WO1998040456A1 - A process for making a selected crystalline calcium carbonate builder for use in detergent compositions - Google Patents

A process for making a selected crystalline calcium carbonate builder for use in detergent compositions Download PDF

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Publication number
WO1998040456A1
WO1998040456A1 PCT/US1998/004470 US9804470W WO9840456A1 WO 1998040456 A1 WO1998040456 A1 WO 1998040456A1 US 9804470 W US9804470 W US 9804470W WO 9840456 A1 WO9840456 A1 WO 9840456A1
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Prior art keywords
calcium carbonate
crystalline calcium
builder
crystalline
detergent
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PCT/US1998/004470
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French (fr)
Inventor
Eugene Joseph Pancheri
Scott William Capeci
William Marion Hoffman
Rose Marie Weitzel
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The Procter & Gamble Company
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Priority to JP53964598A priority Critical patent/JP2001516377A/en
Publication of WO1998040456A1 publication Critical patent/WO1998040456A1/en

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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
    • 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
    • C11D3/1233—Carbonates, e.g. calcite or dolomite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • the invention is directed to a process for producing an inexpensive builder material for use in detergent compositions. More particularly, the process invention provides a selected crystalline calcium carbonate material substantially having a rhombohedral crystalline structure with ⁇ 1,0,-1,1 ⁇ crystallographic indices.
  • This very inexpensive builder material is especially suitable for use in detergent compositions used in fabric laundering, bleaching, automatic or hand dishwashing, hard surface cleaning and in any other application which requires the use of a builder material to remove water hardness.
  • formulators of cleaning compositions to include, in addition to a cleaning active material, a builder to remove hardness cations (e.g. calcium cations and magnesium cations) from washing solution which would otherwise reduce the efficiency of the cleaning active material (e.g. surfactant) and render certain soils more difficult to remove.
  • a builder to remove hardness cations (e.g. calcium cations and magnesium cations) from washing solution which would otherwise reduce the efficiency of the cleaning active material (e.g. surfactant) and render certain soils more difficult to remove.
  • laundry detergent compositions typically contain an anionic surfactant and a builder to reduce the effects of hardness cations in wash solutions.
  • the builder sequesters or "ties up" the hardness cations so as to prevent them from hindering the cleaning action of the anionic surfactant in the detergent composition.
  • water-soluble phosphate materials have been used extensively as detergency builders. However for a variety of reasons, including eutrophication of surface waters allegedly caused by phosphates, there has been a desire to use other builder materials in many geographic areas.
  • Other known builders include water-soluble builder salts, such as sodium carbonate, which can form precipitates with the hardness cations found in washing solutions.
  • water-soluble builder salts such as sodium carbonate
  • calcite typically has to be produced in a very small particle size in order to have a larger surface area which is harder to poison. This, however, renders the very small calcite particle dusty and difficult to handle.
  • the required particle sizes are so small (at least having 15 ⁇ fi/g or more of surface area) that manufacturing of such calcite particles is extremely expensive.
  • production of such small calcite particles may require a controlled "growing" process which is extremely expensive.
  • Another problem associated with the use of calcite as a "seed crystal" for the poisons and precipitates in washing solutions is the difficulty experienced in adequately dispersing the calcite in the washing solution so that it does not deposit on fabrics or articles which have been subjected to cleaning operations. Such deposits or residues are extremely undesirable for most any cleaning operation, especially in fabric laundering and tableware cleaning situations.
  • the prior art is replete with suggestions for dealing with the handling and dispersability problems associated with calcite.
  • Patent 3,981,686 (Intermountain Research and Development Corp.); Mallow et al, U.S. Patent 4,828.620 (Southwest Research Institute); Bjorklund et al, "Adsorption of Anionic and Cationic Polymers on Porous and Non-porous Calcium Carbonate Surfaces," Applied Surface Science 75 pp. 197-203 (1994); Wierzbicki et al, "Atomic Force Microscopy and Molecular Modeling of Protein and Peptide Binding to Calcite,” Calcified Tissue International 54, pp. 133-141 (1994); Park et al, “Tribological Enhancement of CaC03 Dissolution during Scanning Force Microscopy,” Langmuir, pp. 4599-4603, 12 (1996); and Nancollas et al,
  • the present invention provides a process for producing a detergent builder in the form of a crystalline calcium carbonate that is in an especially selected crystalline form.
  • the crystalline calcium carbonate has a substantially rhombohedral crystal structure with ⁇ 1,0,-1,1 ⁇ crystallographic indices.
  • the process involves either milling or compaction rolling starting crystalline calcium carbonate into the rhombohedral crystal structure with ⁇ 1,0,-1,1 ⁇ indices.
  • the process of the present invention is extremely inexpensive because it involves relatively little capital and operating expenditures to convert inexpensive naturally occurring calcite into the desired builder which performs well even when used at large median particle sizes.
  • a process for producing a detergent builder to be used in a detergent composition comprises the steps of: (a) feeding starting crystalline calcium carbonate into an apparatus having an internal chamber and air nozzles directed into the chamber; and (b) milling the crystalline calcium carbonate in the apparatus by inputting air at a pressure from about 1 bar to about 50 bar such that the crystalline calcium carbonate is converted to a rhombohedral crystalline structure with ⁇ 1,0,-1,1 ⁇ crystallographic indices, thereby forming the detergent builder.
  • another process for producing the detergent builder is provided.
  • This particular process comprises the steps of: (a) feeding starting crystalline calcium carbonate into an apparatus having a pair of compaction rollers; (b) milling the crystalline calcium carbonate in the apparatus by feeding the crystalline calcium carbonate between the compaction rollers at a pressure from about 100 bar to about 5000 bar such that a crystalline calcium carbonate slab is formed, wherein said crystalline calcium carbonate has a rhombohedral crystalline structure with ⁇ 1,0,-1, 1 ⁇ crystallographic indices; and (c) grinding the slab into particles, thereby forming the detergent builder. Additionally, the detergent builder produced by the processes described herein is provided.
  • Fig. 1 illustrates a crystalline calcium carbonate detergent builder produced by a process in accordance with the invention
  • Figs. 2-8 illustrate naturally occurring crystalline calcium carbonate structures which can be used as the starting material in the process and which are commonly found in nature (Fig. 8 is a partial perspective depicting only the top portion of the crystal).
  • the detergent builder produced by the present process invention can be used in a variety of compositions including but not limited to fabric laundering, fabric or surface bleaching, automatic or hand dishwashing, hard surface cleaning and any other application which requires the use of a builder material to remove water hardness.
  • the phrase “effective amount” means that the level of the builder material in the composition is sufficient to sequester an adequate amount of hardness in the washing solution such that the detersive surfactant is not overly inhibited.
  • the word “crystalline” means a mixture or material having a regularly repeating internal arrangement (i.e., “lattice") of its atoms and external plane faces.
  • the phrase “substantially having a rhombohedral crystalline structure” means a crystal having the form of a parallelogram and no right angles (e.g., as depicted in Fig. 1).
  • ⁇ 1 ,0,- 1,1 ⁇ crystallographic indices refers to a specific set of crystal planes on a hexagonal coordinate system which defines a selected crystalline structure (also referenced as the "Miller indices” for a hexagonal coordinate system).
  • crystalline calcium carbonate refers to the chemical entity, calcium carbonate, in crystalline form, of which the most common form is referenced as "calcite”. Also see standard texts on all of these subjects, such as Blackburn et al, Principles of Mineralogy, 2nd Ed., pp. 21 -51 ( 1994) and Klein et al, Manual of Mineralogy, p. 405 et seq (1977).
  • the crystalline calcium carbonate in accordance with the invention can be made in a variety of ways so long as the resulting crystal substantially has a rhombohedral crystalline structure with ⁇ 1,0,-1, 1 ⁇ crystallographic indices.
  • the starting ingredient is crystalline calcium carbonate which does not have the aforementioned crystal structure.
  • naturally occurring calcite such as the one depicted in Fig. 5 can be mined or commercially purchased and subjected to the process described hereinafter.
  • the word "milling” means crushing, grinding or otherwise affecting the physical structure of the crystalline calcium carbonate.
  • the process first involves feeding starting crystalline calcium carbonate into an apparatus having an internal chamber and air nozzles directed into the chamber.
  • an Alpine Fluid Bed Jet Mill Model 100 AFG Fluid Bed Jet Mill commercially available from Hosokawa Micron - Alpine, Germany.
  • Other suitable apparatus are commercially available from Hosokawa Micron - Alpine, Germany are sold under the trade names Aeroplex and Turboplex.
  • the starting crystalline calcium carbonate is milled in such apparatus by inputting and grinding with air at a pressure from about 1 bar to about 50 bar, more preferably from about 1.5 bar to about 10 bar, and most preferably from about 2.5 bar to about 5 bar.
  • the starting crystalline calcium carbonate is converted to a rhombohedral crystalline structure with ⁇ 1,0,-1,1 ⁇ crystallographic indices, thereby forming the detergent builder.
  • This selected milling process step in which the starting ingredient (e.g., calcite) is milled involves crushing and/or grinding the starting crystalline calcium carbonate such that it is cleaved to form the aforementioned crystalline calcite structure (Fig. 1).
  • ⁇ 1 ,0,- 1,1 ⁇ crystallographic indices define "low stress" planes of larger naturally occurring calcite along which cleavage can occur if milled with selected process parameters.
  • the aforementioned apparatus can be used in conjunction with an Air Classifier such as Alpine Air Classifier (Model 50 ATP Air Classifier commercially available from Hosokawa Micron - Alpine, Germany) which is mounted on top of the aforementioned Fluid Bed Jet Mill apparatus.
  • Suitable starting crystalline calcium carbonate such as calcite can be purchased from Omya, Inc., or Quincy Carbonates.
  • the median particle size of the such starting crystalline calcium carbonates are from about 50 microns to about 5000 microns, preferably from about 150 microns to about 500 microns.
  • the starting crystalline calcium carbonate is subjected to the aforementioned apparatus operated with the valve (El 2) set open, throttle flap valve set to adjust air chamber to 0 bar air pressure, Air Classifier speed set between about 2000 rpms to about 20,000 rpms, more preferably from about 7000 rpms to about 15,000 rpms, most preferably at 8000 rpms, grinding valve set at 5 bar pressure, and the product feed screw set at 35% of maximum.
  • the Air Classifier and Fluid Bed Jet Mill are run until the desired crystalline calcium carbonate builder is obtained. Actual time and various other process parameters are within the purview of the skilled artisan.
  • apparatus having a pair of compaction rollers can be used to form a slab from starting caclium carbonate into a crystalline calcium carbonate having the desired indices.
  • Table Top Roller Mill and Ecoplex compaction devices that are commercially available from Hosokawa Micron - Alpine, Germany can be used herein.
  • the roll pressure is preferably set at about 100 bar to about 5000 bar, more preferably from about 800 bar to about 4000 bar, most preferably from about 1000 bar to about 2000 bar.
  • the pair of compaction rollers can be substituted with equivalent mechanical apparatus such as a roller and plate device or a dual plate device which is commonly used in a laboratory-scale hydraulic press.
  • the detergent builder produced by the present process invention is a crystalline calcium carbonate substantially rhombohedral crystalline structure 10 as depicted in Fig. 1.
  • This crystalline calcium carbonate is defined by ⁇ 1,0,-1,1 ⁇ crystallographic or Miller indices. It has been surprisingly found that by judiciously selecting a crystalline calcium carbonate of such a crystalline configuration, superior builder performance (i.e., removal of water hardness) can be achieved when used in typical detergent compositions for laundering soiled clothes.
  • the median particle size of this crystalline calcium carbonate as detailed hereinafter is not required to be in the very small range (e.g., less than about 2 microns with a surface areas at least about 15 m ⁇ /g).
  • Figs 2-8 define crystal structures of crystalline calcium carbonate or calcite which do not substantially have a rhombohedral crystalline structure with ⁇ 1,0,-1,1 ⁇ crystallographic indices.
  • Fig. 2 depicts a crystalline calcium carbonate having a rhombohedral structure, but with ⁇ 0,1,-1,2 ⁇ crystallographic indices.
  • Fig. 3 illustrates crystalline calcium carbonate or calcite in a cubic crystal structure 20 having ⁇ 0,2,-2,1 ⁇ crystallographic indices.
  • Fig. 4 depicts a hexagonal crystal structure 22 with ⁇ 1,0,-1,0 ⁇ and ⁇ 0,0,0,1 ⁇ crystallographic indices, while Fig. 5 shows a prismatic structure 24 with ⁇ 0,1,-1,2 ⁇ and ⁇ 0,0,0,1 ⁇ crystallographic indices.
  • Fig. 1 depicts a crystalline calcium carbonate having a rhombohedral structure, but with ⁇ 0,1,-1,2 ⁇ crystallographic indices.
  • Fig. 3 illustrates crystalline calcium carbonate or calcite in a cubic crystal structure 20 having ⁇ 0,2,-2,1 ⁇ crystall
  • Fig. 6 depicts a crystalline calcium carbonate structure 26 having ⁇ 2,1,-3,1 ⁇ crystallographic indices
  • Fig. 7 illustrates a scalenohedral calcite crystal structure 28 with ⁇ 2, 1 ,-3, 1 ⁇ and small faces with the preferred ⁇ 1 ,0,- 1,1 ⁇ crystallographic indices
  • Fig. 8 illustrates a top partial perspective view of yet another calcium carbonate crystalline structure 30 which has ⁇ 0,1,-1,2 ⁇ , ⁇ 2,1,-3,1 ⁇ and ⁇ 1,0,-1,0 ⁇ crystallographic indices. All of the calcium carbonate materials depicted in Figs. 2-8 can be used as the starting crystalline calcium carbonate material in the instant process invention.
  • Figs. 3, 4, 5 and 7 depict the most common calcite crystals found in nature. It should be understood that none of these calcite crystal structures are in the form of Fig. 1 which is within the scope of the invention. Furthermore, it is believed that the calcite crystal structures of Figs. 2-8 do not perform as well as the Fig. 1 structure because the Figs. 2-8 structures have a high population of calcium atoms at their respective crystal planes (i.e., outer surfaces), thereby resulting in poor performance relative to water hardness cation sequestration. To the contrary, as mentioned previously, the calcite crystal depicted in Fig.
  • the "crystalline" nature of the builder material can be detected by X-ray Diffraction techniques known by those skilled in the art.
  • X-ray diffraction patterns are commonly collected using Cu ⁇ p j ⁇ radiation on an automated powder diffractometer with a nickel filter and a scintillation counter to quantify the diffracted X-ray intensity.
  • the X-ray diffraction diagrams are typically recorded as a pattern of lattice spacings and relative X-ray intensities.
  • X-ray diffraction diagrams of corresponding preferred builder materials include, but are not limited to, the following numbers: 5-0586 and 17-0763.
  • the actual amount of crystalline calcium carbonate builder used in a detergent composition will vary widely depending upon the particular application. However, typical amounts are from about 0.1% to about 80%, more typically from about 4% to about 60%, and most typically from about 6% to about 40%, by weight of the detergent composition.
  • the median particle size of the builder is preferably from about 0.2 microns to about 20 microns, more preferably from about 0.3 microns to about 15 microns, even more preferably from about 0.4 microns to about 10 microns, and most preferably from about 0.5 microns to about 10 microns. While the crystalline calcium carbonate builder produced by the process performs at any median particle size, it has been found that optimum overall performance can be achieved within the aforementioned median particle size ranges.
  • median particle size means the particle size as measured by the particle's diameter of a given builder in which 50% by weight of the population has a higher particle size and 50% has a lower particle size.
  • the median particle size is measured at its usage concentration in water (after 10 minutes of exposure to this water solution at a temperature of 50F to 130F) as determined by conventional analytical techniques such as, for example, microscopic determination using a scanning electron microscope (SEM), Coulter Counter or Malvern particle size instruments.
  • SEM scanning electron microscope
  • Coulter Counter Coulter Counter
  • Malvern particle size instruments In general, the particle size of the builder not at its usage concentration in water can be any convenient size.
  • the crystalline calcium carbonate builder preferably has selected surface area for optimal performance.
  • the crystalline calcium carbonate has a surface area of from about 0.01 m ⁇ /g to about 12 m ⁇ /g, more preferably from about 0.1 rn ⁇ /g to about 10 m ⁇ /g, even more preferably from about 0.2 m ⁇ /g to about 5 m ⁇ /g, and most preferably from about 0.2 m ⁇ /g to about 4 m ⁇ /g.
  • Other suitable surface area ranges include from about 0.1 m ⁇ /g to about 4 m ⁇ /g and from about 0.01 m ⁇ /g to about 4 m ⁇ /g.
  • the surface areas can be measured by standard techniques including by nitrogen adsorption using the standard Bruauer, Emmet & Teller (BET) method.
  • a suitable machine for this method is a Carlo Erba Sorpty 1750 instrument operated according to the manufacturer's instructions.
  • the crystalline calcium carbonate builder produced herein also unexpectedly has improved builder performance in that it has a high calcium ion exchange capacity.
  • the builder material has a calcium ion exchange capacity, on an anhydrous basis, of at least about 100 mg equivalent of calcium carbonate hardness/gram, more preferably at least about 200 mg, and even more preferably at least about 300 mg, and most preferably from at least about 400 mg, equivalent of calcium carbonate hardness per gram of builder.
  • the builder unexpectedly has an improved calcium ion exchange rate.
  • the builder material has a calcium carbonate hardness exchange rate of at least about 5 ppm, more preferably from about 10 ppm to about 150 ppm, and most preferably from about 20 ppm to about 100 ppm, CaC ⁇ 3/minute per 200 ppm of the builder material.
  • a wide variety of test methods can be used to measure the aforementioned properties including the procedure exemplified hereinafter and the procedure disclosed in Corkill et al, U.S. Patent No. 4,605,509 (issued August 12, 1986), the disclosure of which is incorporated herein by reference.
  • the detergent composition When the builder is used in detergent compositions, it is preferable for the detergent composition to be substantially free of phosphates and phosphonates. As used herein, “substantially free” means has less than 0.05% by weight of a given material.
  • the detergent composition is substantially free of soluble silicates, especially if magnesium cations are part of the water hardness composition in the particular use and the detergent composition does not include an auxiliary builder to sequester such cations.
  • superior performance of the detergent composition containing the aforedescribed builder can be achieved if the detergent composition is substantially free of polycarboxylates, polycarboxylic oligomer/polymers and the like.
  • the detergent composition is preferably substantially free of potassium salts, or if they are present, are included at very low levels. Specifically, the potassium salts are included at levels of about 0.01% to about 5%, preferably at about 0.01% to about 2% by weight of the detergent composition.
  • sodium sulfate and sodium carbonate are included in the detergent composition in which the builder is contained, they are preferably in a weight ratio of about 1 :50 to about 2: 1, more preferably from about 1 :40 to about 1 :1, most preferably from about 1:20 to about 1: 1 of sodium sulfate to sodium carbonate. While not intending to be bound by theory, it is believed that excessive amounts of sulfate relative to carbonate may interfere with the builder performance of the crystalline calcium carbonate.
  • sodium carbonate is included in the detergent composition in which the builder is contained, it is included preferably in a weight ratio of about 1 : 1 to about 20: 1, more preferably from about 1 : 1 to about 10:1, most preferably from about 1 : 1 to about 5 : 1 of sodium carbonate to crystalline calcium carbonate builder.
  • sodium carbonate is present in the detergent composition in an amount of from about 2% to about 80%, more preferably from about 5% to about 70%, and most preferably from about 10% to about 50% by weight of the detergent composition.
  • Adjunct Builders One or more auxiliary builders can be used in conjunction with the builder material produced by the process invention herein to further improve the performance of the compositions into which the builder material is incorporated.
  • the auxiliary builder can be selected from the group consisting of aluminosilicates, crystalline layered silicates, MAP zeolites, citrates, amorphous silicates, polycarboxylates, sodium carbonates and mixtures thereof.
  • auxiliary builders are described hereinafter.
  • compositions into which the builder material made by the present process is incorporated can also comprise a detergent aluminosilicate builder which are referenced as aluminosilicate ion exchange materials and sodium carbonate.
  • aluminosilicate ion exchange materials used herein as a detergent builder preferably have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced.
  • the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble), the disclosure of which is incorporated herein by reference.
  • the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit the as high of an exchange rate and capacity as provided by the sodium form.
  • the aluminosilicate ion exchange material preferably is in over dried form so as to facilitate production of crisp detergent agglomerates as described herein.
  • the aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders.
  • particle size diameter represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the preferred particle size diameter of the aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle size diameter is from about 1 microns to about 8 microns.
  • the aluminosilicate ion exchange material has the formula Na z [(A10 2 ) z .(Si0 2 ) y ]xH 2 0 wherein z and y are integers of at least 6, the molar ratio of z to y is from about 1 to about 5 and x is from about 10 to about 264. More preferably, the aluminosilicate has the formula Na 12 [(Al ⁇ 2)i2-(Si ⁇ 2)i2]xH 2 0 wherein x is from about 20 to about 30, preferably about 27.
  • These preferred aluminosilicates are available commercially, for example under designations Zeolite A, Zeolite B and Zeolite X.
  • Naturally-occurring or synthetically derived aluminosilicate ion exchange materials suitable for use herein can be made as described in Krummel et al, U.S. Patent No. 3,985,669, the disclosure of which is incorporated herein by reference.
  • the aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaC ⁇ 3 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaC ⁇ 3 hardness/gram. Additionally, the instant aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /gallon minute/-gram/gallon, and more preferably in a range from about 2 grains Ca "H 7gallon/minute/-gram/gallon to about 6 grains Ca "H 7gallon minute/-gram/gallon.
  • compositions into which the builder material made according to the instant process invention are incorporated will comprise at least about 1%, preferably from about 1% to about 55%, and most preferably from about 10 to 40%, by weight, of a detersive surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants and mixtures.
  • a detersive surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants and mixtures.
  • Nonlimiting examples of surfactants useful herein include the conventional Cj j-Cjg alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C ⁇ o-C 2 o alkyl sulfates ("AS"), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH3(CH2) x (CHOS0 " M + ) CH3 and CH3 (CH2) y (CHOS0 3 " M + ) CH 2 CH 3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the Cio-Cjg alkyl alkoxy sulfates ("AE X S”; especially EO 1-7 ethoxy sulfates), C j o-Cjg alkyl alkoxy carboxylates (especially the EO 1-5
  • the conventional nonionic and amphoteric surfactants such as the C ⁇ -Cj g alkyl ethoxylates ("AE") including the so- called narrow peaked alkyl ethoxylates and C -C 2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines ("sultaines"), C i ⁇ -C j g amine oxides, and the like, can also be included in the overall compositions.
  • the C j Q -Ci N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C ⁇ -C j N-methylglucamides.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C i ⁇ -C j N-(3- methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C ⁇ -C j glucamides can be used for low sudsing.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C ⁇ Q -C ⁇ soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • LAS C ⁇ i-Cj alkyl benzene sulfonates
  • Adjunct Detergent Ingredients The builder material made by the present process can include additional detergent ingredients and/or, any number of additional ingredients when incorporated in detergent compositions. These adjunct ingredients include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., incorporated herein by reference.
  • other builders include the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates.
  • alkali metal especially sodium, salts of the above.
  • Preferred for use herein are the phosphates, carbonates, Cjo-i fatty acids, polycarboxylates, and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, and mixtures thereof (see below).
  • crystalline layered sodium silicates exhibit a clearly increased calcium and magnesium ion exchange capacity.
  • the layered sodium silicates prefer magnesium ions over calcium ions, a feature necessary to insure that substantially all of the "hardness" is removed from the wash water.
  • These crystalline layered sodium silicates are generally more expensive than amorphous silicates as well as other builders. Accordingly, in order to provide an economically feasible laundry detergent, the proportion of crystalline layered sodium silicates used must be determined judiciously.
  • the crystalline layered sodium silicates suitable for use herein preferably have the formula NaMSi x 0 2x+ 1 .yH 2 0 wherein M is sodium or hydrogen, x is from about 1.9 to about 4 and y is from about 0 to about 20. More preferably, the crystalline layered sodium silicate has the formula
  • Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, both of which are incorporated herein by reference.
  • Chelating agents are also described in U.S. Patent 4,663,071, Bush et al., from Column 17, line 54 through Column 18, line 68, incorporated herein by reference.
  • Suds modifiers are also optional ingredients and are described in U.S. Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault et al., both incorporated herein by reference.
  • Suitable smectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al, issued August 9, 1988, Column 6, line 3 through Column 7, line 24, incorporated herein by reference.
  • Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S. Patent 4,663,071, Bush et al, issued May 5, 1987, both incorporated herein by reference.
  • This Example illustrates the process of the present invention.
  • 2.5 kg/hr of calcite commercially purchased from Omya, Inc.
  • calcite commercially purchased from Omya, Inc.
  • the Fluid Bed Jet Mill and Air Classifier apparatus are operated with the valve (El 2) set open, throttle flap valve set to adjust air chamber to slightly positive air pressure, Air Classifier speed set at 8000 rpms, grinding valve set at 5 bar pressure, and the product feed screw set at 35% of maximum.
  • the air pressure of the rinse air in the Fluid Bed Jet Mill are set at 0.5 to 0.6 bars, after which the desired crystalline calcium carbonate builder having a rhombohedral crystalline structure with ⁇ 1,0,-1,1 ⁇ crystallographic indices is obtained.
  • EXAMPLE II This Example illustrates another embodiment of the process of the present invention. 2.5 kg/hr of calcite commercially purchased from Omya, Inc. is inputted into the drop chamber of a Alpine High Compression Roller Mill (Model 205 Ecoplex Roller Mill commercially available from Hosokawa Micron - Alpine, Germany) wherein the rollers are set at a pressure of about 2500 bars.
  • a slab of the starting calcite is formed which is fed into a Ball Mill to grind the slab into particles having a median particle size of about 3 microns.
  • the resulting particles have a rhombohedral crystalline structure with ⁇ 1,0,-1,1 ⁇ crystallographic indices, thereby forming the detergent builder.
  • EXAMPLE III Calcium Sequestration and Rate of Sequestration Test The following illustrates a step-by-step procedure for determining the amount of calcium sequestration and the rate thereof for the crystalline calcium carbonate builder produced by the process invention described herein.
  • step 9 at 1 minute, 2 minutes, 4 minutes, 8 minutes, and 16 minutes;
  • Amount of sequestration (in ppm CaC03 per gram/liter of builder) is 171 minus the CaC ⁇ 3 concentration at 16 minutes times five.
  • the base granule is prepared by a conventional spray drying process in which the starting ingredients are formed into a slurry and passed though a spray drying tower having a countercurrent stream of hot air (200-300°C) resulting in the formation of porous granules.
  • the admixed agglomerates are formed from two feed streams of various starting detergent ingredients which are continuously fed, at a rate of 1400 kg/hr, into a L ⁇ dige CB-30 mixer/densifier, one of which comprises a surfactant paste containing surfactant and water and the other stream containing starting dry detergent material containing aluminosilicate, the desired crystalline calcium carbonate builder and sodium carbonate.
  • the rotational speed of the shaft in the L ⁇ dige CB-30 mixer/densifier is about
  • the mean residence time is about 1-10 seconds.
  • the contents from the L ⁇ dige CB-30 mixer/densifier are continuously fed into a L ⁇ dige KM-600 mixer/densifier for further agglomeration during which the mean residence time is about 6 minutes.
  • the resulting detergent agglomerates are then fed to a fluid bed dryer and to a fluid bed cooler before being admixed with the spray dried granules.
  • the remaining adjunct detergent ingredients are sprayed on or dry added to the blend of agglomerates and granules.
  • Admixed Agglomerates C 14.15 alkyl sulfate, Na 5.0 5.0 -
  • Termamyl amylase 60 KNU/g 4 0.3 0.3

Abstract

A process for producing an inexpensive detergent builder in the form of a selected crystalline calcium carbonate is provided. Specifically, the process comprises the steps of: (a) feeding starting crystalline calcium carbonate into an apparatus having an internal chamber and air nozzles directed into the chamber; and (b) milling the crystalline calcium carbonate in the apparatus by inputting air at a pressure from about 1 bar to about 50 bar such that the crystalline calcium carbonate is converted to a rhombohedral crystalline structure with {1,0,-1,1} crystallographic indices, thereby forming the detergent builder.

Description

A PROCESS FOR MAKING A SELECTED CRYSTALLINE CALCIUM CARBONATE BUILDER FOR USE IN DETERGENT COMPOSITIONS
FIELD OF THE INVENTION
The invention is directed to a process for producing an inexpensive builder material for use in detergent compositions. More particularly, the process invention provides a selected crystalline calcium carbonate material substantially having a rhombohedral crystalline structure with { 1,0,-1,1 } crystallographic indices. This very inexpensive builder material is especially suitable for use in detergent compositions used in fabric laundering, bleaching, automatic or hand dishwashing, hard surface cleaning and in any other application which requires the use of a builder material to remove water hardness.
BACKGROUND OF THE INVENTION It is common practice for formulators of cleaning compositions to include, in addition to a cleaning active material, a builder to remove hardness cations (e.g. calcium cations and magnesium cations) from washing solution which would otherwise reduce the efficiency of the cleaning active material (e.g. surfactant) and render certain soils more difficult to remove. For example, laundry detergent compositions typically contain an anionic surfactant and a builder to reduce the effects of hardness cations in wash solutions. In this context, the builder sequesters or "ties up" the hardness cations so as to prevent them from hindering the cleaning action of the anionic surfactant in the detergent composition.
As is well known, water-soluble phosphate materials have been used extensively as detergency builders. However for a variety of reasons, including eutrophication of surface waters allegedly caused by phosphates, there has been a desire to use other builder materials in many geographic areas. Other known builders include water-soluble builder salts, such as sodium carbonate, which can form precipitates with the hardness cations found in washing solutions. Unfortunately, the use of such builders alone does not reduce the level of hardness cations at a sufficiently rapid rate. For practical purposes, the acceptable level is not reached within the limited time required for the desired application, e.g. within 10 to 12 minutes for fabric laundering operations in North America and Japan. Moreover, some of these water-soluble builder salts, while attractive from the point of view of cost, have several disadvantages, among which are the tendency of the precipitates formed in aqueous washing solutions (e.g. insoluble calcium carbonate) to become deposited on fabrics or other articles to be cleaned. One alleged solution to this problem has been to include a water-insoluble material which would act as a "seed crystal" for the precipitate (i.e. calcium carbonate). Of the many materials suggested for such use, very small particle size calcite has been the most popular.
However, the inclusion of calcite in detergent compositions has been problematic because of the sensitivity of the hardness cation/salt anion (e.g. calcium/carbonate) reaction product to poisoning by materials (e.g. polyacrylate or certain anionic surfactants) which may be present in the washing solution. Without being limited by theory, the poisoning problem prevents the reaction product from forming in that crystallization onto the seed crystal is inhibited. Consequently, calcite typically has to be produced in a very small particle size in order to have a larger surface area which is harder to poison. This, however, renders the very small calcite particle dusty and difficult to handle. Moreover, the required particle sizes are so small (at least having 15 πfi/g or more of surface area) that manufacturing of such calcite particles is extremely expensive. For example, production of such small calcite particles may require a controlled "growing" process which is extremely expensive. Another problem associated with the use of calcite as a "seed crystal" for the poisons and precipitates in washing solutions is the difficulty experienced in adequately dispersing the calcite in the washing solution so that it does not deposit on fabrics or articles which have been subjected to cleaning operations. Such deposits or residues are extremely undesirable for most any cleaning operation, especially in fabric laundering and tableware cleaning situations. The prior art is replete with suggestions for dealing with the handling and dispersability problems associated with calcite. One previously proposed means for handling calcite is to incorporate it into a slurry, but this involves high storage and transportation costs. Another proposed option involves granulating calcite with binding and dispersing agents to ensure adequate dispersment in the wash solution. However, this option also has been difficult to implement effectively in modern day detergent compositions because the calcite granules have poor mechanical strength which continue to make them difficult to handle and process. Additionally, effective binding and dispersing agents for the calcite have not been discovered to date. Specifically, most of the binding and dispersing agents proposed by the prior art are themselves poisons which reduce the "seed activity" of the calcite. Consequently, it would be desirable to have an improved inexpensive builder material which overcomes the aforementioned limitations and is easy to handle, readily dispersible in washing solutions and exhibits improved builder performance.
Several additional builder materials and combinations thereof have also been used extensively in various cleaning compositions for fabric laundering operations and dish or tableware cleaning operations. By way of example, certain clay minerals have been used to adsorb hardness cations, especially in fabric laundering operations. Further, the zeolites (or aluminosilicates) have been suggested for use in various cleaning situations. Various aluminosilicates have also been used as detergency builders. For example, water-insoluble aluminosilicate ion exchange materials have been widely used in detergent compositions throughout the industry. While such builder materials are quite effective and useful, they account for a significant portion of the cost in most any fully formulated detergent or cleaning composition. In addition, such builders have a limited calcium sequestration capacity, and thus, are not very effective in hard water. Therefore, it would be desirable to have a builder material which performs as well as or better than the aforementioned builders, and importantly, is also less expensive. It would also be desirable to have an inexpensive and convenient process for making such a builder.
Accordingly, despite the aforementioned disclosures, there remains a need in the art for a process for making an inexpensive builder material that is suitable for use in detergent compositions, and which exhibits superior performance and is less expensive to manufacture in that it does not require a very small particle size. There is also a need in the art for such a process which produces a builder material that is easy to handle (i.e., is not "dusty"), easy to process and readily disperses in washing solutions.
BACKGROUND ART The following references are directed to builders for various detergent compositions: Atkinson et al, U.S. Patent 4,900,466 (Lever); Houghton, WO 93/2241 1 (Lever); Allan et al, EP 518 576 A2; (Lever); Zolotoochin, U.S. Patent No. 5,219,541 (Tenneco Minerals Company); Garner-Gray et al, U.S. Patent No. 4,966,606 (Lever); Davies et al, U.S. Patent No. 4,908, 159 (Lever); Carter et al, U.S. Patent No. 4,711 ,740 (Lever); Greene, U.S. Patent No. 4,473,485 (Lever); Davies et al, U.S. Patent No. 4,407,722 (Lever); Jones et al, U.S. Patent No. 4,352,678 (Lever); Clarke et al, U.S. Patent No. 4,348,293 (Lever); Clarke et al, U.S. Patent No. 4,196,093 (Lever); Benjamin et al, U.S. Patent No. 4,171,291 (Procter & Gamble); Kowalchuk, U. S. Patent No. 4,162,994 (Lever); Davies et al, U.S. Patent No. 4,076,653 (Lever); Davies et al, U.S. Patent No. 4,051 ,054 (Lever); Collier, U.S. Patent No. 4,049,586 (Procter & Gamble); Benson et al, U.S. Patent No. 4,040,988 (Procter & Gamble); Cherney, U.S. Patent No. 4,035,257
(Procter & Gamble); Curtis, U.S. Patent No. 4,022,702 (Lever); Child et al, U.S. Patent 4,013,578 (Lever); Lamberti, U.S. Patent No. 3,997,692 (Lever); Cherney, U.S. Patent 3,992,314 (Procter & Gamble); Child, U.S. Patent No. 3,979,314 (Lever); Davies et al, U.S. Patent No. 3,957,695 (Lever); Lamberti, U.S. Patent No. 3,954,649 (Lever); Sagel et al U.S. Patent 3,932,316 (Procter & Gamble); Lobunez et al, U.S. Patent 3,981,686 (Intermountain Research and Development Corp.); Mallow et al, U.S. Patent 4,828.620 (Southwest Research Institute); Bjorklund et al, "Adsorption of Anionic and Cationic Polymers on Porous and Non-porous Calcium Carbonate Surfaces," Applied Surface Science 75 pp. 197-203 (1994); Wierzbicki et al, "Atomic Force Microscopy and Molecular Modeling of Protein and Peptide Binding to Calcite," Calcified Tissue International 54, pp. 133-141 (1994); Park et al, "Tribological Enhancement of CaC03 Dissolution during Scanning Force Microscopy," Langmuir, pp. 4599-4603, 12 (1996); and Nancollas et al,
"The Crystallization of Calcium Carbonate," Journal of Colloid and Interface Science, Vol. 37, No. 4, pp. 824-829 (Dec. 1971).
SUMMARY OF THE INVENTION The aforementioned needs in the art are met by the present invention which provides a process for producing a detergent builder in the form of a crystalline calcium carbonate that is in an especially selected crystalline form. Specifically, the crystalline calcium carbonate has a substantially rhombohedral crystal structure with { 1,0,-1,1 } crystallographic indices. The process involves either milling or compaction rolling starting crystalline calcium carbonate into the rhombohedral crystal structure with { 1,0,-1,1 } indices. The process of the present invention is extremely inexpensive because it involves relatively little capital and operating expenditures to convert inexpensive naturally occurring calcite into the desired builder which performs well even when used at large median particle sizes.
In accordance with one aspect of the invention, a process for producing a detergent builder to be used in a detergent composition is provided. This process comprises the steps of: (a) feeding starting crystalline calcium carbonate into an apparatus having an internal chamber and air nozzles directed into the chamber; and (b) milling the crystalline calcium carbonate in the apparatus by inputting air at a pressure from about 1 bar to about 50 bar such that the crystalline calcium carbonate is converted to a rhombohedral crystalline structure with { 1,0,-1,1 } crystallographic indices, thereby forming the detergent builder. In accordance with another aspect of the invention, another process for producing the detergent builder is provided. This particular process comprises the steps of: (a) feeding starting crystalline calcium carbonate into an apparatus having a pair of compaction rollers; (b) milling the crystalline calcium carbonate in the apparatus by feeding the crystalline calcium carbonate between the compaction rollers at a pressure from about 100 bar to about 5000 bar such that a crystalline calcium carbonate slab is formed, wherein said crystalline calcium carbonate has a rhombohedral crystalline structure with { 1,0,-1, 1 } crystallographic indices; and (c) grinding the slab into particles, thereby forming the detergent builder. Additionally, the detergent builder produced by the processes described herein is provided.
Accordingly, it is an object of the invention to provide a process for producing an inexpensive builder material which exhibits superior performance and is less expensive to manufacture in that it does not require a very small particle size. It is also an object of the invention to provide such a process that produces a builder material which is easy to handle (i.e., is not "dusty"), easy to process and readily disperses in washing solutions. These and other objects, features and attendant advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiment and the appended claims.
All percentages, ratios and proportions used herein are by weight (anhydrous basis) unless otherwise specified. All documents including patents and publications cited herein are incorporated herein by reference. BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 illustrates a crystalline calcium carbonate detergent builder produced by a process in accordance with the invention; and
Figs. 2-8 illustrate naturally occurring crystalline calcium carbonate structures which can be used as the starting material in the process and which are commonly found in nature (Fig. 8 is a partial perspective depicting only the top portion of the crystal). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The detergent builder produced by the present process invention can be used in a variety of compositions including but not limited to fabric laundering, fabric or surface bleaching, automatic or hand dishwashing, hard surface cleaning and any other application which requires the use of a builder material to remove water hardness.
As used herein, the phrase "effective amount" means that the level of the builder material in the composition is sufficient to sequester an adequate amount of hardness in the washing solution such that the detersive surfactant is not overly inhibited. As used herein, the word "crystalline" means a mixture or material having a regularly repeating internal arrangement (i.e., "lattice") of its atoms and external plane faces. As used herein, the phrase "substantially having a rhombohedral crystalline structure" means a crystal having the form of a parallelogram and no right angles (e.g., as depicted in Fig. 1). As used herein, " { 1 ,0,- 1,1 } crystallographic indices" refers to a specific set of crystal planes on a hexagonal coordinate system which defines a selected crystalline structure (also referenced as the "Miller indices" for a hexagonal coordinate system). As used herein, the phrase "crystalline calcium carbonate" refers to the chemical entity, calcium carbonate, in crystalline form, of which the most common form is referenced as "calcite". Also see standard texts on all of these subjects, such as Blackburn et al, Principles of Mineralogy, 2nd Ed., pp. 21 -51 ( 1994) and Klein et al, Manual of Mineralogy, p. 405 et seq (1977).
Process The crystalline calcium carbonate in accordance with the invention (Fig. 1 ) can be made in a variety of ways so long as the resulting crystal substantially has a rhombohedral crystalline structure with { 1,0,-1, 1 } crystallographic indices. Preferably, the starting ingredient is crystalline calcium carbonate which does not have the aforementioned crystal structure. There are a multitude of possible starting crystalline calcium carbonates suitable for use in the process. By way of example, naturally occurring calcite such as the one depicted in Fig. 5 can be mined or commercially purchased and subjected to the process described hereinafter.
As used herein, the word "milling" means crushing, grinding or otherwise affecting the physical structure of the crystalline calcium carbonate. In a preferred embodiment, the process first involves feeding starting crystalline calcium carbonate into an apparatus having an internal chamber and air nozzles directed into the chamber. One convenient apparatus in which such milling can occur is an Alpine Fluid Bed Jet Mill (Model 100 AFG Fluid Bed Jet Mill commercially available from Hosokawa Micron - Alpine, Germany). Other suitable apparatus are commercially available from Hosokawa Micron - Alpine, Germany are sold under the trade names Aeroplex and Turboplex. In this step of the process, the starting crystalline calcium carbonate is milled in such apparatus by inputting and grinding with air at a pressure from about 1 bar to about 50 bar, more preferably from about 1.5 bar to about 10 bar, and most preferably from about 2.5 bar to about 5 bar. In this way, the starting crystalline calcium carbonate is converted to a rhombohedral crystalline structure with { 1,0,-1,1 } crystallographic indices, thereby forming the detergent builder. This selected milling process step in which the starting ingredient (e.g., calcite) is milled involves crushing and/or grinding the starting crystalline calcium carbonate such that it is cleaved to form the aforementioned crystalline calcite structure (Fig. 1). While not intending to be bound by theory, it is believed that the { 1 ,0,- 1,1 } crystallographic indices define "low stress" planes of larger naturally occurring calcite along which cleavage can occur if milled with selected process parameters.
Optionally, the aforementioned apparatus can be used in conjunction with an Air Classifier such as Alpine Air Classifier (Model 50 ATP Air Classifier commercially available from Hosokawa Micron - Alpine, Germany) which is mounted on top of the aforementioned Fluid Bed Jet Mill apparatus. Suitable starting crystalline calcium carbonate such as calcite can be purchased from Omya, Inc., or Quincy Carbonates. The median particle size of the such starting crystalline calcium carbonates are from about 50 microns to about 5000 microns, preferably from about 150 microns to about 500 microns. In this configuration, the starting crystalline calcium carbonate is subjected to the aforementioned apparatus operated with the valve (El 2) set open, throttle flap valve set to adjust air chamber to 0 bar air pressure, Air Classifier speed set between about 2000 rpms to about 20,000 rpms, more preferably from about 7000 rpms to about 15,000 rpms, most preferably at 8000 rpms, grinding valve set at 5 bar pressure, and the product feed screw set at 35% of maximum. The Air Classifier and Fluid Bed Jet Mill are run until the desired crystalline calcium carbonate builder is obtained. Actual time and various other process parameters are within the purview of the skilled artisan.
Alternatively, apparatus having a pair of compaction rollers can be used to form a slab from starting caclium carbonate into a crystalline calcium carbonate having the desired indices. To that end, Table Top Roller Mill and Ecoplex compaction devices that are commercially available from Hosokawa Micron - Alpine, Germany can be used herein. The roll pressure is preferably set at about 100 bar to about 5000 bar, more preferably from about 800 bar to about 4000 bar, most preferably from about 1000 bar to about 2000 bar. The pair of compaction rollers can be substituted with equivalent mechanical apparatus such as a roller and plate device or a dual plate device which is commonly used in a laboratory-scale hydraulic press.
Detergent Builder The detergent builder produced by the present process invention is a crystalline calcium carbonate substantially rhombohedral crystalline structure 10 as depicted in Fig. 1. This crystalline calcium carbonate is defined by { 1,0,-1,1 } crystallographic or Miller indices. It has been surprisingly found that by judiciously selecting a crystalline calcium carbonate of such a crystalline configuration, superior builder performance (i.e., removal of water hardness) can be achieved when used in typical detergent compositions for laundering soiled clothes. The median particle size of this crystalline calcium carbonate as detailed hereinafter is not required to be in the very small range (e.g., less than about 2 microns with a surface areas at least about 15 m^/g).
While not intending to be bound by theory, it is believed that the outer surfaces, e.g., 12, 14 and 16 depicted in Fig. 1, have a significantly high population of oxygen atoms which lends the entire crystalline structure to have more of an affinity to calcium cations which is the predominant source of water hardness. Those skilled in the art will appreciate that this is a crystal having { 1,0,-1,1 } crystallographic indices and its crystal faces are defined thereby. By contrast, Figs 2-8 define crystal structures of crystalline calcium carbonate or calcite which do not substantially have a rhombohedral crystalline structure with { 1,0,-1,1 } crystallographic indices. Moreover, all of the crystal faces or cleavage planes of the calcite crystal structures depicted in Figs. 2-8 can have a much higher population of calcium atoms, thereby creating a strong positive charge on the outer surfaces of these crystals. This, as those skilled in the art will appreciate, does cause these crystalline structures to be less effective at sequestering water hardness cations.
Specifically, Fig. 2 depicts a crystalline calcium carbonate having a rhombohedral structure, but with {0,1,-1,2} crystallographic indices. Fig. 3 illustrates crystalline calcium carbonate or calcite in a cubic crystal structure 20 having {0,2,-2,1 } crystallographic indices. Fig. 4 depicts a hexagonal crystal structure 22 with { 1,0,-1,0} and {0,0,0,1 } crystallographic indices, while Fig. 5 shows a prismatic structure 24 with {0,1,-1,2} and {0,0,0,1 } crystallographic indices. Fig. 6 depicts a crystalline calcium carbonate structure 26 having {2,1,-3,1 } crystallographic indices, and Fig. 7 illustrates a scalenohedral calcite crystal structure 28 with {2, 1 ,-3, 1 } and small faces with the preferred { 1 ,0,- 1,1 } crystallographic indices. Lastly, Fig. 8 illustrates a top partial perspective view of yet another calcium carbonate crystalline structure 30 which has {0,1,-1,2}, {2,1,-3,1 } and { 1,0,-1,0} crystallographic indices. All of the calcium carbonate materials depicted in Figs. 2-8 can be used as the starting crystalline calcium carbonate material in the instant process invention.
Figs. 3, 4, 5 and 7 depict the most common calcite crystals found in nature. It should be understood that none of these calcite crystal structures are in the form of Fig. 1 which is within the scope of the invention. Furthermore, it is believed that the calcite crystal structures of Figs. 2-8 do not perform as well as the Fig. 1 structure because the Figs. 2-8 structures have a high population of calcium atoms at their respective crystal planes (i.e., outer surfaces), thereby resulting in poor performance relative to water hardness cation sequestration. To the contrary, as mentioned previously, the calcite crystal depicted in Fig. 1 has a high population of oxygen atoms and low population of calcium atoms on its respective cleavage planes (i.e., {1,0,-1,1 } crystallographic indices) rendering it a particularly effective seed crystal for water hardness cation (e.g., calcium cations) sequestration. This results in a superior performing detergent composition as the deleterious effects of water hardness on surfactant performance is eliminated or severely inhibited.
The "crystalline" nature of the builder material can be detected by X-ray Diffraction techniques known by those skilled in the art. X-ray diffraction patterns are commonly collected using Cu ^pj^ radiation on an automated powder diffractometer with a nickel filter and a scintillation counter to quantify the diffracted X-ray intensity. The X-ray diffraction diagrams are typically recorded as a pattern of lattice spacings and relative X-ray intensities. In the Powder Diffraction File database by the Joint Committee on Powder Diffraction Standards - International Centre for Diffraction Data, X-ray diffraction diagrams of corresponding preferred builder materials include, but are not limited to, the following numbers: 5-0586 and 17-0763. The actual amount of crystalline calcium carbonate builder used in a detergent composition will vary widely depending upon the particular application. However, typical amounts are from about 0.1% to about 80%, more typically from about 4% to about 60%, and most typically from about 6% to about 40%, by weight of the detergent composition. The median particle size of the builder is preferably from about 0.2 microns to about 20 microns, more preferably from about 0.3 microns to about 15 microns, even more preferably from about 0.4 microns to about 10 microns, and most preferably from about 0.5 microns to about 10 microns. While the crystalline calcium carbonate builder produced by the process performs at any median particle size, it has been found that optimum overall performance can be achieved within the aforementioned median particle size ranges. The phrase "median particle size" as used herein means the particle size as measured by the particle's diameter of a given builder in which 50% by weight of the population has a higher particle size and 50% has a lower particle size. The median particle size is measured at its usage concentration in water (after 10 minutes of exposure to this water solution at a temperature of 50F to 130F) as determined by conventional analytical techniques such as, for example, microscopic determination using a scanning electron microscope (SEM), Coulter Counter or Malvern particle size instruments. In general, the particle size of the builder not at its usage concentration in water can be any convenient size. In addition to the median particle size or in the alternative to it, the crystalline calcium carbonate builder preferably has selected surface area for optimal performance. More specifically, the crystalline calcium carbonate has a surface area of from about 0.01 m^/g to about 12 m^/g, more preferably from about 0.1 rn^/g to about 10 m^/g, even more preferably from about 0.2 m^/g to about 5 m^/g, and most preferably from about 0.2 m^/g to about 4 m^/g. Other suitable surface area ranges include from about 0.1 m^/g to about 4 m^/g and from about 0.01 m^/g to about 4 m^/g. The surface areas can be measured by standard techniques including by nitrogen adsorption using the standard Bruauer, Emmet & Teller (BET) method. A suitable machine for this method is a Carlo Erba Sorpty 1750 instrument operated according to the manufacturer's instructions. The crystalline calcium carbonate builder produced herein also unexpectedly has improved builder performance in that it has a high calcium ion exchange capacity. In that regard, the builder material has a calcium ion exchange capacity, on an anhydrous basis, of at least about 100 mg equivalent of calcium carbonate hardness/gram, more preferably at least about 200 mg, and even more preferably at least about 300 mg, and most preferably from at least about 400 mg, equivalent of calcium carbonate hardness per gram of builder. Additionally, the builder unexpectedly has an improved calcium ion exchange rate. On an anhydrous basis, the builder material has a calcium carbonate hardness exchange rate of at least about 5 ppm, more preferably from about 10 ppm to about 150 ppm, and most preferably from about 20 ppm to about 100 ppm, CaCθ3/minute per 200 ppm of the builder material. A wide variety of test methods can be used to measure the aforementioned properties including the procedure exemplified hereinafter and the procedure disclosed in Corkill et al, U.S. Patent No. 4,605,509 (issued August 12, 1986), the disclosure of which is incorporated herein by reference.
When the builder is used in detergent compositions, it is preferable for the detergent composition to be substantially free of phosphates and phosphonates. As used herein, "substantially free" means has less than 0.05% by weight of a given material. Alternatively, or in addition to the foregoing phosphate limitation, the detergent composition is substantially free of soluble silicates, especially if magnesium cations are part of the water hardness composition in the particular use and the detergent composition does not include an auxiliary builder to sequester such cations. In this regard, superior performance of the detergent composition containing the aforedescribed builder can be achieved if the detergent composition is substantially free of polycarboxylates, polycarboxylic oligomer/polymers and the like. It has also been found that optimal performance can be achieved using such materials in the detergent composition so long as the polycarboxylate is pre-blended with the surfactant before exposure to the crystalline calcium carbonate, either during manufacture of the detergent composition or during use. In another preferred aspect of the builder as used in detergent compositions, the detergent composition is preferably substantially free of potassium salts, or if they are present, are included at very low levels. Specifically, the potassium salts are included at levels of about 0.01% to about 5%, preferably at about 0.01% to about 2% by weight of the detergent composition. Preferably, if sodium sulfate and sodium carbonate are included in the detergent composition in which the builder is contained, they are preferably in a weight ratio of about 1 :50 to about 2: 1, more preferably from about 1 :40 to about 1 :1, most preferably from about 1:20 to about 1: 1 of sodium sulfate to sodium carbonate. While not intending to be bound by theory, it is believed that excessive amounts of sulfate relative to carbonate may interfere with the builder performance of the crystalline calcium carbonate. Preferably, if sodium carbonate is included in the detergent composition in which the builder is contained, it is included preferably in a weight ratio of about 1 : 1 to about 20: 1, more preferably from about 1 : 1 to about 10:1, most preferably from about 1 : 1 to about 5 : 1 of sodium carbonate to crystalline calcium carbonate builder. Additionally or in the alternative, sodium carbonate is present in the detergent composition in an amount of from about 2% to about 80%, more preferably from about 5% to about 70%, and most preferably from about 10% to about 50% by weight of the detergent composition. Adjunct Builders One or more auxiliary builders can be used in conjunction with the builder material produced by the process invention herein to further improve the performance of the compositions into which the builder material is incorporated. For example, the auxiliary builder can be selected from the group consisting of aluminosilicates, crystalline layered silicates, MAP zeolites, citrates, amorphous silicates, polycarboxylates, sodium carbonates and mixtures thereof. Other suitable auxiliary builders are described hereinafter.
Optionally, the compositions into which the builder material made by the present process is incorporated can also comprise a detergent aluminosilicate builder which are referenced as aluminosilicate ion exchange materials and sodium carbonate. The aluminosilicate ion exchange materials used herein as a detergent builder preferably have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced. In that regard, the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble), the disclosure of which is incorporated herein by reference. Preferably, the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit the as high of an exchange rate and capacity as provided by the sodium form. Additionally, the aluminosilicate ion exchange material preferably is in over dried form so as to facilitate production of crisp detergent agglomerates as described herein. The aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders. The term "particle size diameter" as used herein represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM). The preferred particle size diameter of the aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle size diameter is from about 1 microns to about 8 microns.
Preferably, the aluminosilicate ion exchange material has the formula Naz[(A102)z.(Si02)y]xH20 wherein z and y are integers of at least 6, the molar ratio of z to y is from about 1 to about 5 and x is from about 10 to about 264. More preferably, the aluminosilicate has the formula Na12[(Alθ2)i2-(Siθ2)i2]xH20 wherein x is from about 20 to about 30, preferably about 27. These preferred aluminosilicates are available commercially, for example under designations Zeolite A, Zeolite B and Zeolite X. Alternatively, naturally-occurring or synthetically derived aluminosilicate ion exchange materials suitable for use herein can be made as described in Krummel et al, U.S. Patent No. 3,985,669, the disclosure of which is incorporated herein by reference.
The aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaCθ3 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaCθ3 hardness/gram. Additionally, the instant aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca++/gallon minute/-gram/gallon, and more preferably in a range from about 2 grains Ca"H7gallon/minute/-gram/gallon to about 6 grains Ca"H7gallon minute/-gram/gallon.
Detersive Surfactant Preferably, the compositions into which the builder material made according to the instant process invention are incorporated will comprise at least about 1%, preferably from about 1% to about 55%, and most preferably from about 10 to 40%, by weight, of a detersive surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants and mixtures. Nonlimiting examples of surfactants useful herein include the conventional Cj j-Cjg alkyl benzene sulfonates ("LAS") and primary, branched-chain and random Cιo-C2o alkyl sulfates ("AS"), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH3(CH2)x(CHOS0 "M+) CH3 and CH3 (CH2)y(CHOS03 "M+) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the Cio-Cjg alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy sulfates), Cjo-Cjg alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the Cj .j glycerol ethers, the Cjø-Cig alkyl polyglycosides and their corresponding sulfated polyglycosides, and Ci2"Cj g alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C ^-Cj g alkyl ethoxylates ("AE") including the so- called narrow peaked alkyl ethoxylates and C -C 2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines ("sultaines"), C iø-C j g amine oxides, and the like, can also be included in the overall compositions. The C jQ-Ci N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C^-Cj N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C iø-Cj N-(3- methoxypropyl) glucamide. The N-propyl through N-hexyl C^-Cj glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C \Q-C\ soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
It should be understood, however, that certain surfactants are less preferred than others. For example, the C\ i-Cj alkyl benzene sulfonates ("LAS") are less preferred, although they may be included in the compositions herein, in that they may interfere or otherwise act as a poison with respect to the builder material.
Adjunct Detergent Ingredients The builder material made by the present process can include additional detergent ingredients and/or, any number of additional ingredients when incorporated in detergent compositions. These adjunct ingredients include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., incorporated herein by reference. Although preferably avoided or used at very low levels, other builders include the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of the above. Preferred for use herein are the phosphates, carbonates, Cjo-i fatty acids, polycarboxylates, and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, and mixtures thereof (see below).
In comparison with amorphous sodium silicates, crystalline layered sodium silicates exhibit a clearly increased calcium and magnesium ion exchange capacity. In addition, the layered sodium silicates prefer magnesium ions over calcium ions, a feature necessary to insure that substantially all of the "hardness" is removed from the wash water. These crystalline layered sodium silicates, however, are generally more expensive than amorphous silicates as well as other builders. Accordingly, in order to provide an economically feasible laundry detergent, the proportion of crystalline layered sodium silicates used must be determined judiciously.
The crystalline layered sodium silicates suitable for use herein preferably have the formula NaMSix02x+ 1.yH20 wherein M is sodium or hydrogen, x is from about 1.9 to about 4 and y is from about 0 to about 20. More preferably, the crystalline layered sodium silicate has the formula
NaMSi205.yH20 wherein M is sodium or hydrogen, and y is from about 0 to about 20. These and other crystalline layered sodium silicates are discussed in Corkill et al, U.S. Patent No. 4,605,509, previously incorporated herein by reference.
Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, both of which are incorporated herein by reference. Chelating agents are also described in U.S. Patent 4,663,071, Bush et al., from Column 17, line 54 through Column 18, line 68, incorporated herein by reference. Suds modifiers are also optional ingredients and are described in U.S. Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault et al., both incorporated herein by reference.
Suitable smectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al, issued August 9, 1988, Column 6, line 3 through Column 7, line 24, incorporated herein by reference. Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S. Patent 4,663,071, Bush et al, issued May 5, 1987, both incorporated herein by reference.
In order to make the present invention more readily understood, reference is made to the following examples, which are intended to be illustrative only and not intended to be limiting in scope. EXAMPLE I
This Example illustrates the process of the present invention. 2.5 kg/hr of calcite commercially purchased from Omya, Inc., is continuously inputted into the chamber of a Alpine Fluid Bed Jet Mill (Model 100 AFG Fluid Bed Jet Mill commercially available from Hosokawa Micron - Alpine, Germany) having an Air Classifier such as Alpine Air Classifier (Model 50 ATP Air Classifier commercially available from Hosokawa Micron - Alpine, Germany) mounted thereon. The Fluid Bed Jet Mill and Air Classifier apparatus are operated with the valve (El 2) set open, throttle flap valve set to adjust air chamber to slightly positive air pressure, Air Classifier speed set at 8000 rpms, grinding valve set at 5 bar pressure, and the product feed screw set at 35% of maximum. The air pressure of the rinse air in the Fluid Bed Jet Mill are set at 0.5 to 0.6 bars, after which the desired crystalline calcium carbonate builder having a rhombohedral crystalline structure with { 1,0,-1,1 } crystallographic indices is obtained. EXAMPLE II This Example illustrates another embodiment of the process of the present invention. 2.5 kg/hr of calcite commercially purchased from Omya, Inc. is inputted into the drop chamber of a Alpine High Compression Roller Mill (Model 205 Ecoplex Roller Mill commercially available from Hosokawa Micron - Alpine, Germany) wherein the rollers are set at a pressure of about 2500 bars. A slab of the starting calcite is formed which is fed into a Ball Mill to grind the slab into particles having a median particle size of about 3 microns. The resulting particles have a rhombohedral crystalline structure with { 1,0,-1,1 } crystallographic indices, thereby forming the detergent builder.
EXAMPLE III Calcium Sequestration and Rate of Sequestration Test The following illustrates a step-by-step procedure for determining the amount of calcium sequestration and the rate thereof for the crystalline calcium carbonate builder produced by the process invention described herein.
1. Add to 750 ml of 35°C distilled water, sufficient water hardness concentrate to produce 171 ppm of CaC03;
2. Stir and maintain water temperature at 35°C during the experiment;
3. Add 1.0 ml of 8.76% KOH to the water; 4. Add 0.1085 gm of KC1;
5. Add 0.188 gm of Glycine;
6. Stir in 0.15 gm of Na2C03;
7. Adjust pH to 10.0 using 2N HC1 and maintain throughout the test;
8. Stir in 0.15 gm of a builder according the invention and start timer; 9. Collect an alliquot of solution at 30 seconds, quickly filter it through a 0.22 micron filter, quickly acidify it to pH 2.0 - 3.5 and seal the container;
10. Repeat step 9 at 1 minute, 2 minutes, 4 minutes, 8 minutes, and 16 minutes;
11. Analyze all six alliquots for CaCθ3 content via ion selective electrode, titration, quantitative ICP or other appropriate technique; 12. The Sequestration rate in ppm CaC03 sequestered per 200 ppm of builder is
171 minus the CaC03 concentration at one minute;
13. Amount of sequestration (in ppm CaC03 per gram/liter of builder) is 171 minus the CaCθ3 concentration at 16 minutes times five.
For the builder material particle sizes according to the instant invention which are on the low end of the median particle size range, a reference sample is needed which is run without hardness in order to determine how much of the builder passes through the filter. The above calculations should then be corrected to eliminate the contribution of the builder to the apparent calcium concentration.
EXAMPLES IV-VI Several detergent compositions including the detergent builder made in accordance with the process invention and specifically for top-loading washing machines are exemplified below. The base granule is prepared by a conventional spray drying process in which the starting ingredients are formed into a slurry and passed though a spray drying tower having a countercurrent stream of hot air (200-300°C) resulting in the formation of porous granules. The admixed agglomerates are formed from two feed streams of various starting detergent ingredients which are continuously fed, at a rate of 1400 kg/hr, into a Lδdige CB-30 mixer/densifier, one of which comprises a surfactant paste containing surfactant and water and the other stream containing starting dry detergent material containing aluminosilicate, the desired crystalline calcium carbonate builder and sodium carbonate. The rotational speed of the shaft in the Lδdige CB-30 mixer/densifier is about
1400 rpm and the mean residence time is about 1-10 seconds. The contents from the Lδdige CB-30 mixer/densifier are continuously fed into a Lόdige KM-600 mixer/densifier for further agglomeration during which the mean residence time is about 6 minutes. The resulting detergent agglomerates are then fed to a fluid bed dryer and to a fluid bed cooler before being admixed with the spray dried granules. The remaining adjunct detergent ingredients are sprayed on or dry added to the blend of agglomerates and granules. IV V VI
Base Granule
Calcite (rhombohedral, { 1 ,0,- 1,1 })* 3.0 16.0 1 1.0
Aluminosilicate 15.0 2.0 1 1.0
Sodium sulfate 10.0 10.0 19.0 Sodium polyacrylate polymer 3.0 3.0 2.0
Polyethylene Glycol (MW=4000) 2.0 2.0 1.0
C-12-13 ϋnear alkylbenzene sulfonate, Na 6.0 6.0 7.0
C 14.16 secondary alkyl sulfate, Na 3.0 3.0 3.0
C 4_ 15 alkyl ethoxylated sulfate, Na 3.0 3.0 9.0 Sodium silicate - 0.1 0.2
Brightener 24^ 0.3 0.3 0.3
Sodium carbonate 7.0 7.0 25.7
DTPA 1 0.5 0.5 -
Admixed Agglomerates C 14.15 alkyl sulfate, Na 5.0 5.0 -
C j 2- 13 linear alkylbenzene sulfonate, Na 2.0 2.0 -
NaKCa(Cθ3)2 - 7.0 -
Sodium Carbonate 4.0 4.0 -
PolyethyleneGlycol (MW=4000) 1.0 1.0 - Admix 12-15 alkvI ethoxylate (EO = 7) 2.0 2.0 0.5
Perfume 0.3 0.3 1.0
Polyvinylpyrrilidone 0.5 0.5 -
Polyvinylpyridine N-oxide 0.5 0.5 - Polyvinylpyrrolidone-polyvinylimidazole 0.5 0.5 - Distearylamine & Cumene sulfonic acid 2.0 2.0 - Soil Release Polymer 2 0.5 0.5 - Lipolase Lipase (100.000 LU/I)4 0.5 0.5
Termamyl amylase (60 KNU/g)4 0.3 0.3
CAREZYME® cellulase (1000 CEVU/g)4 0.3 0.3
Protease (40mg/g)5 0.5 0.5 0.5
NOBS 3 5.0 5.0
Sodium Percarbonate 12.0 12.0
Polydi ethylsiloxane 0.3 0.3
Miscellaneous (water, etc.) balance balance balance
Total 100 100 100 Made in accordance with Example I 1 Diethylene Triamine Pentaacetic Acid 2Made according to U.S. Patent 5,415,807, issued May 16, 1995 to Gosselink et al
3 Nonanoyloxybenzenesulfonate
4 Purchased from Novo Nordisk A/S 5 Purchased from Genencor
" Purchased from Ciba-Geigy
Having thus described the invention in detail, it will be clear to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.

Claims

WHAT IS CLAIMED IS:
1. A process for producing a detergent builder to be used in a detergent composition characterized by the steps of:
(a) feeding starting crystalline calcium carbonate into an apparatus having an internal chamber and air nozzles directed into said chamber; and
(b) milling said crystalline calcium carbonate in said apparatus by inputting air at a pressure from 1 bar to 50 bar such that said crystalline calcium carbonate is converted to a rhombohedral crystalline structure with { 1,0,-1,1 } crystallographic indices, thereby forming said detergent builder.
2. A process according to claim 1 wherein said pressure is from 1.5 bar to 10 bar.
3. A process according to claims 1-2 wherein the median particle size of said starting crystalline calcium carbonate is from 50 microns to 5000 microns.
4. A process according to claims 1-3 wherein the median particle size of said detergent builder is from 0.2 microns to 20 microns.
5. A process according to claims 1-4 wherein said detergent builder has a surface area of from 0.1 m^ g to 4 m^/g.
6. A process according to claims 1-5 wherein said starting crystalline calcium carbonate is calcite.
7. A process according to claims 1-6 wherein said apparatus includes an air classifier mounted on said chamber such that the said step of milling said crystalline calcium carbonate can be controlled via controlling the extent to which said crystalline calcium carbonate exits said chamber of said apparatus.
8. A process according to claim 7 wherein said air classifier is operated at a speed of from 2000 rpms to 20,000 rpms.
9. A process for producing a detergent builder to be used in a detergent composition characterized by the steps of:
(a) feeding starting crystalline calcium carbonate into an apparatus having a pair of compaction rollers; (b) milling said crystalline calcium carbonate in said apparatus by feeding said crystalline calcium carbonate between said compaction rollers at a pressure from 100 bar to 5000 bar such diat a crystalline calcium carbonate slab is formed, wherein said crystalline calcium carbonate has a rhombohedral crystalline structure with { 1,0,-1,1 } crystallographic indices; and
(c) grinding said slab into particles, thereby forming said detergent builder.
10. A process according to claims 1-9 wherein the median particle size of said starting crystalline calcium carbonate is from 50 microns to 5000 microns.
PCT/US1998/004470 1997-03-11 1998-03-06 A process for making a selected crystalline calcium carbonate builder for use in detergent compositions WO1998040456A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6100232A (en) * 1998-03-02 2000-08-08 The Procter & Gamble Company Process for making a granular detergent composition containing a selected crystalline calcium carbonate builder
SG82677A1 (en) * 1999-02-25 2001-08-21 Mitsubishi Gas Chemical Co Resist stripping agent and process of producing semiconductor devices using the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1795502A1 (en) * 2005-12-12 2007-06-13 SOLVAY (Société Anonyme) Particles of precipitated calcium carbonate, process for making the particles and use of the particles as filler

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2240888A1 (en) * 1973-08-15 1975-03-14 Unilever Nv
FR2296594A1 (en) * 1974-09-27 1976-07-30 Procter & Gamble GRANULES CONTAINING CALCIUM CARBONATE AND DRIED BY SPRAYING

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2240888A1 (en) * 1973-08-15 1975-03-14 Unilever Nv
FR2296594A1 (en) * 1974-09-27 1976-07-30 Procter & Gamble GRANULES CONTAINING CALCIUM CARBONATE AND DRIED BY SPRAYING

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6100232A (en) * 1998-03-02 2000-08-08 The Procter & Gamble Company Process for making a granular detergent composition containing a selected crystalline calcium carbonate builder
SG82677A1 (en) * 1999-02-25 2001-08-21 Mitsubishi Gas Chemical Co Resist stripping agent and process of producing semiconductor devices using the same

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