EP0649898A2 - Verdicktes wässriges, phasenstabiles Scheuermittel mit Bleichwirkung - Google Patents

Verdicktes wässriges, phasenstabiles Scheuermittel mit Bleichwirkung Download PDF

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Publication number
EP0649898A2
EP0649898A2 EP94307710A EP94307710A EP0649898A2 EP 0649898 A2 EP0649898 A2 EP 0649898A2 EP 94307710 A EP94307710 A EP 94307710A EP 94307710 A EP94307710 A EP 94307710A EP 0649898 A2 EP0649898 A2 EP 0649898A2
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EP
European Patent Office
Prior art keywords
cleanser
bleach
aqueous abrasive
effective amount
surfactant
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP94307710A
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English (en)
French (fr)
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EP0649898A3 (de
Inventor
Kevin J. Brodbeck
Amy M. Penticoff
Aram Garabedian
Clement K. Choy
Brian P. Argo
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Clorox Co
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Clorox Co
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Publication of EP0649898A2 publication Critical patent/EP0649898A2/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • the present invention relates to thickened aqueous abrasive cleansers containing hypochlorite bleach with improved phase stability.
  • Thickened hypochlorite bleach solutions or compositions have long been used in a variety of applications including hard surface cleaning, disinfecting and the like. These compositions are typically provided with increased viscosity for a number of reasons, principally to increase residence time of the composition on non-horizontal surfaces.
  • thickened hypochlorite bleach compositions have been available from a wide variety of sources for use in hard surface cleaning.
  • Finley et al. European Patent Application EP 373.864 and Prince et al., U.S. Patent 5,130,043, disclosed hypochlorite bleach compositions consisting of polyacrylate thickeners, amine oxide detergent, and optional fatty acid soap and/or a bleach stable synthetic anionic detergent for cleaning hard surfaces such as toilet bowls, bathroom tiles and shower walls.
  • both of these references do not disclose, teach, or suggest the need to reduce or limit the free electrolyte, or ionic strength, of thickened cleaners.
  • hypochlorite-containing abrasive cleansers in the art, but they typically require either a colloidal clay thickener, such as disclosed in Hartman, U.S. Patents 3,985,668, 4,005,027 and 4,051,056, a mixture of surfactants, such as disclosed in Jones et al., U.S. Patent 4,352,678, or a stearate soap, such as disclosed in Chapman, U.S. Patent 4,240,919. All of these systems suffer from disadvantages, such as premature hardening in the colloidal clay-thickened systems, or poor phase stability, as in the stearate-thickened systems.
  • compositions have performed satisfactorily for their intended purpose.
  • thickened aqueous abrasive cleansers containing hypochlorite bleach with improved phase and bleach stability offering improved characteristics and benefits.
  • the invention provides a phase stable, thickened aqueous abrasive cleanser comprising:
  • the invention provides a method of preparing a phase stable, thickened aqueous abrasive cleanser comprising the steps of adding together:
  • the cleanser contains about 0.1-50% calcium carbonate abrasive.
  • the formulations having a higher calcium carbonate content tend to have a plastic, creamy, flowable rheology, while those of lower calcium carbonate content (0.1-25%) will tend to have a shear-thinning rheology.
  • the viscosity as measured in centipoise, with each unit representing 1,000, is plotted on the y axis, while the time in days is plotted on the x axis. Measurements at different temperatures are represented by a box (21.1°C), cross-hatch (37.7°C) and a diamond (48.8°C).
  • the invention provides a hard surface, hypochlorite-containing, abrasive scouring cleanser having no significant syneresis, undue viscosity or yield stress value increase, stably suspends abrasives, and has excellent rinsing characteristics. All of the foregoing advantages are present over time and after these compositions have been subjected to storage at elevated temperatures.
  • the present invention provides a stably suspended abrasive scouring cleanser which uses relatively small amounts of surfactants, thus lowering the total cost of producing these cleansers.
  • the absence of solvents results in a less irritating product as well.
  • the invention provides a phase stable, thickened aqueous abrasive cleanser comprising:
  • a further embodiment of the invention provides a method of preparing a phase stable, thickened aqueous abrasive cleanser comprising the steps of adding together:
  • inventive cleansers are described more particularly below. As used herein, all percentages are weight percentages of actives, unless otherwise specified. Additionally, the term “effective amount” means an amount sufficient to accomplish the intended purpose, e.g., thickening, suspending, cleaning, etc.
  • the cross-linked polyacrylate polymers of the present invention are generally characterized as resins in the form of acrylic acid polymers. These resins are well known for use in a number of applications and it is commonly theorized that the carboxyl groups in the polymers are responsible for desirable characteristics resulting from the polymers.
  • cross-linked polyacrylate polymers are available from a number of sources including materials available under the trade name CARBOPOL® from B. F. Goodrich Company and under the trade name POLYGEL® available from 3V Chemical Company.
  • Cross-linked polyacrylate polymers of a type contemplated by the present invention are also believed to be available from other sources which are also contemplated for use within the present invention and as defined herein.
  • the cross-linked polyacrylate polymers are generally characterized as acrylic acid polymers which are non-linear and water-dispersible while being cross-linked with an additional monomer or monomers in order to exhibit a molecular weight in the range from eighty thousand to about seven million g/mole, preferably about one hundred thousand to about seven million g/mole, more preferably about one million to seven million g/mole. Additionally, an average formula weight for a polymer subunit is about 60-120 g/mole, preferably 75-95 g/mole. The most preferred CARBOPOLs average about 86 g/mole.
  • the polymers are cross-linked with a polyalkenyl polyether, the cross-linking agents tending to interconnect linear strands of the polymers to form the resulting cross-linked product.
  • the pH of an aqueous polymer solution provides a rough measure of the number of carboxyl groups in the polymer, and thus is an estimate of the degree of cross-linking and/or degree of branching of the polymer.
  • the pH of a 2% polymer solution at 21° C should be between 1.8 and 5.0, more preferably 2.0 and 3.0. The pH is measured before neutralization.
  • cross-linked polyacrylate polymers are effective for achieving, in conjunction with the surfactant, the desired viscosity and stability in compositions of the type contemplated by the present invention. However, some differences particularly in terms of stability have been observed for different cross-linked polyacrylate polymers.
  • Suitable cross-linked polyacrylate polymers for purposes of the present invention include the CARBOPOL 600 series, 900 series, 1300 series and 1600 series resins Most. preferred are the CARBOPOL 1621 and 1610 resins (formerly known as 613 and 623 resins, respectively), which include a cross-linking agent plus hydrophobe. Also suitable is CARBOPOL 672 (formerly 614). More specific examples of polymers selected from these series are included in the examples set forth in the Experimental Section below.
  • effective cross-linked polyacrylate polymers for purposes of the present invention also include those available under the trade name POLYGEL and specified as DA, DB, and DK, available from 3V Chemical Company, and the SOKOLAN® polymers produced by the BASF Corporation.
  • certain of the cross-linked polyacrylate polymers noted above may provide particular advantages or features within a thickened composition as contemplated by the present invention. Accordingly, it is also contemplated by the present invention to particularly employ mixtures or combinations of such polymers in order to produce compositions exhibiting combined characteristics of the respective polymers.
  • the cross-linked polyacrylate polymers of the present invention are believed to be tightly coiled in a presolvated condition with relatively limited thickening capabilities. Upon being dispersed in water, the polymer molecules are hydrated and uncoil or relax to varying degrees. Thickening is particularly effective with the polyacrylate polymers when they are uncoiled or relaxed as noted above. Uncoiling of the polyacrylate polymers may be achieved for example by neutralizing or stabilizing the polymer with inorganic bases such as sodium hydroxide, potassium hydroxide, ammonium hydroxide or low molecular weight amines and alkanolamines.
  • inorganic bases such as sodium hydroxide, potassium hydroxide, ammonium hydroxide or low molecular weight amines and alkanolamines.
  • Neutralization or stabilization of the polyacrylate polymers in this manner rapidly results in almost instantaneous thickening of an aqueous solution containing the polymers and surfactants. It is noted that the highest viscosity occurs when the polymer is completely neutralized; however, it has been empirically determined that elasticity is greater when the polymer is only partially neutralized. For some applications, it may be preferable to enhance elasticity rather than viscosity, for example, to aid in dispensing through restricted orifices, or to improve residence time on non-horizontal surfaces. Elasticity is also important to suspend abrasives, although even when fully neutralized the polymer retains sufficient elasticity for this purpose.
  • the particular effectiveness of the cross-linked polyacrylate polymers in the present invention is believed to be due to a characteristic yield point or yield value.
  • a typical liquid tends to deform as long as it is subjected to a tensile or shear stress of the type created by dispensing the liquid from a spray-type dispenser or the like.
  • the rate of deformation or shear rate is generally proportional to the shear stress. This relationship was originally set forth in Newton's Law and a liquid exhibiting such proportional or straight-line characteristics are commonly termed Newtonian liquids.
  • thickening While there are many types of inorganic and organic thickeners, not all will provide the proper type of shear-thinning rheology desired in the invention. Common clays, for instance, will likely lead to a false body rheology, which, at rest, turn very viscous. A thixotropic rheology is also not desirable in this invention since in the thixotropic state, a liquid at rest also thickens dramatically. If the thixotrope has a yield stress value, as typically found in clay-thickened liquid media, the fluid at rest may not re-achieve flowability without shaking or agitation.
  • the surfactants included in the formulas of this invention are important in achieving the shear-thinning rheology.
  • the formulations of this invention can develop viscosities in the range of 20-70,000 centipoise (cP), preferably 1,000-40,000 cP, and most preferably 10,000-30,000 cP.
  • cP centipoise
  • a viscosity of between about 4,000 to about 25,000, more preferably 5,000 to 15,000 is obtained.
  • the most preferred bleach-stable surfactants are the amine oxides, especially trialkyl amine oxides, as represented below. Additionally, it may be suitable to use mono-short chain C1 ⁇ 4 alkyl, di-long chain C10 ⁇ 20 alkyl amine oxides.
  • R' and R'' can be alkyl of 1 to 3 carbon atoms, and are most preferably methyl, and R is alkyl of about 10 to 20 carbon atoms. When R' and R'' are both methyl and R is alkyl averaging about 12 carbon atoms, the structure for dimethyldodecylamine oxide, a preferred amine oxide, is obtained.
  • amine oxides include the C14 alkyl (tetradecyl) and C16 (hexadecyl) amine oxides. It is particularly preferred to use mixtures of any of the foregoing, especially a mixture of C12 and C16 dimethyl amine oxide.
  • C14 alkyl (tetradecyl) and C16 (hexadecyl) amine oxides It is particularly preferred to use mixtures of any of the foregoing, especially a mixture of C12 and C16 dimethyl amine oxide.
  • these particular type of bleach-stable nonionic surfactants include the dimethyldodecylamine oxides sold under the trademarks AMMONYX® LO and CO by Stepan Chemical.
  • amine oxides are those sold under the trademark BARLOX® by Lonza, Conco XA sold by Continental Chemical Company, AROMAXTM sold by Akzo, and SCHERCAMOXTM sold by Scher Brothers, Inc. These amine oxides preferably have main alkyl chain groups averaging about 10 to 20 carbon atoms.
  • Betaines and their derivatives may also be useful in the compositions of the invention.
  • Particularly preferred are betaines such as those described in the previously mentioned Choy et al. references, the disclosures of which are incorporated herein by reference.
  • the polyacrylates of the present invention are highly branched and, as described previously, are relatively tightly coiled in a presolvated condition. When dispersed in water, the polymer molecules are hydrated and uncoil to some degree, providing some thickening. However, full viscosity development occurs only when the polymer is neutralized, creating a net negative charge on the carboxyl group. Owing to the proximity of the carboxyl groups, the negatives tend to repel each other, thus greatly increasing the volume occupied by the polymer and resulting in significant thickening.
  • the surfactant affords viscosity stability to the polyacrylate by "surfactant shielding," that is, the positive pole of the surfactant is attracted to the negatively charged carboxyl groups of the polymer, thus shielding the carboxyl groups from positively charged species.
  • shielding-effective surfactants have a hydrophobic - lipophobic balance (HLB) of between about 11-13. Most preferred is an amine oxide.
  • the surfactant is present in a shielding-effective amount, generally about 0.1 to 10% by weight, more preferably about 0.5 to 3% by weight.
  • a cosurfactant may be selected from anionic surfactants such as soaps (alkyl carboxylates), alkali metal alkyl sulfates, alkyl aryl sulfonates, primary and secondary alkane sulfonates (SAS, also referred to as paraffin sulfonates), alkyl diphenyl ether disulfonates, and mixtures thereof.
  • anionic surfactants will preferably have alkyl groups averaging about 8 to 20 carbon atoms. Most preferred are the soaps, especially potassium soaps.
  • the soaps utilized are typically formed in situ, by using the appropriate carboxylic acid (e.g., a C6-18 carboxylic acid, such as, without limitation, lauric, stearic, myristic acids, and unsaturated acids, such as coco fatty acid), and neutralizing with e.g., potassium hydroxide (KOH).
  • carboxylic acid e.g., a C6-18 carboxylic acid, such as, without limitation, lauric, stearic, myristic acids, and unsaturated acids, such as coco fatty acid
  • KOH potassium hydroxide
  • alkali metal hydroxides such as sodium hydroxides
  • commercial sources of these fatty acids include Henkel KGaA's Emery Division.
  • alkali metal salts of alkyl aryl sulfonic acids might be useful, such as linear alkyl benzene sulfonates, known as LAS's.
  • Typical LAS's have C8 ⁇ 16 alkyl groups, examples of which include Stepan Chemical Company's BIOSOFT®, and CALSOFT® manufactured by Pilot Chemical Company.
  • Still further potentially suitable cosurfactants include the alkyl diphenyl ether disulfonates, such as those sold by Dow Chemical Company under the name "Dowfax,” e.g., Dowfax 3B2.
  • Other potentially suitable anionic cosurfactants include alkali metal alkyl sulfates such as Conco Sulfate WR, sold by Continental Chemical Company, which has an alkyl group of about 16 carbon atoms; and secondary alkane sulfonates such as HOSTAPUR SAS, manufactured by Farbwerke Hoechst A.G., Frankfurt, Germany.
  • a stabilizing agent may be necessary to maintain viscosity and/or phase stability when certain anionic cosurfactants are present.
  • Preferred stabilizing agents are hydrotropes, which are generally described as non-micelle-forming substances, either liquid or solids, organic or inorganic, capable of solubilizing insoluble compounds in a liquid medium.
  • hydrotropes must interact or associate with both hydrophobic and hydrophilic media.
  • typical hydrotropes do not appear to readily form micelles in aqueous media on their own. In the present invention, it is important that the hydrotrope act as a dispersant and not as a surfactant.
  • a hydrotrope is a dispersant which does not affect the critical micelle concentration ("CMC") of the liquid system.
  • CMC critical micelle concentration
  • the hydrotrope acts to prevent micelle formation by any anionic surfactants present.
  • concentration or amount of the material, as well as type may also be critical towards determining whether such material is a hydrotrope.
  • materials which ordinarily are classified surfactants may in fact behave as hydrotropes if the amount used is limited.
  • the preferred hydrotropes are alkali metal salts of benzoic acid and its derivatives; alkyl sulfates and sulfonates with 6-10 carbons in the alkyl chain, C8 ⁇ 14 dicarboxylic acids, anionic polymers such as polyacrylic acid and their derivatives; and most preferably, unsubstituted and substituted, especially the alkali metal salts of, aryl sulfonates; and unsubstituted and substituted aryl carboxylates.
  • aryl includes benzene, napthalene, xylene, toluene, cumene and similar aromatic nuclei.
  • substituted aryl means that one or more substituents known to those skilled in the art, e.g., halo (chloro, bromo, iodo, fluoro), nitro, or C1 ⁇ 4 alkyl or alkoxy, can be present on the aromatic ring.
  • substituents known to those skilled in the art, e.g., halo (chloro, bromo, iodo, fluoro), nitro, or C1 ⁇ 4 alkyl or alkoxy.
  • Other good dispersants include other derivatives of aryl sulfonates, salts of phthalic acid and its derivatives and certain phosphate esters. Most preferred are alkyl naphthalene sulfonates (such as Petro 22 available from Petro Chemicals Company) and sodium xylene sulfonate (such as Stepanate X, available from Stepan Chemical Company.
  • stabilizing agents are soaps, discussed above under cosurfactants. It is noted here, though, that especially soluble alkali metal soaps of a fatty acid, such as C6 ⁇ 14 fatty acid soaps, may perform a stabilizing function. Especially preferred are sodium and potassium soaps of lauric and myristic acid. When present, sufficient stabilizing agent is added to stabilize, generally 0 to no more than 1% by weight, preferably about 0.1 to 0.5 weight percent.
  • pH adjusting agents may be added to adjust the pH, and/or buffers may act to maintain pH.
  • alkaline pH is favored for purposes of both rheology and cleaning effectiveness.
  • buffers include the alkali metal silicates, metasilicates, polysilicates, carbonates, hydroxides, and mixtures of the same.
  • Control of pH may be necessary to maintain the stability of a halogen source and to avoid protonating the amine oxide.
  • the pH should be maintained above the pKa of the amine oxide.
  • the pH should be above about 6.
  • the pH is maintained above about pH 10.5, preferably above or about pH 12.
  • Most preferred for this purpose are the alkali metal hydroxides, especially potassium hydroxide.
  • the total amount of pH adjusting agent/buffer including that inherently present with bleach plus any added, can vary from about 0.1% to 5%, preferably from about 0.1-1.0%.
  • hypochlorite In the invention, it has been found necessary to minimize or avoid the presence of salts, such as sodium chloride, which contribute to ionic strength within the compositions.
  • the hypochlorite would thus preferably be selected or formed in a manner to avoid the presence of such undesirable salts.
  • hypochlorite bleaches are commonly formed by bubbling chlorine gas through liquid sodium hydroxide or corresponding metal hydroxide to result in formation of the corresponding hypochlorite.
  • hypochlorite bleaches are commonly formed by bubbling chlorine gas through liquid sodium hydroxide or corresponding metal hydroxide to result in formation of the corresponding hypochlorite.
  • such reactions commonly result in formation of a salt such as sodium chloride.
  • the present invention thus preferably uses hypochlorites formed for example by reaction of hypochlorous acid with alkali metal hydroxide in order to produce the corresponding hypochlorite with water as the only substantial by-product.
  • Hypochlorite bleach produced in this manner is referred to as "high purity, high strength" bleach, or also, as low salt, high purity” bleach, and is available from a number of sources, for example Olin Corporation which produces hypochlorite bleach as a 30% solution in water. The resulting solution is then diluted to produce the hypochlorite composition of the present invention.
  • hypochlorite may be formed with other alkaline metals as are well known to those skilled in the art.
  • hypochlorite is employed herein, it is not intended to limit the invention only to the use of chloride compounds but is also intended to include other halides or halites, as discussed in greater detail below.
  • the present invention preferably uses potassium hypochlorite and, somewhat less preferably, sodium hypochlorite, produced by the high strength bleach process.
  • a hypochlorite of any alkali metal including a chloride salt of the corresponding alkali metal is similarly to be minimized.
  • the hypochlorite of the invention either avoids the inclusion of a chloride salt as noted above or includes such a chloride salt only within a range of up to about 5% by weight of the composition.
  • the hypochlorite component is increased from about 1% by weight of the composition, the chloride salt should be even further reduced since the chloride salt, particularly in the presence of the hypochlorite component, makes it difficult to achieve desirable thickening of the composition, or stability.
  • the hypochlorite and any salt present within the composition are also the principal source of ionic strength for the composition.
  • the ionic strength of the composition has an effect on thickening, that is, if the percentage of salt as noted above is exceeded, it becomes difficult to achieve desirable thickening in the composition.
  • high ionic strength may be detrimental to the stability of the composition as it can cause collapse of the polymer structure.
  • the ionic strength of the compositions of the present invention is maintained preferably less than about 5M, more preferably less than about 3M. It is to be noted, however, that control of ionic strength is an additional avenue by which viscosity and rheology can be controlled, if desired.
  • hypochlorite is preferably present in an amount ranging from about 0.1 weight percent to about 10 weight percent, more preferably about 0.2% to 5%, and most preferably about 0.5% to 3%.
  • Abrasives such as a perlite, silica sand may be used herein and various other insoluble, inorganic particulate abrasives are also possible, such as quartz, pumice, feldspar, tripoli and calcium phosphate. However, it is most preferred to use calcium carbonate (also known as "calcite").
  • Calcium carbonate used in this invention appears to have a dual role. On the one hand, it is an abrasive and thus is used in the invention to promote cleaning action by providing a scouring action when the cleansers of the invention are used on hard surfaces.
  • the abrasive can be present in amounts ranging from about .1% to 70% by weight of the compositions of this invention, preferably about 20-50% by weight.
  • the abrasive -- preferably, calcium carbonate -- content will be from about 0.5 to about 25%, which results in a more fluid product, which has the ability to sheet and cling onto vertical surfaces.
  • Particle size will range from average particle size of about ten to eight hundred, more preferably forty to six hundred, most preferably fifty to five hundred microns. In general, about 50% or more of the particles will have particle diameters of greater than one hundred microns (pass through U.S. 150 mesh sieves).
  • Particle hardness of the abrasives can range from Mohs hardness of about 2-8, more preferably 3-6.
  • Calcium carbonate, also known as calcite, is available from numerous commercial sources such as Georgia Marble Company, and has a Mohs hardness of about 3.
  • a size of U.S. 140 mesh is selected, although others may be appropriate.
  • Abrasives can affect the viscosity of the formulations. It is known that there can be a "hard sphere" thickening phenomenon merely by the addition of insoluble materials into a liquid phase. In the systems of the invention, moreover, it appears that the abrasives help to thicken somewhat by compressing the polyacrylate polymer.
  • the polyacrylate as the last step in the manufacture.
  • the reaction of free calcium ions and the polyacrylate is essentially mitigated, apparently because the calcium carbonate particles have become coagulated by the surfactants.
  • an alternate order of addition can be beneficial. For example, when calcium carbonate, or other porous abrasives, are added in the last step, the formulation becomes aerated, entraining air bubbles, thus resulting in enhanced thickening and stability.
  • the main ingredient in the inventive compositions is water, preferably water with minimal ionic strength.
  • Water provides the continuous liquid phase into which the other ingredients are added to be dissolved/dispersed. This provides the unique fluid properties of the invention.
  • the amount of water present generally exceeds 30% and, indeed, can be as high as 99%, although generally, it is present in a quantity sufficient (q.s.) to provide the appropriate fluid characteristics desired of the product.
  • the composition of the present invention can be formulated to include such components as fragrances, coloring agents, whiteners, solvents, chelating agents and builders, which enhance performance, stability or aesthetic appeal of the composition.
  • a fragrance such as those commercially available from International Flavors and Fragrance, Inc.
  • Dyes and pigments may be included in small amounts.
  • Ultramarine Blue (UMB) and copper phthalocyanines are examples of widely used pigments which may be incorporated in the composition of the present invention.
  • Buffer materials e.g. carbonates, silicates and polyacrylates also may be added, although there is the caveat that amounts of such buffers should not be present so as to elevate the ionic strength of the compositions.
  • certain less water soluble or dispersible organic solvents may be included. These bleach stable solvents include those commonly used as constituents for proprietary fragrance blends, such as terpene derivatives.
  • the terpene derivatives herein include terpene hydrocarbons with a functional group. Effective terpenes with a functional group include, but are not limited to, alcohols, ethers, esters, aldehydes and ketones.
  • Terpene alcohols including, for example, verbenol, transpinocarveol, cis -2-pinanol, nopol, iso-borneol, carbeol, piperitol, thymol, ⁇ -terpineol, terpinen-4-ol, menthol, 1,8-terpin, dihydro-terpineol, nerol, geraniol, linalool, citronellol, hydroxycitronellol, 3,7-dimethyl octanol, dihydro-myrcenol, ⁇ -terpineol, tetrahydro-alloocimenol and perillalcohol; Terpene ethers and esters, including, for example, 1,8-cineole, 1,4-cineole, isobornyl methylether, rose pyran,
  • compositions of this invention In one method for preparing the compositions of this invention, all of the ingredients are charged into an appropriate volume vessel and mixed. However, because large scale processing is sometimes facilitated by addition order, numerous methods of preparation were explored and tested herein.
  • pH adjusting agent low ionic strength, high purity hypochlorite bleach, preferably, potassium hypochlorite
  • abrasive typically, calcium carbonate
  • surfactants such as the bleach-stable nonionic surfactant, and, if used, an anionic surfactant
  • Adjuncts such as fragrances may be emulsified by the surfactant(s) and can be added either prior to, or after, polymer addition.
  • mixing speed and duration may be adjusted as necessary to incorporate any adjuncts.
  • all ingredients except for the abrasive are combined.
  • a gel such as described in Garabedian et al. (U.S. Patent Application Serial No. 08/097,738, filed July 27, 1993, of common assignment herewith, and incorporated herein by reference thereto).
  • the abrasive is charged directly into the gel and dispersed with good mixing.
  • the gel breaks down, forming a somewhat lumpy dispersion, at first, then gradually resulting in an opaque, creamy, thickened liquid, wherein the abrasives are well suspended.
  • good mixing was used, aeration of the product occurs, resulting in entrained air bubbles, causing somewhat higher viscosity. This somewhat higher viscosity (above 25,000 cp) may have performance benefits for cleaning applications requiring a stiffer formulation.
  • Example I a preferred formulation is set forth.
  • Example I the first four ingredients were added, resulting in a thin liquid.
  • the potassium hypochlorite/calcium carbonate preblend was then added, with good mixing.
  • the polyacrylate and the fragrance oil were added, resulting in good, controllable thickening.
  • the fragrance oil can, optionally, be added with the surfactants.
  • the resulting product had a thick and creamy consistency. Using a Brookfield RVT Rotoviscometer, loaded with a #4 spindle, at 5 rpm, after 5 minutes of mixing, at 24.9°C, the resulting viscosity was 23,960 cp.
  • Example I had excellent viscosity stability.
  • the Table 1 below demonstrates the stability at room and elevated temperatures, and over an extended period.
  • Table 1 Time Temperature Viscosity Time 0 21.1°C 24,800 cp 48.8°C 24,800 cp Time 7 days 21.1°C 25,720 cp 48.8°C 31,320 cp
  • Example II also had excellent viscosity stability.
  • the Table 2 below demonstrates the stability at room and elevated temperatures, and over extended time periods.
  • Example III a further preferred formulation was prepared Example III Ingredient Wt. % Actives Wt.% D.I. H2O 23.85 q.s. KOH 1.25 0.55 KOCl 7.60 0.125 CaCO3 35.00 35.00 Amine oxide 3.00 0.90 Soap Solution 5.60 0.49 Polyacrylate Dispersion 23.69 0.385 Fragrance Oil 0.04 0.04 100.00% ⁇
  • Example III additionally had excellent viscosity and syneresis stability, except for at the highest temperature over extended time.
  • the Table 3 below demonstrates the viscosity stability at room and elevated temperatures, and over extended time periods. This is also graphically depicted in Fig. 1 of the Drawings.
  • Table 4 demonstrates syneresis stability. (Syneresis was determined by metering the liquid formulations into clear, 16 fluid oz. bottles and measuring the height of the watery layer over the opaque, creamy liquid layer.)
  • Table 4 Syneresis Time Temperature 21.1°C 37.7°C 48.8°C 0 0% 0% 0% 0% 5 days 0% 0% 0% 11 days 0% 3% 3% 18 days 0% 3% 30%
  • Example IV a still further preferred formulation was prepared.
  • Example IV Ingredient Wt. % Actives Wt.% D.I. H2O 23.85 q.s. KOH 1.25 0.55 KOCl 7.60 0.125 CaCO3 35.00 35.00 Amine oxide 3.00 0.90 Soap Solution 5.60 0.49 Polyacrylate Dispersion 25.00 0.40 Fragrance Oil 0.04 0.04 100.00% ⁇
  • Example IV additionally had excellent viscosity and syneresis stability, even at the highest temperature over extended time.
  • the Table 5 below demonstrates the viscosity stability at room and elevated temperatures, and over extended time periods. This is also graphically depicted in Fig. 2 of the Drawings.
  • Table 6 demonstrates syneresis stability.
  • Example V a still further preferred formulation was prepared.
  • the amount of cross-linked polyacrylate is increased, resulting in increasing longterm viscosity and syneresis stability.
  • Example V Ingredient Wt. % Actives Wt.% D.I. H2O 23.85 q.s. KOH 1.25 0.55 KOCl 7.60 0.125 CaCO3 35.00 35.00 Amine oxide 3.00 0.90 Soap Solution 5.60 0.49 Polyacrylate Dispersion 26.25 0.42 Fragrance Oil 0.04 0.04 100.00% ⁇
  • Example V additionally had excellent viscosity and syneresis stability, even at the highest temperature over extended time.
  • the Table 7 below demonstrates the viscosity stability at room and elevated temperatures, and over extended time periods. This is also depicted graphically in Fig. 3 of the Drawings.
  • Table 8 demonstrates syneresis stability.
  • Example VI a further embodiment of the invention is portrayed.
  • the cleaner of Example VI has, in contrast to the preceding examples, a lower calcium carbonate content, and a higher cross-linked polyacrylate content.
  • the resulting cleaner has, again, excellent viscosity and syneresis stability.
  • This Example VI also had excellent viscosity and syneresis stability, even at the highest temperature over extended time.
  • the Table 9 below demonstrates the viscosity stability at room and elevated temperatures, and over extended time periods.
  • Table 10 demonstrates syneresis stability.
  • Table 9 Viscosity Time Temperature Viscosity 1 week 21.1°C 10,400 cp 37.7°C 11,000 cp 48.8°C 10,000 cp 2 weeks 21.1°C 10,300 cp 37.7°C 11,800 cp 48.8°C 10,400 cp 3 weeks 21.1°C 10,400 cp 37.7°C 11,600 cp 48.8°C 10,300 cp 4 weeks 21.1°C N/A 37.7°C 11,200 cp 48.8°C 6,200 cp
  • Table 10 Syneresis Time Temperature 21.1°C 37.7°C 48.8°C 1 week trace slight trace N/A 2 weeks 2.25% ⁇ 1% 1.4% 3 weeks 2.7% 2.0% 2.0%

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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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  • Dispersion Chemistry (AREA)
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EP94307710A 1993-10-22 1994-10-20 Verdicktes wässriges, phasenstabiles Scheuermittel mit Bleichwirkung. Withdrawn EP0649898A3 (de)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0651051A2 (de) * 1993-10-29 1995-05-03 The Clorox Company Auf Hypochloriten basierender gelförmiger Reiniger
GB2300643A (en) * 1995-05-11 1996-11-13 Reckitt & Colman Inc Hard Surface Cleaners
WO1997011147A1 (en) * 1995-09-19 1997-03-27 Reckitt & Colman S.A. Cleaning compositions with enhanced rheology
GB2311996A (en) * 1996-04-12 1997-10-15 Reckitt & Colman Inc Hard surface scouring cleansers `
WO1997043372A1 (en) * 1996-05-14 1997-11-20 S.C. Johnson & Son, Inc. Rinseable hard surface cleaner
WO1998030672A1 (en) * 1997-01-10 1998-07-16 Reckitt & Colman South Africa (Pty) Limited Improvements in or relating to organic compositions
WO1999032596A1 (en) * 1997-12-22 1999-07-01 S. C. Johnson & Son, Inc. Stabilized acidic chlorine bleach composition and method of use
US5985817A (en) * 1997-02-24 1999-11-16 Reckitt & Colman South Africa Ltd. Pourable, thickened aqueous bleach and abrasive containing compositions
US5997764A (en) * 1997-12-04 1999-12-07 The B.F. Goodrich Company Thickened bleach compositions
WO2000011128A1 (en) * 1998-08-19 2000-03-02 Jeyes Group Limited Liquid bleaching compositions
WO2001005931A1 (en) * 1999-07-16 2001-01-25 Unilever N.V. Liquid abrasive cleaning compositions
US6511953B1 (en) 1998-06-09 2003-01-28 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Hard surface cleaners
GB2393909A (en) * 2002-10-12 2004-04-14 Reckitt Benckiser Inc Thickened, abrasive containing bleach
WO2004108875A1 (en) * 2003-06-07 2004-12-16 Reckitt Benckiser Inc Hard surface cleaning compositions containing soaps
WO2018045924A1 (zh) * 2016-09-08 2018-03-15 南京联创慧驾汽车服务有限公司 高效环保无水洗车清洁液及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
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EP0129980A2 (de) * 1983-05-25 1985-01-02 The Procter & Gamble Company Bleichmittelzusammensetzungen

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JPS5936198A (ja) * 1982-08-25 1984-02-28 花王株式会社 液体洗浄剤組成物
US4857226A (en) * 1986-10-29 1989-08-15 Colgate-Palmolive Company Thixotropic clay aqueous suspensions containing polyacrylic acid polymer or copolymer stabilizers
CA2003857C (en) * 1988-12-15 1995-07-18 Lisa Michele Finley Stable thickened aqueous bleach compositions
US5470499A (en) * 1993-09-23 1995-11-28 The Clorox Company Thickened aqueous abrasive cleanser with improved rinsability

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
EP0129980A2 (de) * 1983-05-25 1985-01-02 The Procter & Gamble Company Bleichmittelzusammensetzungen

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0651051A2 (de) * 1993-10-29 1995-05-03 The Clorox Company Auf Hypochloriten basierender gelförmiger Reiniger
GB2300643A (en) * 1995-05-11 1996-11-13 Reckitt & Colman Inc Hard Surface Cleaners
GB2305434B (en) * 1995-09-19 1999-03-10 Reckitt & Colmann Sa Abrasive cleaning composition
GB2305434A (en) * 1995-09-19 1997-04-09 Reckitt & Colmann Sa Abrasive cleaning compositions
US6268325B1 (en) 1995-09-19 2001-07-31 Reckitt & Colman Sa Cleaning compositions containing thickeners and abrasive materials
AU710976B2 (en) * 1995-09-19 1999-09-30 Reckitt Benckiser France Cleaning compositions with enhanced rheology
WO1997011147A1 (en) * 1995-09-19 1997-03-27 Reckitt & Colman S.A. Cleaning compositions with enhanced rheology
GB2311996A (en) * 1996-04-12 1997-10-15 Reckitt & Colman Inc Hard surface scouring cleansers `
WO1997039099A1 (en) * 1996-04-12 1997-10-23 Reckitt & Colman Inc. Stable bleach-containing cleansing compositions with soft abrasives
US5821214A (en) * 1996-04-12 1998-10-13 Reckitt & Colman Inc. Stable bleach-containing cleansing compositions with soft abrasives
AU718606B2 (en) * 1996-04-12 2000-04-20 Reckitt Benckiser Inc. Stable bleach-containing cleansing compositions with soft abrasives
WO1997043372A1 (en) * 1996-05-14 1997-11-20 S.C. Johnson & Son, Inc. Rinseable hard surface cleaner
WO1998030672A1 (en) * 1997-01-10 1998-07-16 Reckitt & Colman South Africa (Pty) Limited Improvements in or relating to organic compositions
US5985817A (en) * 1997-02-24 1999-11-16 Reckitt & Colman South Africa Ltd. Pourable, thickened aqueous bleach and abrasive containing compositions
US5997764A (en) * 1997-12-04 1999-12-07 The B.F. Goodrich Company Thickened bleach compositions
US6083422A (en) * 1997-12-04 2000-07-04 The B.F. Goodrich Company Thickened bleach compositions
US6162371A (en) * 1997-12-22 2000-12-19 S. C. Johnson & Son, Inc. Stabilized acidic chlorine bleach composition and method of use
WO1999032596A1 (en) * 1997-12-22 1999-07-01 S. C. Johnson & Son, Inc. Stabilized acidic chlorine bleach composition and method of use
US6511953B1 (en) 1998-06-09 2003-01-28 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Hard surface cleaners
WO2000011128A1 (en) * 1998-08-19 2000-03-02 Jeyes Group Limited Liquid bleaching compositions
WO2001005931A1 (en) * 1999-07-16 2001-01-25 Unilever N.V. Liquid abrasive cleaning compositions
GB2393909A (en) * 2002-10-12 2004-04-14 Reckitt Benckiser Inc Thickened, abrasive containing bleach
WO2004035727A1 (en) * 2002-10-12 2004-04-29 Reckitt Benckiser Inc Liquid bleaching composition
WO2004108875A1 (en) * 2003-06-07 2004-12-16 Reckitt Benckiser Inc Hard surface cleaning compositions containing soaps
WO2018045924A1 (zh) * 2016-09-08 2018-03-15 南京联创慧驾汽车服务有限公司 高效环保无水洗车清洁液及其制备方法

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EP0649898A3 (de) 1996-02-28

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