  • 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 competition.
  • 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-cross-linked polyacrylic acid is from 800 to 200,000, preferably 1000 to 150,000, especially from 2,000 to 100,000.
  • the non-cross-linked polyacrylic acid is used in amounts from 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 100 microns in diameter, preferably from 20 to 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 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, optionally, 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 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 know 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.
  • Example 1 The following formulations A-F were prepared as described below:
  • 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, added sequentially, in the order stated, with the mixing continued at medium shear for several minutes before adding the next ingredient.
  • NaTPP sodium tripolyphosphate
  • TKPP tetrapotassium pyrophosphate
  • KTPP potassium tripolyphosphate
  • the surfactant emulsion as described below
  • bleach and color 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 Wf Wo x 100 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: Ingredient Amount (wt. %) Deionized water q.s.
  • the composition has a pH of 11.3 + 0.1 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.

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EP92201527A 1991-06-07 1992-05-27 Lineares viscoelastisches wässriges flüssiges Waschmittel, insbesondere für Geschirrspülautomaten mit verbesserter Temperaturstabilität Withdrawn EP0517309A1 (de)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0560615A1 (de) * 1992-03-11 1993-09-15 Colgate-Palmolive Company Lineares, viskoelastisches, wässriges, flüssiges Waschmittel für Geschirrspülautomaten
WO1997038075A1 (en) * 1996-04-05 1997-10-16 S.C. Johnson & Son, Inc. Method of stabilizing the viscosity of a thickened composition
EP0992574A1 (de) * 1998-10-05 2000-04-12 The Procter & Gamble Company Reinigungsmittelzusammensetzungen

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2203163A (en) * 1987-04-03 1988-10-12 Sandoz Ltd Dishwasher detergents
EP0346112A2 (de) * 1988-06-09 1989-12-13 The Procter & Gamble Company Flüssige Zusammensetzungen für die automatische Geschirreinigung mit einem Silberschutz
EP0373864A2 (de) * 1988-12-15 1990-06-20 The Procter & Gamble Company Stabile, verdickte wässrige Bleichmittelzusammensetzungen
EP0446761A1 (de) * 1990-03-13 1991-09-18 Colgate-Palmolive Company Lineare viskoelastische wässerig-flüssige Detergenszusammensetzungen, insbesondere für Geschirrspülautomaten, oder mit verbesserter Stabilität bei erhöhter Temperatur

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2203163A (en) * 1987-04-03 1988-10-12 Sandoz Ltd Dishwasher detergents
EP0346112A2 (de) * 1988-06-09 1989-12-13 The Procter & Gamble Company Flüssige Zusammensetzungen für die automatische Geschirreinigung mit einem Silberschutz
EP0373864A2 (de) * 1988-12-15 1990-06-20 The Procter & Gamble Company Stabile, verdickte wässrige Bleichmittelzusammensetzungen
EP0446761A1 (de) * 1990-03-13 1991-09-18 Colgate-Palmolive Company Lineare viskoelastische wässerig-flüssige Detergenszusammensetzungen, insbesondere für Geschirrspülautomaten, oder mit verbesserter Stabilität bei erhöhter Temperatur

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0560615A1 (de) * 1992-03-11 1993-09-15 Colgate-Palmolive Company Lineares, viskoelastisches, wässriges, flüssiges Waschmittel für Geschirrspülautomaten
WO1997038075A1 (en) * 1996-04-05 1997-10-16 S.C. Johnson & Son, Inc. Method of stabilizing the viscosity of a thickened composition
US5869601A (en) * 1996-04-05 1999-02-09 S. C. Johnson & Son, Inc. Method of stabilizing the viscosity of a thickened composition
EP0992574A1 (de) * 1998-10-05 2000-04-12 The Procter & Gamble Company Reinigungsmittelzusammensetzungen
WO2000020547A1 (en) * 1998-10-05 2000-04-13 The Procter & Gamble Company Cleaning compositions

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NO922055L (no) 1992-12-08
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GR920100227A (el) 1993-04-28
CA2070025A1 (en) 1992-12-08
AU1617092A (en) 1992-12-10
FI922496A0 (fi) 1992-05-29
TR26584A (tr) 1995-03-15
PT100547A (pt) 1993-09-30
NO922055D0 (no) 1992-05-25
IE921741A1 (en) 1992-12-16

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