MXPA99008413A - A selected crystalline calcium carbonate builder for use in detergent compositions - Google Patents

Abstract

A detergent composition containing an inexpensive detergent builder in the form of a selected crystalline calcium carbonate is provided. Specifically, the crystalline calcium carbonate has a substantially rhombohedral crystal structure with {1,0,-1,1} crystallographic indices. The crystalline calcium carbonate can be calcite that has been specially modified to a rhombohedral crystal structure with {1,0,-1,1} indices. The crystalline calcium carbonate of the present invention is extremely inexpensive because it can be readily formed from inexpensive naturally occurring calcite, and it performs well even when used at large median particle sizes.

Description

A SELF-DETERGENT IMPROVEMENT BASED ON CALCIUM CARBONATE TO BE USED IN COMPOSITIONS DETERGENTS FIELD OF THE INVENTION The invention is directed to a cheap builder material for use in detergent compositions. More particularly, the invention provides a select material based on crystalline calcium carbonate having a substantially rhombohedral structure with crystallographic indices. { 1, 0-1, 1} . This truly inexpensive builder material is especially suitable for use in detergent compositions used in fabric washing, bleaching, automatic or manual dishwashing, hard surface cleaning or any other application requiring the use of a detergency builder material. Remove the hardness of the water.

BACKGROUND OF THE INVENTION It is common practice for formulators of cleaning compositions to include, in addition to the active cleaning material, a builder to remove hardness cations (eg, calcium and magnesium cations) from the wash solution which otherwise This would reduce the efficiency of the active cleaning material (for example, surfactant) and make certain spots 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 detergency builder sequesters or "traps" the hardness cations so as to prevent them from preventing the cleaning action of the anionic surfactant in the detergent composition. As is well known, water-soluble phosphate-based materials have been widely used as builders. However, for a variety of reasons, including the eutrophication of surface waters that is believed to be caused by phosphates, there has been a desire to use other builders in many geographic areas. Other known detergency builders include water soluble builder salts, such as sodium carbonate, which can form precipitates with the hardness cations found in the wash solutions. Unfortunately, the use of such enhancers by themselves does not reduce the level of hardness cations at a sufficiently fast rate. For practical purposes, the acceptable level is not reached within the time limit required for the desired application, for example within 10 to 12 minutes for fabric washing operations in North America and Japan.

In addition, some of these water-soluble builder salts, while attractive from a cost standpoint, have several disadvantages, among which is the tendency of the precipitates formed in aqueous wash solutions (for example carbonate unsoluble calcium) to be deposited on fabrics or other items to be cleaned. A sustained solution to this problem has been to include a water-insoluble material that would act as a "seed crystal" for the precipitate (ie, calcium carbonate). Of the various materials suggested for such use, calcite with very small particle size has been the most popular. However, the inclusion of calcite in the detergent compositions has been problematic due to the sensitivity of the reaction product hardness / anion cation (eg calcium / carbonate) to be poisoned by materials (eg polyacrylates or certain surfactants). anionic) which may be present in the washing solution. Without being limited by theory, the problem of poisoning prevents the reaction product from forming and inhibits crystallization on the seed crystal. Consequently, calcite typically has to be produced in a very small particle size to properly have a larger surface area which is more difficult to poison. Nevertheless, this causes the very small calcite particle to acquire dust characteristics and be difficult to handle. Furthermore, the particle sizes are so small (having at least 15 m2 / g or more of surface area) that the manufacture of such calcite particles is extremely expensive. For example, the production of such small particles of calcite may require a controlled "growth" procedure that is extremely expensive.

Another problem associated with the use of calcite as a "seed crystal" for poisons and precipitates in wash solutions is the difficulty experienced in properly dispersing the calcite in the wash solution so that it does not settle on fabrics or fabrics. Items that are undergoing cleaning operations. Such deposits or residues are extremely undesirable for most cleaning operations, especially in fabric laundry and dishwashing situations. The prior art is replete with suggestions for dealing with the handling and dispersibility problems associated with calcite. A previously proposed method to handle calcite is to incorporate it into a suspension, but this involves high storage and transportation costs. Another proposed option involves granulating the calcite with binding and dispersing agents to ensure adequate dispersion in the wash solution. However, this option has also been difficult to implement effectively in current detergent compositions because the calcite granules have low mechanical strength which continues to make it difficult to handle and process. Additionally, the effective binding and dispersing agents for calcite have not yet been discovered. Specifically, most of the binding and dispersing agents proposed by the prior art are by themselves poisons that reduce the "seed activity" of calcite. Accordingly, it is desired to have an improved inexpensive builder material that overcomes the aforementioned limitations and is easy to handle, easily dispersible in wash solutions and exhibits improved builder performance. Various additional builder materials and combinations thereof have also been used in various cleaning compositions for fabric laundry operations and dishwashing operations. As an example, certain mineral clays have been used to adsorb hardness cations, especially in fabric laundry operations. In addition, zeolites (or aluminosilicates) have been suggested to be used in various cleaning situations. Various aluminosilicates have also been used as builders. For example, ion exchange materials of water-insoluble aluminosilicates have been widely used in industrial detergent compositions. While such builder materials are completely effective and useful, they account for a significant portion of the costs in most any of the fully formulated detergent or cleaning compositions. In addition, such detergency builders have a limited ability to sequester calcium and therefore, are not very effective in hard water. Therefore, it would be desirable to have a builder material having an equal or better performance than the aforementioned builders and also important, that it be less expensive. Accordingly, in spite of the aforementioned descriptions, there still remains a need in the art for cheap builder material to be used in detergent compositions exhibiting superior performance and which is less expensive to manufacture in that it does not require a size of very small particle. There is also a need in the art for a builder material as such that it is easy to handle (ie not "dusty"), easy to process and easily dispersed in wash solutions.

TECHNICAL BACKGROUND The following references indicate builders for various detergent compositions: Atkinson et al., U.S. Pat. 4,900,466 (Lever); Houghton, WO 93/22411 (Lever); Alian et al., EP 518 576 A2; (Lever); Zolotoochin, Patent E.U.A. No. 5,219,541 (Tenneco Minerals Company); Gamer-Gray et al., Patent E.U.A. No. 4,966,606 (Lever); Davies et al., U.S. Patent. No. 4,908,159 (Lever); Carter and others, Patent E.U.A. No. 4.71 1, 740 (Lever); Greene, Patent E.U.A. No. 4,473,485 (Lever); Davies et al., Patent E.U.A. No. 4,407,722 (Lever); Jones et al., Patent E.U.A. No. 4,352,678 (Lever); Clarke et al., Patent E.U.A. No. 4,348,293 (Lever); Clarke et al., Patent E.U.A. No. 4,196,093 (Lever); Benjamín et al., Patent E.U.A. No. 4,171, 291 (Procter &Gamble); Kowalchuk, Patent E.U.A. No. 4,162,994 (Lever); Davies et al., Patent E.U.A. No. 4,076,653 (Lever); Davies et al., Patent E.U.A. No. 4,051,054 (Lever), Collier, Patent E.U.A. No. 4,049,586 (Procter &Gamble); Benson et al., Patent E.U.A. No. 4,040,988 (Procter &Gamble); Cherney, Patent E.U.A. No. 4,035,257 (Procter &Gamble); Curtis, Patent E.U.A. No. 4,022,702 (Lever); Child et al., Patent E.U.A. No. 4,013,578 (Lever); Lamberti, Patent E.U.A. No. 3,997,692 (Lever); Cherney, Patent E.U.A. No. 3,992,314 (Procter &Gamble); Child, Patent E.U.A. No. 3,979,314 (Lever); Davies et al., Patent E.U.A. No. 3,957,695 (Lever); Lamberti, Patent E.U.A. No. 3,954,649 (Lever); Sagel et al., Patent E.U.A. No. 3,932,316 (Procter &Gamble); Lobunez et al., Patent E.U.A. No. 3,981, 686 (Intermountain Research and Development Corp.); Mallow et al., Patent E.U.A. No. 4,828,620 (Southwest Research Institute); Bjorkiund 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 CaCO3 Dissolution during Scanning Force Microscopy," Langmuir, p. 4599-4603, 12 (1996); and Nancollas et al., "The Crystallization of Calcium Carbonate" Journal of Colloid and interface Science, Vol. 37, No. 7, pp. 824-829 (Dec. 1971).

BRIEF DESCRIPTION OF THE INVENTION The present invention meets the aforementioned needs in the art by providing a builder in the form of a calcium carbonate which is in a specially selected crystalline form. Specifically, crystalline calcium carbonate has a substantially rhombohedral crystal structure with crystallographic indices. { 1, 0-1, 1]. The crystalline calcium carbonate can be calcite that has been specially modified towards the rhombohedral crystal structure with indexes. { 1, 0-1, 1]. The crystalline calcium carbonate of the present invention is extremely inexpensive because it can be easily formed from cheap calcite that occurs in nature and has an adequate yield even when used in moderately large particle sizes. In accordance with one aspect of the invention, a detergent composition is provided. The detergent composition comprises: (a) an effective amount of crystalline calcium carbonate, the crystalline calcium carbonate having a substantially rhombohedral crystal structure with crystallographic indices. { 1, 0-1, 1]; and (b) at least about 1% by weight of a detersive surfactant. In a preferred aspect of the invention, a detergent composition having especially preferred characteristics is provided. This detergent composition comprises: (a) from 0.1% to 80% in crystalline calcium carbonate, the crystalline calcium carbonate having a substantially rhombohedral crystalline structure with crystallographic indices. { 1, 0-1, 1] and a surface area of 0.01 m2 / g at approximately 4 m2 / g; (b) at least about 1% by weight of a detersive surfactant; and (c) from 1% to about 80% by weight of sodium carbonate, wherein the sodium carbonate and the crystalline calcium carbonate are in a weight ratio of from about 1: 5 to about 5: 1. This detergent composition is substantially free of phosphates. The invention also provides a method for laundry of soiled fabrics consisting of the steps of contacting the soiled fabrics in an aqueous solution containing an effective amount of a detergent composition as described in the present invention. In addition, a method for cleaning surfaces comprising the steps of contacting the surfaces with an aqueous solution containing an effective amount of a detergent composition such as that described in the present invention is provided. Any of the detergent compositions described in the present invention may be in the form of a laundry bar. Even in another aspect of the method of the invention, a method is provided for the removal of calcium hardness ions from the aqueous solution. This method consists of the steps of dispersing crystalline calcium carbonate having a substantially rhombohedral crystal structure with crystallographic indices. { 1, 0-1, 1]. in the aqueous solution, crystallizing the calcium hardness ions on the crystalline calcium carbonate resulting in the removal of the calcium hardness ions from the aqueous solution. Accordingly, it is an object of the invention to provide a detergent composition containing a cheap builder material exhibiting superior performance and which is less expensive to manufacture in the sense that it does not require a very small particle size. It is also an object of the invention to provide a builder as such that is easy to handle (ie is not "dusty"), easy to process and easily dispersed in wash solutions. These and other objects, features and attendant advantages of the present invention will become apparent to those skilled in the art upon reading the following detailed description and preferred embodiments and appended claims. All percentages, ratios and proportions used in the present invention are by weight (anhydrous base) unless otherwise indicated. All documents including patents and publications cited in the present invention are incorporated therein for reference.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates a crystalline calcium carbonate structure according to the invention; and Figures 2-8 illustrate the structures of crystalline calcium carbonate commonly found in nature (Figure 8 is a partial perspective view showing only the upper portion of the crystal), of which all are outside the field of the invention.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES The detergent composition of the invention can be used in a variety of applications including, but not limited to, fabric washing, fabric or surface bleaching, automatic or manual dishwashing, hard surface cleaning and any other application that requires the use of a builder material to remove the hardness of the water. As used herein, the phrase "effective amount" means that the level of builder material in the composition is sufficient to sequester an appropriate amount of hardness in the wash solution such that the detersive surfactant does not be completely inhibited. As used herein, the word "crystalline" means a mixture or material that has an internal arrangement that repeats itself regularly (ie, "crystal lattice") of its outer flat atoms and faces. As used herein, the phrase "having a substantially rhombohedral crystal structure" means a crystal having the shape of a parallelogram and having no right angles (eg, as shown in Figure 1). As used herein, "crystallographic indices". { 1, 0, -1, 1} refers to a set of crystal planes in a hexagonal coordinated system which defines a selected crystalline structure (also referred to as "Miller indices" for a hexagonal coordinated system). As used herein, the phrase "crystalline calcium carbonate" refers to the chemical entity calcium carbonate, in crystalline form, whose most common form is known as "calcite". Also see the normal texts on all these subjects, such as Blackbum and others, Principies of Mineralogy, 2a. Ed., Pp. 21-51 (1994) and Klein et al., Manual of Mineralogy, p. 405 et seq (1977).

DETERGENT IMPROVEMENT BASED ON CALCIUM CARBONATE CRYSTALLINE The crystalline calcium carbonate used in the detergent composition of the present invention has a substantially rhombohedral crystal structure 10 as shown in Figure 1. This crystalline calcium carbonate is defined by the crystallographic or Miller. { 1, 0, -1, 1} . It has surprisingly been found that by judiciously selecting a crystalline calcium carbonate of such a crystalline configuration, a superior builder performance (ie, water hardness removal) can be achieved when it is used in typical detergent compositions for wash soiled clothes The average particle size of this crystalline calcium carbonate as described hereinabove is not required to be in too small a range (eg, less than about 2 microns with a surface area of at least 15 microns). m2 / g). While not intended to be limited by theory, it is believed that the external surfaces, for example 12, 14 and 16 shown in Figure 1, have a significantly high population of oxygen atoms which leads to the complete crystalline structure to have more affinity towards the calcium cations which are the predominant source of water hardness. Those skilled in the art will appreciate that this is a crystal having crystallographic indices. { 1, 0, -1, 1} . and their crystal faces are defined by them. In contrast, Figures 2-8 define crystal structures of crystalline calcium carbonate or calcite that do not have a substantially rhombohedral crystal structure with crystallographic indices. { 1, 0, -1, 1} . In addition, all the faces of the crystal or rupture planes of the calcite crystal structures shown in Figures 2-8 can have a much larger population of calcium atoms, thus creating a strongly positive charge on the outer surfaces of these crystals. This, as will be appreciated by those skilled in the art, causes crystalline structures to be less effective in sequestering water hardness cations. Specifically, Figure 2 shows a crystalline calcium carbonate having a rhombohedral structure 18, but with crystallographic indices. { 1, 0, -1, 2} . Figure 3 illustrates crystalline calcium carbonate or calcite in a cubic crystalline structure having crystallographic indices . { 0.2, -2.1} . Figure 4 shows a hexagonal crystal structure 22 with crystallographic indices. { 1, 0, -1, 0} Y . { 0,0,0,1} , while Figure 5 shows a prismatic structure 24 with crystallographic indices. { 1, 0, -1, 0} Y . { 0.1, -1, 2 } . Figure 6 shows a crystalline calcium carbonate 26 having crystallographic indices. { 2.1, -3.1} and Figure 7 illustrates a scalenohedric calcite crystal structure 28 with. { 2.1, -3.1} and small faces with crystallographic indices. { 1, 0, -1, 0} preferred. Finally, Figure 8 illustrates a top partial perspective view of even another crystal structure of calcium carbonate 30 which has crystallographic indices. { 1, 0, -1, 2} ,. { 2.1, -3.1} Y . { 1, 0, -1, 0} . Figures 3, 4, 5 and 7 show the most common calcite crystals found in nature. It should be understood that none of these crystalline calcite structures is in the form of Figure 1 which is within the scope of the invention. In addition, it is believed that the crystallite structures of calcite of Figures 2-8 do not yield the same as the structure of Figure 1 because the structures of Figures 2-8 have a high population of calcium atoms in their crystal planes. respective (ie, external surfaces), thus resulting in a low yield in relation to the sequestration of water hardness cations. On the contrary, as mentioned previously, the calcite crystal shown in Figure 1 has a high population of oxygen atoms and a low population of calcium atoms on their respective rupture planes (ie, crystallographic indices. 1, 0, -1, 1.}.) Making it a seed crystal particularly effective for the sequestration of hardness cations from water (eg calcium cations). This results in a detergent composition of superior performance since the detrimental effect of water hardness on the performance of the surfactant is severely suppressed or inhibited. The "crystalline" nature of the builder material can be detected by X-ray diffraction techniques known to those skilled in the art. X-ray diffraction patterns are commonly collected using CuKaifa radiation in an automated powder diffractometer with a nickel filter and a flash counter to quantify the intensity of the diffracted X-rays. X-ray diffraction patterns are typically recorded as a pattern of separation of the crystal structure and the relative intensities of X-rays. In the Powder Diffraction File database by the Joint Committee on Powder Diffraction Standards-International Center for Diffraction Data, X-ray diffraction diagrams of the corresponding preferred builder materials include, but are not limited to, the following numbers: 5-0586 and 17-0763. The normal amount of crystalline calcium carbonate builder based on the detergent composition of the invention will vary widely depending on the particular application. However, typical amounts range from 0.1% to 80%, more typically from 4% about 60%, and more typically still from 6% to about 40% by weight of the detergent composition. The average particle size of the builder preferably based on 0.2 microns to 20 microns, more preferably 0.3 microns to about 15 microns, and even more preferred from 0.4 microns to 10 microns, and more preferably 0.5 microns to about 10 microwaves While the crystalline calcium carbonate used in the detergent composition in the present invention performs well in an average particle size, it has been found that the optimum overall yield can be achieved within the aforementioned average particle size ranges. The phrase "average particle size" as used herein, means the particle size as measured by the diameter of the particles of a given builder in which 50% by weight of the population has a larger particle size and 50% has a smaller particle size . The average particle size is measured at its normal concentration of use in water (after 10 minutes of exposure to this aqueous solution at a temperature of 10 ° C to 54.4 ° C) as determined by conventional analytical techniques, such as such as, for example, microscopic determination using an electron scanning microscope (MBE), Coulter counter or Malvern particle size instruments. In general, the particle size of the builder that is not in its water usage concentration can be any convenient size. In addition to the average particle size or in the alternative thereto, the crystalline carbonate-based builder preferably has a surface area selected for optimum performance. More specifically, crystalline calcium carbonate has a surface area of 0.01 m2 / ga about 12m2 / g, more preferably 0.1 m2 / ga about 10 m2 / g, even more preferably 0.2 m2 / g at 5 m2 / g. , and still more preferred from 0.2 m2 / g to approximately 4 m2 / g. Other appropriate surface area ranges include from about 0.1 m2 / g to about 4 m2 / g and from about 0.01 m2 / g to about 4 m2 / g. Surface areas can be measured by standard techniques including by nitrogen absorption using the Bruauer standard method, Emmet &; Teller (BET). An appropriate machine for this method is a Cario Erba Sorpty 1750 instrument operated in accordance with the manufacturer's instructions. The crystalline calcium carbonate builder based on the detergent composition herein also, unexpectedly, has improved builder performance in the sense that it has a high calcium ion exchange capacity. In this sense, the builder material has a calcium ion exchange capacity, in an anhydrous base, of at least 100 mg calcium carbonate hardness equivalent / gram, more preferably at least 200 mg, and even more preferred at least 300 mg, and still more preferred at least 400 mg, calcium carbonate hardness equivalents per gram of detergency builder.

Additionally, unexpectedly, the builder has an improved calcium ion exchange rate. On an anhydrous basis, the builder material has a calcium carbonate hardness exchange rate of at least 5 ppm, preferably from 10 ppm to 150 ppm, and more preferred from 20 ppm to 100 ppm of CaCO3 / minute. per 200 ppm of the builder material. A wide variety of test methods can be used to measure the aforementioned properties including the method exemplified hereinbefore and the procedure described in US Patent E.U.A. No. 4,605,509 (issued August 12, 1986), the description of which is incorporated herein by reference. In a preferred embodiment of the invention, the detergent composition is substantially free of phosphates and phosphonates. As used herein, "substantially free" means that it has less than 0.05% by weight of a given material. Alternatively, or in addition to the above limitation to phosphates, the detergent composition is substantially free of soluble silicates, especially if the magnesium cations are part of the water hardness composition in the particular use and the detergent composition of the invention is not It includes an auxiliary detergency builder to sequester said cations. In this regard, a superior performance of the detergent composition containing the detergent builder described above can be achieved if the detergent composition is substantially free of polycarboxylates, polycarboxylic oligomers / polymers or the like. It has been found that optimum performance can be achieved by using such materials in the detergent composition as long as the polycarboxylate is pre-mixed with the surfactant before being exposed to the crystalline calcium carbonate, either during the manufacture of the detergent composition or during Its use. In another preferred aspect of the invention, the detergent composition is substantially free of potassium salts, or if these are present, they are included in very low levels. Specifically, the potassium salts are included at levels from 0.01% to 5%, preferably from 0.01% to 2% by weight of the detergent composition. Preferably, if sodium sulfate and sodium carbonate are included in the detergent composition, these are preferably in a weight ratio of from about 1: 50 to about 2: 1, preferably from 1: 40 to 1: 1, more preferred from 1: 20 to 1: 1 of sodium sulfate to sodium carbonate. While not intended to be limited by theory, it is believed that excessive amounts of sulfate relative to carbonate may interfere with the performance of the crystalline calcium carbonate builder. Preferably, if sodium carbonate is included in the detergent composition, it is preferably included in a weight ratio of from about 1: 1 to about 20: 1, more preferably from 1: 1 to about 10: 1, more preferred close to 1: 1 to about 5: 1 of sodium carbonate to detergent builder based on crystalline calcium carbonate. Additionally or alternatively, sodium carbonate is present in the detergent composition in an amount of 2% to 80%, preferably 5% to 70%, and more preferably 10% to 50% by weight of the detergent composition. The crystalline calcium carbonate according to the invention (Figure 1) can be made in a variety of ways so long as the resulting crystal has a substantially rhombohedral crystal structure, with crystallographic indices. { 1, 0, -1, 1} . Preferably, the starting ingredient is crystalline calcium carbonate which does not have the aforementioned crystalline 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 that shown in Figure 5 can be extracted or purchased commercially and subjected to to the method described hereinafter. As used herein, the word "grinding" means to grind, grind or otherwise affect the physical structure of crystalline calcium carbonate. In a preferred embodiment, the method involves first feeding the crystalline calcium carbonate starting in an apparatus having an internal chamber and air nozzles directed towards the chamber. A convenient apparatus in which such grinding may occur is a Alpine Fluidized Bed Jet Mill (Bed Jet Mill) Fluidized model 100 AFG commercially available at Hosokawa Micron-Alpine, Germany). Other suitable apparatuses are commercially available in Hosokawa Micron-Alpine, Germany and sold under the trade names Table Top Roller Mill, Aeroplex, Ecoplex and Turboplex. In this step of the process, the starting crystalline calcium carbonate is milled in such an apparatus by introducing it and grinding it with air at a pressure between 1 bar and about 50 bar, preferably from 1.5 bar to about 10 bar, and more preferably 2.5 bar. at 5 bar. In this manner, the starting crystalline calcium carbonate is converted to a rhombohedral crystal structure with crystallographic indices. { 1, 0, -1, 1} , thus forming the detergency builder. This selected grinding process step in which the starting ingredient (eg calcite) is milled involves crushing and / or milling the starting crystalline calcium carbonate such that it is cut to form the aforementioned crystalline calcite structure (Figure 1 ). While it is not intended to be limited by theory, it is believed that the crystallographic indices. { 1, 0, -1, 1} define "low voltage" planes of larger calcite that occurs naturally together with which breakage can occur if it is milled with the selected procedure parameters. One or more auxiliary detergency builders may be used in conjunction with the crystalline calcium carbonate described herein to further improve the performance of the detergent composition described herein. For example, the auxiliary detergency builder can be selected from the group consisting of aluminosilicates, layered crystalline silicates, MAP zeolites, citrates, polycarboxylates, sodium carbonates, and mixtures thereof. Other suitable auxiliary detergency builders are described hereinafter.

DETERGENT COMPOSITIONS The detergent compositions of the invention may contain all kinds of organic water-soluble detergent compounds, as long as the builder material is compatible with such materials. In addition to a detersive surfactant, at least one suitable adjunct detergent ingredient is included in the detergent composition. The adjunct detergent ingredient is preferably selected from the group consisting of auxiliary detergency builders, enzymes, bleaching agents, bleach activators, foam suppressants, soil release agents, brighteners, perfumes, hydrotropes, dyes, pigments, dispersing polymeric agents , pH controlling agents, chelators, processing aids, crystallization aids and mixtures thereof. The following list of detergent ingredients and mixtures thereof which may be used in the compositions herein is representative of the detergent ingredients, but is not intended to be limiting.

DETERSIVE SURGICAL AGENT Preferably, the detergent compositions herein consist of at least 1%, preferably from 1% to 55%, and more preferably from 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. Non-limiting examples of surfactants useful herein include C, -? - C-? 8 ("LAS") alkylbenzene sulphonates and primary C10-C or branched chain randomized ("AS") alkyl sulfates, (2) , 3) secondary C-io-C-iß alkyl sulphates of the formula CH3 (CH2)? (CHOS? 3"M +) CH3 and CH3 (CH2) and (CHOS? 3" M +) CH2CH3 where xy (y + l ) are integers of at least 7, preferably at least 9, and M is a solubilization cation in water, especially sodium, unsaturated sulfates such as oleyl sulfate, C10-C18 alkyl alkoxy sulfates ("AEXS"; especially ethoxysulfates EO 1-7), alkyl alkoxy carboxylates of C-io-C-is (especially the ethoxycarboxylates EO 1-5), the glycerol ethers of C-? o-C18, the alkyl polyglucosides of C-io-C-is and their corresponding sulphated polyglucosides and the fatty acid esters of C-? 2-C ? 8 alpha-sulfonated. If desired, conventional non-ionic and amphoteric surfactants such as the C 2 -C 8 alkylethoxylates ("AE") including the so-called narrow peak alkyl ethoxylates and the C 6 -C 12 alkyl phenoxyalkoxylates (especially mixed ethoxylates and ethoxy / propoxy), C-? 2-C? 8 betaines and sulfobetaines ("sultaines"), C0-C? 8 amine oxides and the like can also be included in the total compositions. The N-alkyl polyhydroxy fatty acid amides of C-C-is can also be used. Typical examples include the N-methylglucamides of C? O-C- | 8. See WO 9,206,154. Other surfactants derived from sugar include the polyhydroxy fatty acid amides of N-alkoxy, such as N- (3-methoxypropyl) glucamide of C? O-C-? 8. The glucamides of N-propyl to N-hexyl of C? O-C? S can also be used for low foam formation. Conventional C10-C20 soaps can also be used. If a high foaming is desired, the branched-chain C10-Ci6 soaps can be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in the standard books. It should be understood, however, that certain surfactants are less preferred than others. For example, Cn-C-iß alkylbenzenesulfonates ("LAS") and sugar-based surfactants are less preferred, although these may be included in the compositions herein, as these may interfere or otherwise act as a poison with respect to the builder material.

AUXILIARY INGREDIENTS Auxiliary detergent-based detergency builder Auxiliary builders can optionally be included with the builder material described above in the compositions herein to further assist in controlling the mineral hardness in the wash solutions. Inorganic as well as organic builders can be used.

In addition, crystalline as well as amorphous builder materials can be used. Builders are typically used in fabric washing compositions to aid in the removal of particulate stains. The level of builder can vary widely depending on the final use of the composition and its desired physical form. When present, the compositions will typically consist of at least 1% builder. Granulated formulations typically consist of 10% to 80%, more typically 15% to 50% by weight of the builder. However, the major or minor levels of detergency builder are not excluded. Phosphorus-containing or inorganic builders include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by polymeric tripolyphosphates, pyrophosphates and metaphosphates of vitreous appearance), phosphonates, phytic acid, silicates , carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. However, non-phosphate builders are required in some locations. Importantly, the compositions herein work surprisingly well even in the presence of so-called "weak" enhancers (as compared to phosphates) such as citrate, or in the so-called "reduced detergency improvement" situation that may occur with zeolite or with detergents based on layered silicate. Preferably, as mentioned, phosphate-based builders should be excluded, but if they are used, they are present at levels less than 10% of the composition. Laminated silicates and sodium carbonate are the most preferred co-builders for detergency builder based on the present invention. Examples of silicate-based detergency builders are alkali metal silicates, particul those having a Si 2: Na 2 O ratio in the range 1.6: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described. in the USA patent 4,664,839, issued May 12, 1987 for H.P. Rieck NaSKS-6 is the commercial name of a crystalline layered silicate sold by Hoechst (commonly abbreviated here as "SKS-6"). Unlike zeolite-based builders, the NaSKS-6 silicate does not contain aluminum. The NaSKS-6 has the form of a laye-Na2SiO5 morphology of stratified silicate. This can be prepared by methods such as those described in German documents DE-A-3, 417,649 and DE-A-3,742,043. SKS-6 is a highly preferred stratified silicate to be used herein, but other such layered silicates, such as those having the general formula NaMSi? O2? +? and H O where M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 may be used herein. Some other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-1 1, such as the alpha, beta and gamma forms. As indicated above, deIta-Na2SiOs (NaSKS-6 form) is most preferred to be used herein. Examples of carbonate-based builders are the alkali metal and alkaline earth metal carbonates described in German Patent Application no. 2,321, 001 published November 15, 1973. As mentioned previously, aluminosilicate-based builders are auxiliary builders useful in the present invention. Aluminosilicate-based builders are of great importance in most heavy duty granular detergent compositions sold today, and can also be a significant detergency builder ingredient in liquid detergent formulations. The aluminosilicate-based detergency builders include those having the empirical formula: Mz [(AIO2) z- (SiO2) and] xH2O where z and e are integers of at least 6, the molar ratio of zay is in the range of 1.0 to about 0.5, and x is an integer from 15 to about 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in their structure and can be aluminosilicates that occur in nature or that are obtained synthetically. A method for producing aluminosilicate ion exchange materials is described in US Patent E.U.A. 3,985,669, Krummel, et al., Issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein can be obtained under the names Zeolite A. Zeolite P (B), Zeolite MAP and Zeolite X In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na12 [(AIO2) i2- (Si? 2) -i2] xH2O wherein x is from 20 to about 30, especially from about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used here. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. As mentioned, the use of organic builders in relation to the wide variety of polycarboxylate compounds should be minimal, and preferably should not be used. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.

The polycarboxylate-based builder can generally be added to the composition in acid form, but can also be added in the form of a neutral salt. When used in saline, alkali metal salts, such as sodium, potassium and lithium or alkanolammonium salts, are preferred. Polycarboxylate builders include a variety of useful material categories. An important category of detergents based on polycarboxylate includes ether polycarboxylates, including oxydisuccinate, as described in Berg, Patent E.U.A. 3,128,287, issued April 7, 1964 and Lamberti et al., Patent E.U.A. 3,635,830, issued January 18, 1972. See also "TMS / TDS" builders of the U.S. Patent. No. 4,663,071, issued to Bush et al., May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds such as those described in US Patents. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other similar detergency builders include ether hydroxypolycarboxylates, maleic anhydride copolymers with ethylene or vinyl methyl ether, 1,3-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the various alkali metal salts, ammonium salts and substituted ammonium of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof. Citrate-based builders, for example citric acid and soluble salts thereof (particularly the sodium salt), are builders based on polycarboxylates which are suitable for availability from renewable sources and their capacity for biodegradation . The citrates can also be used in granular compositions, especially in combination with zeolite and / or builders based on layered silicate. Oxidic isnes are also especially useful in such compositions and combinations. The 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds described in the US Pat. 4,566,984, for Bush, issued January 28, 1986, are also suitable in the detergent compositions of the present invention. Useful succinic acid builders include the alkyl and alkenyl succinic acids of C5-C2o and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate-based builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate and the like. Lauryl succinates are the preferred builders of this group and are described in the European Patent Application 86200690. 5 / 0,200,263, published November 5, 1986. Other similar polycarboxylates are described in the U.S. Patent. 4,144,226, for Crutchfield et al., Issued March 13, 1979 and U.S. Patent. 3,308,067, for Diehl, issued March 7, 1967. See also Patent E.U.A. 3,723,322, for Diehl. Fatty acids, for example C 12 -C 8 monocarboxylic acids, can also be incorporated into the compositions alone or in combination with the aforementioned builders, especially builders based on citrate and / or succinate, to supply a Additional builder activity. Such use of the fatty acids will generally result in a decrease in the foam, which should be considered by the formulator. In situations where phosphorus-based detergency builders are used, and especially in the formulation of soap bars used for manual washing operations, the various alkali metal phosphates may be used such as the well-known sodium tripolyphosphates, pyrophosphate sodium and sodium orthophosphate at low levels. The phosphonate-based detergency builders, such as ethan-1-hydroxy-1,1-diphosphonate and other known phosphonates (see for example US Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used at low levels, although the removal of such materials in the composition is preferred.

ENZYMES Enzymes can be included in the formulations of the present invention for a variety of fabric washing purposes, including, for example, the removal of protein-based, carbohydrate-based or triglyceride-based stains and to prevent the transfer of migratory dye and for the restoration of fabrics. Additional enzymes to be incorporated include cellulases, proteases, amylases, lipases and peroxidases, as well as mixtures thereof. Other types of enzymes can also be included. These can be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. However, their choice depends on several factors such as optimal levels of pH activity and / or stability, thermostability, stability versus active detergents, builders and their potential to create bad odors during use. In this sense, bacterial or fungal enzymes, such as bacterial amylases and proteases, are preferred. Normally the enzymes are incorporated at levels sufficient to supply approximately up to 5 mg by weight, very typically 0.01 mg to 3 mg, of active enzyme per gram of the composition. In other words, the compositions of the present invention will typically consist of 0. 001% to 5%, preferably 0.01% -1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to supply from 0. 005 to 0.1 Anson units (AU) of activity per gram of composition. Suitable cellulases for the present invention include both bacterial and fungal cellulose. Preferably, these will have an optimum pH between 5 and 9.5. Suitable celluloses are described in the patent E.U.A. 4,435,307, Barbesgoard et al., Issued March 6, 1984, which describes fungal cellulase produced by Humicola insolens and Humicola strain DSM 1800 or a fungus that produces cellulase 212 belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusc. (Dolabella Auricular Solander), suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. In addition, cellulases especially suitable for use in the present invention are described in WO 92-13057 (Procter &Gamble). More preferred, the cellulases used in the detergent compositions herein are purchased commercially from NOVO Industries A / S under the tradenames CAREZYME® and CELLUZYME®.

Suitable examples of proteases are the subtilisins that are obtained from particular strains of B.subtiiis and B.licheniforms. Other suitable proteases are obtained from a Bacillus strain, having a maximum activity throughout the pH range of 8 to 12, developed and sold by Novo Industries A / S under the trademark name ESPERASE. The preparation of this enzyme and analogous enzymes are described in the Report Descriptive of British Patent No. 1, 243,784 of Novo. Suitable proteolytic enzymes for removing protein-based stains that are commercially available include those sold under the brand names ALCALASE and SAVINASE by Novo Industries A / S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands). Other proteases include Protease A (see European Patent Application Serial No. 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed on April 28, 1987 and the Application of European Patent 130,756, to Bott et al., published January 9, 1985) Amylases include, for example, α-amylases described in British Patent Specification No. 1, 296,839 (Novo), RAPIDASE, International Bio -Synthetics, Inc. and TERMAMYL, Novo Industries. Lipase enzymes suitable for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, as described in British Patent No. 1, 372,034. See also lipases in Japanese Patent Application No. 53-20487, open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co.

Ltd., Nagoya, Japan, under the brand name Lipase P "Amano", hereinafter referred to as "Amano-P". Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, for example Chromobacter viscosum var.lipoliticum NRRLB 3673, commercially available in Toyo Jozo Co., Tagata, Japan; and also Chromobacter viscosum lipases from U.S. Biochemicals Corp., E.U.A. and Disoynth Co., The Countries Low, and lipases ex Pseudomonas gladioli. The LIPOLASE enzyme obtained from Humicola lanuginosa and commercially available from Novo (see also EPO document 341, 947) is a preferred lipase to be used in the present invention. Peroxidase enzymes are used in combination with oxygen sources, eg, percarbonate, perborate, persulfate, hydrogen peroxide, etc. These are used for "bleaching in solution", that is, to avoid the transfer of dyes or pigments removed from the substrates during washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and halogenoperoxidase such as chlorine and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A / S.

A wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are also described in the U.S. Patent. 3,553,139, issued January 5, 1971, to McCarty et al. Enzymes are further described in the U.S. Patent. 4,101, 457, Place et al., Issued July 18, 1978 and in the U.S. Patent. 4,507,219, Hughes, issued March 26, 1985, both. Enzyme materials useful for detergent formulations, and their incorporation into such formulations, are described in US Patent 4,261, 868, Hora et al., Issued April 14, 1981. Enzymes for use in detergents can be stabilized through various techniques. Typical granular or powder detergents can be effectively stabilized by the use of enzyme-based granules. Enzyme stabilization techniques are described and exemplified in U.S. Pat. 3,600,319. issued August 17, 1971 to Gedge et al., and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Pat. 3,519,570.

Enzyme Stabilizers The enzymes used herein are stabilized by the presence of water soluble sources of calcium and / or magnesium ions in the finished compositions, which supply such ions to the enzymes.

(Generally calcium ions are more effective than magnesium ions and are preferred here if only one type of cation is used). Additional stability can be provided by the presence of some other stabilizers described in the art, especially the borate species: see Severson, E.U.A. 4,537,706. Typical detergents, especially liquids, will consist of about 1 to 30, preferably 2 to , more preferably from 5 to 15 and preferably from 8 to 12 millimoles of calcium ion per liter of finished composition. This may vary a bit, depending on the amount of enzyme present and its response to calcium or magnesium ions. The level of calcium or magnesium ions should be selected so that there is always a minimum level available for the enzyme, after allowing complexation with detergency builders, fatty acids, etc., in the composition. Any water soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate and calcium acetate and the corresponding magnesium salts. A small amount of calcium ion, generally from 0.05 to 0.4 millimoles per liter, is often present in the composition due to calcium in the enzyme suspension and formula water. In solid detergent compositions the formulation may include a sufficient amount of a water soluble calcium ion source to supply such amounts in the wash solution. As an alternative, the hardness of the natural water may be sufficient. It should be understood that the above levels of calcium and / or magnesium ions are sufficient to provide stability to the enzyme. More calcium and / or magnesium ions must be added to the compositions to provide an additional measure of fat removal performance. Accordingly, as a general proposition, compositions herein will typically consist of 0.05% to about 2% by weight of a water soluble source of calcium or magnesium ions, or both. The amount may, of course, vary with the amount and type of enzyme used in the composition. The compositions herein may also optionally, but preferably, contain various additional stabilizers especially the borate type stabilizers. Typically, such stabilizers will be used in the compositions at levels ranging from 0.25% to 10% preferably from 0.5% to 5%, more preferably from 0.75% to 3% by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid). Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (eg ortho-, meta- and sodium pyroborate and sodium pentaborate) are suitable. Substituted boric acids (for example, phenylboronic acid, butan boronic acid and p-bromo phenylboronic acid) may also be used in place of boric acid.

The compositions herein may also include ammonium salts and other chlorine scavengers such as those described by Pancheri et al., Patent E.U.A. No. 4,810,413 (issued March 7, 1989), the description of which is incorporated herein by reference.

BLEACHING COMPOUNDS Whitening and Whitening Activating Agents The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When the bleaching compounds are present, they will typically be at levels of from about 1% to about 30%, very typically from about 5% to about 20%, of the detergent composition, especially for fabric washing. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, very typically from about 0.5% to about 40% of the bleaching composition consisting of the bleaching agent plus the bleach activator. The bleaching agents used herein may be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning or other cleaning purposes that are now known or will be known. These include oxygen-based bleaches as well as other bleaching agents. Perborate-based bleaches, eg sodium perborate (for example, mono- or tetrahydrate) may also be used in the present category of another bleaching agent that can be used without restriction encompassing percarboxylic acid-based bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyl acid and diperoxydecandioic acid. Said bleaching agents are described in Patent of E.U.A. 4,483,781 Hartman, issued November 20, 1984, patent application of E.U.A. No. 740,446, Burns et al., Filed July 3, 1985, European Patent Application 0,133,354 Banks et al., Published February 20, 1985, and US Pat. 4,412,934, Chung et al., Issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Pat. 4,634,551, issued on January 6, 1987 to Burns et al. Peroxygen-based bleaching agents can also be used. Peroxygen-based bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate-based bleach can also be used (for example, OXONE, manufactured commercially by DuPont). A preferred bleach based on percarbonate consists of dry particles having an average particle size in the range of 500 microns to about 1,000 microns, with no more than 10% by weight of said particles smaller than 200 microns and being no more of 10% by weight of said particles greater than 1, 250 microns. Optionally, the percarbonate can be coated with silicate, borate or water soluble surfactants. Percarbonate can be obtained from various commercial sources such as FMC, Solvay and Tokai Denka. Mixtures of bleaching agents can also be used. Peroxygen-based bleaching agents, perborates, percarbonates, etc., are preferably combined with bleach activators, which lead to in situ production in aqueous solution (i.e. during the washing process) of the peroxyacid corresponding to the activator bleaching. Several non-limiting examples of activators are described in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al and U.S. Patent 4,412,934. The nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also E.U.A. 4,634,551, for other typical bleaches and activators useful herein. Preferred amido-derived bleach activators are those of the formulas R1N (R5) C (O) R2C (O) L or R1C (O) N (R5) R2C (O) L wherein R1 is an alkyl containing from 6 to 12 carbon atoms, R2 is an alkylene containing from 1 to 6 carbon atoms, R5 is H or alkyl, aryl or alkaryl containing from 1 to 10 carbon atoms, and L is any suitable outgoing group. A leaving group is any group that moves from the bleach activator as a result of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenylsulfonate. Preferred examples of bleach activators of the above formulas include (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate and mixtures thereof as described in US Pat. No. 4,634,551, incorporated in the present for reference. Another class of bleach activators consists of the benzoxazine-like activators described by Hodge et al. In U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference. A highly preferred activator of the benzoxazine type is: Even another class of preferred bleach activators includes the acyllactam activators, especially the acylcaprolactams and acylvalerolactams of the formulas: wherein R6 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms. Highly preferred lactam activators include benzoylcaprolactam, octanoyl caprolactam, octanil caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3, 5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed on sodium perborate. Bleaching agents other than oxygen-based bleaching agents are known in the art and can be used herein. A bleaching agent of the non-oxygen type of particular interest includes photoactivated bleaching agents such as sulfonated zinc and aluminum phthalocyanines. See the Patent of E.U.A. 4,033,718, issued July 5, 1977 to Holcombe et al. If used, the detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonated zinc phthalocyanine. If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts described in US Pat. 5,246,621, Patent E.U.A. 5,244,594; Patent E.U.A. 5,194,416; Patent E.U.A. 5,114,606; and European Patent Application Publication Nos. 549,271 A1, 549,272A1, 544,440A2, and 544,490A1: Preferred examples of these catalysts include Mn? v 2 (uO) 3 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2 (PF6) 2, Mn '"2 (uO) 1 (u-Oac) 2 (1, 4,7-trimeti-1, 4,7-triazac Clononane) 2- (CIO4) 2, Mn? V 4 (uO) 6 (1, 4,7-triazac-clononane) 4 (Cl? 4) 4, Mn "lMniV4 (uO) 1 (u-OAc) 2 - (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2 (CIO 4) 3, Mn v (1, 4,7-trimethyl-1, 4,7-triazacyclononane) - (OCH 3) 3 ( PF8), and mixtures thereof. Other metal-based bleach catalysts include those described in U.S. Patent 4,430,243 and U.S. Pat. 5,114,611. Also reported is the use of manganese with various complex ligands to increase bleaching in the following U.S. Patents. 4,728,455; 5,248,944; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084. As a practical matter, and not by way of limitation, the compositions and methods herein can be adjusted to provide the order of at least one part per ten million species of bleach catalyst in the aqueous wash solution, and preferably supplying from 0.1 ppm to about 700 ppm, preferably from 1 ppm to about 500 ppm, of the catalyst species in the wash solution. Preferably, the detergent composition of the present invention includes at least 5 ppm of perborate or percarbonate.

Polymeric dirt releasing agent Any polymeric soil release agent known to those skilled in the art can optionally be used in the compositions and methods of this invention. The polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to be deposited on hydrophobic fibers and remain adhered thereto until the washing cycles are completed and rinsed and, therefore, serve as an anchor for the hydrophilic segments. This may allow stains that occur after treatment with the soil release agent to be more easily cleaned in subsequent washing procedures. The particularly useful soil release polymeric agents include those soil release agents having: (a) one or more nonionic hydrophilic components that consist essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2 or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of 2 to 10, wherein said hydrophilic segment does not encompass any oxypropylene unit unless it is attached to portions adjacent to each end by ether linkages, or (iii) a mixture of oxyalkylene units consisting of oxyethylene and 1 to oxypropylene units wherein said mixture contains a sufficient quantity of oxyethylene units such that the hydrophilic component has a higher hydrophilic character to increase the hydrophilic character of the surfaces of conventional synthetic polyester fibers after the soil release agent is deposited on said surface, said hydrophilic segment preferably consisting of at least 25% oxyethylene units and preferably, especially for such components having from 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobic components comprising (i) segments of C3 oxyalkylene terephthalate, wherein, if said hydrophobic component also consists of oxyethylene terephthalate, the ratio of oxyethylene terephthalate: C3 oxyalkylene terephthalate is about 2: 1 or less, (i) C4-C6 alkylene segments or C4-C6 oxyalkylene segments, or mixtures thereof, (iii) poly (vinyl ester) segments, (preferably polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) substituents of C1-C4 alkyl ether or C4-alkyl ether, or mixtures thereof, wherein said substituents are present in the form of alkyl ether derivatives of cellulose DC or cellulose C4 hydroxyalkylether, or mixtures thereof, and such cellulose derivatives are amphiphilic, whereby they have a sufficient level of C4 alkyl ether units and / or C4 hydroxyalkylether units to be deposited SW the synthetic polyester fiber surfaces conventional and maintain a sufficient level of hydroxyls, once they adhere to said surfaces of conventional synthetic fibers, to increase the hydrophilic character of the surface of the fiber, or a combination of (a) and (b) Typically, the polyoxyethylene segments of (a) (!) Will have a degree of polymerization of at least 200, although higher levels, preferably from 3 to about 150, more preferably from 6 to about 100, may be used. Suitable C4-C6 oxyalkylene hydrophobes include, but are not limited to, polymeric soil release agents end blockers such as MO3S (CH2) nOCH2CH2? -, where M is sodium and n is an integer of 4-6, such and as described in US Patent 4,721, 580, issued on January 26, 1988 to Gosselink. The soil release polymeric agents useful in the present invention also include cellulose derivatives such as hydroxyether cellulose polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene terephthalate oxide or propylene terephthalate oxide and the like. Such agents are commercially available and include cellulose hydroxyethers such as METHOCEL (Dow). The cellulosic soil release agents to be used herein also include those selected from the group consisting of C -? - C4 - cellulose alkyl and C4 - cellulose hydroxyalkyl.; see Patent E.U.A. 4,000,093, issued on December 28, 1976 to Nicol, and others. Dirt releasing agents characterized by hydrophobic polyvinyl ester segments include polyvinyl ester graft copolymers, for example vinyl esters of C-? -C6, preferably polyvinyl acetate grafted to polyalkylene oxide base structures, as the base structures of polyethylene oxide. See Request for European Patent 0 219 048, published on April 22, 1987 for Kud, and others. Commercially available dirt release agents of this type include the SOKALAN type material, for example SOKALAN HP-22, available from BASF (Germany). One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide terephthalate (PEO). The molecular weight of this polymeric soil release agent is in the range of 25,000 to about 55,000. See Patent E.U.A. 3,959,230 for Hays, issued May 25, 1976 and Patent E.U.A. 3,893,929 to Basadur issued July 8, 1975. Another preferred polymeric soil release agent is a polyester with repeated units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, obtained from polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from DuPon) and MILEASE T (from ICI). See also Patent E.U.A. 4,702,857, issued October 27, 1987 to Gosselink. Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer consisting of an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeat units and terminal portions covalently attached to the base structure. These soil release agents are fully described in US Patent E.U.A. 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include the terephthalate polyesters of E.U.A. 4.71 1, 730, issued December 8, 1987 to Gosselink et al., The oligomeric anionic esters with blocked end of the patent document E.U.A. 4,721, 580, issued January 26, 1988 to Gosselink, and the oligomeric polyester block composites of the patent document E.U.A. 4,702,857, issued October 27, 1987 to Gosselink. Preferred polymeric soil release agents include the soil release agents of US Patent E.U.A. 4,877,896, issued October 31, 1989 to Maldonado et al., Which discloses blocked esters of terephthalate at the end, especially esters of sulfoaroyl terephthalate blocked at the anion end.

If used, the soil release agents will generally comprise from 0.01% to 10% by weight of the detergent composition herein, typically from 0.1% to about 5%, preferably from 0.2 to 3%. Even another preferred soil release agent is an oligomer with repeated units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy units and oxy-1,2-propylene units. The repeating units form the base structure of the oligomer and are preferably terminated with modified isethionate end blockers. A particularly preferred soiling agent of this type consists of a sulfoisophthaloyl unit, 5-terephthaloyl units, oxyethyleneoxy units, and oxy-1,2-propyleneoxy units in a ratio of about 1.7 to about 1. 8, and two end blockers of sodium 2- (2-hydroxyethoxy) -ethansulfonate. Said soil release agent also comprises about 0.5% to 20% by weight of the oligomer, of a crystallinity reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, toluene sulfonate eunum sulfonate and mixtures thereof .

Chelating Agents The detergent compositions herein may also optionally contain one or more iron and manganese chelating agents. Said chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all as defined below. Without intending to be limited to theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from wash solutions through the formation of soluble chelates. Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylene diamine triacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetramine-hexaacetates, diethylenetriaminpentaacetates and ethanololdiglicines, alkali metal salts, ammonium and substituted ammonium thereof and mixtures thereof. While it is preferred to remove the following chelating agents from the detergent compositions of the invention, minimal amounts of aminophosphonates can be used, and ethylene diamine tetrakis (methylene phosphonates) are included as DEQUEST. It is preferred that these amoinophosphonates contain no alkyl or alkenyl groups with more than 6 carbon atoms. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044 issued May 21, 1974, to Connor et al. Preferred compounds of this type in the acid form are dihydroxydisulfobenzenes, such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator to be used herein is ethylene diamine disuccinate ("EDDS"), especially the [S, S] isomer as described in US Pat. 4,704,233, from November 3, 1987, for Hartman and Perkins. If used, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. Most preferably, if used, the chelating agents will comprise from about 0.1% to about 3.0% by weight of said compositions.

Clay Dirt Removal / Anti-redeposition Agents The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines. The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Illustrative ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1987, incorporated herein by reference. Another group of preferred clay soil removal / anti-redeposition agents are the cationic compounds described in European Patent Application 1 1 1, 965, Oh and Gosselink, published June 27, 1984. Other clay soil removal agents / antirredpositing which may be used include the ethoxylated amine polymers described in the Patent Application European 1 1 1, 984, Gosselink, published on June 27, 1984; the zwitterionic polymers described in European Patent Application 1 12,592, Gosselink, published July 4, 1984; and the amine oxides described in the U.S. Patent. No. 4,548,744, Connor, issued October 22, 1985. Other clay soil removal agents and / or anti-redeposition known in the art can also be used in the compositions herein.

Another type of preferred anti-redeposition agent includes the carboxymethyl cellulose (CMC) materials. These materials are well known in the art.

Polymeric Dispersing Agents Polymeric dispersing agents can be advantageously used at levels of 0.1% to 7% by weight in the compositions herein, especially in the presence of zeolite builders and / or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although the polycarboxylates should be used at very low levels, removed or premixed with the surfactant as discussed previously. It is believed that, although not intended to be limited by theory, polymeric dispersing agents increase the overall builder performance when used in combination with other builders (including lower molecular weight polycarboxylates) by inhibiting crystal growth. , peptization of particulate dirt and anti-redeposition. One such polymeric material that is especially suitable for the current composition is polyethylene glycol (PEG). The PEG can show dispersing agent performance and act as a clay soil removal / anti-redeposition agent. Typical molecular weight scales for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, most preferably from about 1,500 to about 10,000. Dispersants based on polyaspartate and polyglutamate, especially in conjunction with zeolite-based builders, can also be used. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) Of about 10,000.

Brightener Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from 0.05% to 1.2% by weight, in the detergent compositions herein. Commercial optical brighteners which may be useful in the present invention can be classified into groups including, but not necessarily limited to, stilbene, pyrazoline, coumarin, carboxylic acid, methinocyanin, dibenzotifen-5, 5-dioxide, azole, heterocycle derivatives 5 ring and 6 members, and other diverse agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents ", M. Zahradnik, Published by John Wiley &Sons, New York (1982) Specific examples of optical brighteners that may be useful in the present invention are those identified in the US Pat.

E.U.A. 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the Verana PHORWHITE series of brighteners.

Other brighteners described in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Arctic White CC and Artic White CWD, available from Hilton-Davis, located in Italy; 2- (4-styryl-phenyl) -2H-naphthol [1,2-d] triazoles; 4,4'-bis- (1, 2,3-triazol-2-yl) -stilbenes; 4,4'-bis (styryl) bis-phenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl-aminocoumarin; 1,2-bis (-benzimidazol-2-yl) -ethylene; 1,3-diphenylpyrazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphthyl- [1,2-s] oxazoI; and 2- (stiiben-4-yl) -2H-naphtho- [1,2-d] triazole. See the Patent of E.U.A. 3,646,015, issued on February 29, 1972 to Hamilton. At present, anionic brighteners are preferred.

Dye transfer inhibition agents The detergent compositions of the present invention can include one or more materials effective to inhibit the transfer of dyes from one fabric to another during the cleaning process.

Generally, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-polyvinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases and mixtures thereof. If used, typically these agents will comprise from 0.01% to 10% by weight of the composition, more preferably from 0.01% to 5%, and most preferably from 0.05% to 2%. More specifically, the polyamine N-oxide polymers suitable for use contain units having the following structural formula: R-Ax-P; wherein P is a polymerizable unit, to which the group N-O may be attached, or wherein the group N-O forms part of the polymerizable unit or the group N-O may be attached to both units; A is one of the following structures: -NC (O) -, -C (O) O-, -S-, -O-, -N =; x is 0 or 1; and R are aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group or the N-O group may be attached is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, midazole, pyrrolidine, piperidine and derivatives thereof. The group N-O can be represented by the following general structures: wherein R-i, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y, and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or forms part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides have a PKa < 10, preferably PKa < 7, very preferably PKa < 6. Any polymer based structure can be used as long as the amine oxide polymer formed is soluble in water and has dye transfer inhibiting properties. Examples of suitable polymeric base structures are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers wherein one type of monomer is an amine N-oxide and the other type of monomer is an N-oxide. The amine N-oxide polymers of the present invention typically have an amine to amine N-oxide ratio of 10: 1 to 1: 1,000,000. However, the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; preferably from 1,000 to 500,000, most preferably from 5,000 to 100,000. It can refer to this class of preferred materials as "PVNO".

The most preferred useful polyamine N-oxide in the detergent compositions herein is poly (4-vinylpyridine-N-oxide) which has an average molecular weight of 50,000 and a ratio of amine to amine N-oxide of about 1. :4. The copolymers of N-vinylpyrrolidone and N-vinylimidazole (referred to as a class which is known as "PVPVI") are also preferred for use herein. Preferably the PVPVI have an average molecular weight scale of 5,000 to 1, 000,000, preferably 5,000 to 200,000, and more preferred 10,000 to 20,000. (The average molecular weight scale is determined by light scattering as described in Barth et al., Chemical Analysis Vol. 1 13. "Modern Methods of Polymer Characterization", the descriptions of which are incorporated herein by reference). PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1: 1 to 0.2: 1, preferably from 0.8: 1 to 0.3: 1, more preferred from 0.6: 1 to 0.4: 1. These polymers can be linear or branched. The compositions of the present invention may also use a polyvinylpyrrolidone ("PVP") having an average molecular weight of 5,000 to 400,000, preferably 5,000 to 200,000, most preferably 5,000 to 50,000. PVP's are known to those skilled in the art in the field of detergents; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference. Compositions containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of 500 to 100,000, preferably from 1,000 to ,000. Preferably, the ratio of PEG to PVP on a ppm basis supplied in the wash solutions ranges from 2: 1 to about 50: 1 and more preferred from 3: 1 to about 10: 1. The detergent compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibiting action. If used, the compositions herein will preferably comprise from 0.01% to 1% by weight of said optical brighteners. The hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein R-i is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl and N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula Ri is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis [(4-anilino-6- (N-2- hydroxyeti) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and the disodium salt. This particular kind of brightener is sold commercially under the trade name Tinopal-UNPA-GX by the Ciba-Geigy corporation. He Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein. When in the above formula, Ri is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [4- anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. This particular kind of brightener is sold commercially under the trade name Tinopal 5BM-GX by the Ciba-Geigy corporation. When in the above formula, Ri is anilino, R2 is morpholino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [(4-anilino-6-morpholino-s-triazin- 2-yl) amino] -2,2'-styrene-disulfonic acid. This particular kind of brightener is sold commercially under the trade name Tinopal AMS-GX by the Ciba-Geigy corporation. The specific species of optical brightener selected for use in the present invention provides especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents described hereinbefore. The combination of such selected polymeric materials (e.g., PVNO and / or PVPVI) with such selected optical brighteners (eg, Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides inhibition of dye transfer significantly better in aqueous wash solutions than either of those two components of the detergent compositions if they will be used alone. Without being limited by theory, it is believed that such brighteners work in that way because they have high affinity to the fabrics in the wash solution and therefore they deposit relatively quickly on these fabrics. The degree to which the brighteners are deposited on the fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient". The depletion coefficient is in general the ratio of a) the polishing material deposited on the fabric to b) the initial concentration of polish in the washing solution. Brighteners with relatively high depletion coefficients are most suitable for inhibiting dye transfer in the context of the present invention. Of course, it will be appreciated that other types of optical brightening compounds may be used, optionally, in the present compositions to provide conventional "brightness" benefits to the fabric, rather than a real effect of dye transfer inhibition. Such use is conventional and well known for detergent formulations.

Foam Suppressants Compounds for reducing or suppressing foaming can be incorporated into the compositions of the present invention. The suppression of foam can be of particular importance in the so-called "high-level cleaning procedures" and in European-style front-loading washing machines. A wide variety of materials can be used as foam suppressors, and foam suppressors are well known to those skilled in the art. See, for example, in the Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley &Sons, Inc., 1979). A category of foam suppressors of particular interest comprises monocarboxylic fatty acids and soluble salts thereof. See the Patent of E.U.A. 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, used as suds suppressors typically have hydrocarbyl chains of 10 to about 24 atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium salts, and the ammonium and alkanolamide salts. The detergent compositions may also contain foam suppressants that are not surfactants. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., triglycerides of fatty acid), fatty acid esters of monovalent alcohols, aliphatic C18-40 ketones (e.g. , stearone), etc. Other foam inhibitors include N-alkylated aminotriazines such as tri- to hexa-alkylmelamines or chlorotriazines of di to tetra-alkylamines formed as cyanuric chloride products with 2 or 3 moles of primary or secondary amine containing from 1 to 24 carbon atoms , propylene oxide and monostearyl phosphates such as monostearyl alcohol phosphate ester and alkali metal monostearyl diphosphates (e.g., Na, K, Li) and phosphate esters, the latter being used only at very low levels. Hydrocarbons such as paraffin and halogenoparaffins can be used in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point on the scale of around minus 40 ° C and about 50 ° C, and a minimum boiling point not less than about 1 10 ° C (pressure atmospheric). The use of waxy hydrocarbons is also known, preferably having a melting point below about 100 ° C. Hydrocarbons constitute a preferred category of foam suppressors for detergent compositions. The hydrocarbon foam suppressors are described, for example, in the U.S. Patent. 4,265,779, issued May 5, 1981 to Gandolfo et al. Thus, the hydrocarbons include saturated, aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin", as used in this description of foam suppressors, is intended to include mixtures of true paraffins and cyclic hydrocarbons. Another preferred category of foam suppressors that are not surfactants comprise silicone foam suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles in which the polyorganosiloxane is chemoabsorbed or fused to the silica. Silicone foam suppressors are well known in the art and, for example, are described in the U.S. Patent. 4,265,779, issued May 5, 1981 to Gandolfo et al., And European Patent Application No. 89397851.9, published on February 7, 1990, by Starch, M. S. Other silicone foam suppressors are described in the U.S. Patent. No. 3,455,839, which relates to compositions and methods for removing foams from aqueous solutions by incorporating in them small amounts of polydimethylsiloxane fluids. Mixtures of silicone and silanated silica are described, for example, in German Patent Application DOS 2,124,526. Silicone foam scavengers and foam controlling agents in granular detergent compositions are described in the U.S. Pat. 3,933,672, Bartolotta et al., And in U.S. Pat. 4,652,392, Baginski et al., Issued March 24, 1987.

An illustrative silicone-based foam suppressant for use herein is a foaming suppressant amount of foaming agent consisting essentially of: (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs to about 1,500 cs at 25 ° C. (ii) from about 5 to about 50 parts per 100 parts by weight of (i) siloxane resin composed of (CH 3) 3 SiO-1/2 SiO 2 units in a proportion of (CH 3) 3 SiO- units 1/2 to SiO2 units of about 0.6: 1 to about 1.2: 1; and (iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel. In the preferred silicone-based foam suppressors used herein, the solvent for a continuous phase is made of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone-based foam suppressor is branched / crosslinked and preferably non-linear. To further illustrate this point, typical liquid laundry detergent compositions with controlled foams optionally consist of 0.001 to 1, preferably 0.01 to 0.7, more preferred of 0. 05 to 0.5% by weight of said silicone-based foam suppressors, which consist of (1) a non-aqueous emulsion of a primary anti-foaming agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone compound that produces silicone resin, (c) a finely divided filler material and (d) a catalyst to promote the reaction of the mixture of components (a), (b) and (c), to form silanolates; (2) at least one nonionic surfactant based on silicone; and (3) polyethylene glycol or a polyethylene glycol propylene glycol copolymer having a solubility in water at room temperature of more than about 2% by weight; and without propylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471, Starch, issued December 18, 1990 and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., Issued February 22, 1994 and U.S. Patents. 4,639,489 and 4,749,740, Aizawa and others in column 1, line 46 to column 4, line 35. The silicone-based foam suppressors herein preferably consist of polyethylene glycol and a polyethylene glycol / propylene glycol copolymer, all having a weight average molecular weight of less than 1,000, preferably between 100 and 800. The polyethylene glycol and the polyethylene / propylene copolymers herein have a solubility in water at room temperature of about more than 2% by weight, preferably more than 5% in weigh. The preferred solvent herein is polyethylene glycol having an average molecular weight of less than 1,000, preferably about 100 to 800, more preferred between 200 and 400, and a polyethylene glycol / propylene glycol copolymer, preferably PPG 200 / PEG 300 A weight ratio of about 1: 3 1: 6 polyethylene glycol is preferred: polyethylene-propylene glycol copolymer. The preferred silicone-based foam suppressors used herein do not contain polypropylene glycol, particularly of molecular weight of 4,000. These also preferably do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101. Other foam suppressants useful herein include secondary alcohols (eg, 2-alkylalkanols) and mixtures of such alcohols with silicone oils, such as the silicones described in US Pat. 4,798,679, 4,075.1 18 and EP 150,872. Secondary alcohols include the C6-Ci6 alkyl alcohols having a C-i-Cß chain. A preferred alcohol is 2-butyloctanol, which can be obtained from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trade names ISALCHEM 123 by Enichem. Mixed foam suppressors typically consist of alcohol + silicone in a weight ratio of 1: 5 to 5: 1. For any detergent composition for use in automatic washing machines, the foam should not be formed to the extent that it flows excessively out of the washing machine. The foam suppressors, when used, are preferably present in a "foam suppressant amount". By "foam suppressant amount" is meant that the formulator of the composition can select an amount of this foam controlling agent that will sufficiently control the foams which will result in a laundry detergent with low foaming to be used in automatic washing machines. The compositions herein will generally consist of 0% to about 5% foam suppressant. When used as suds suppressors, the monocaboxylic fatty acids and salts thereof will typically be present in amounts of up to 5% by weight of the detergent composition. Preferably, 0.5% to 3% of fatty monocarboxylate foam suppressant is used. Silicone foam suppressors are typically used in amounts of up to 2% by weight, of the detergent composition although larger amounts may be used. This upper limit is of a practical nature, mainly due to the concern to keep costs to a minimum and the effectiveness of smaller quantities to effectively control the foam. Preferably from 0.01% to 1% of silicone foam suppressant is used, more preferably from 0.25% to about 0.5%. As used herein, these weight percent values include any silica that could be used in combination with polyorganosiloxane, as well as any auxiliary material that could be used. The monostearyl phosphate foam suppressors are generally used in amounts ranging from 0.1% to 2% by weight of the composition. Hydrocarbon foam suppressors are typically used in amounts ranging from 0.01% to 5%, although higher levels can be used. Alcohol foam suppressors are typically used at 0.2% -3% by weight of the finished compositions.

Fabric softeners Various fabric softeners applied in the wash, especially the non-palpable smectite clays of the E.U.A. 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softening clays known in the art, can optionally be used at levels typically from 0.5% to 10% by weight in the compositions herein to provide benefits of softening fabrics together with cleaning the fabric. Clay-based softeners can be used in combination with cationic and amine softeners as described, for example, in US Pat. 4,375,416, Crisp et al., March 1, 1983 and Patent E.U.A. 4,291, 071, Harris et al., Issued September 22, 1981.

Other Ingredients A wide variety of other useful ingredients may be included in detergent compositions in the compositions herein, including other active ingredients, vehicles, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions , etc. If high foaming is desired, foaming enhancers such as C-io-C-iß alkanolamides, typically at levels of 1% -10%, can be incorporated into the compositions. C-? 0-C14 monoethanol and diethanol amides illustrate a typical class of such foam enhancers. The use of such foam enhancers with adjuncts of high foaming surfactants such as the amine, betaine and sultaine oxides indicated above is also advantageous. If desired, soluble magnesium salts such as MgCl.sub.2, MgSO.sub.2, and the like can be added at typically 0.1% -2% levels, to provide additional foam and to increase fat removal performance although the addition of magnesium ions does not leads to the highest performance levels of the builder material described herein. Various detersive ingredients used in the compositions of the present invention can optionally be additionally stabilized by absorbing said ingredients in a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is mixed with a surfactant before being absorbed into the porous substrate. During use, the detersive ingredient is released from the substrate in the aqueous washing liquid, where it fulfills its intended detersive function. To illustrate this technique in greater detail, a porous hydrophobic silica material (trade name SIPERNAT D10, DeGussa) is mixed with a proteolytic enzyme solution containing 3% -5% non-ionic ethoxylated alcohol surfactant of C-13- C15 (EO 7). Typically the enzyme / surfactant solution is 2.5 X the weight of the silica material. The resulting powder is dispersed with stirring in silicone oil (various silicone oils with viscosities in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this method, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use. in detergents, including liquid laundry detergent compositions. The detergent compositions herein will preferably be formulated so that, during use in aqueous cleaning operations, the wash water has a pH of between 6.5 and 11, preferably between 7.5 and 10.5. Laundry products typically have a pH 9-11. Techniques for controlling the pH to the recommended levels of use include the use of buffer solutions, alkalis, acids, etc., and are well known to those skilled in the art. Various amounts of processing aids such as sugars can be used, for example those sugars described in US Pat. 4,908,159, Davies et al., Issued March 13, 1990, and starches in the compositions of the present invention. Other suitable processing aids include those described in US Pat. 4,013,578 Child et al., Issued March 22, 1977.

Various amounts of crystallization aids such as those described in Patent E.U.A. 3,957,695, Davies et al., Issued May 18, 1976, can be used in the compositions of the present invention in the same way. The hydrotropes can also be used in the compositions of the invention such as those described in the patent.

E.U.A. 5,478,503, Swift, issued December 26, 1995. In addition, combinations of citric acid and sodium carbonate blended can be included as described in US Pat. 5,338,476, Pancheri et al., August 16, 1994. To make the present invention more easily understood, reference is made to the following examples, which are designed solely to illustrate and not to limit the scope of the invention.

EXAMPLE 1 Calcium sequestration and speed of sequestration test A step-by-step procedure for determining the amount of calcium sequestration and the rate thereof for the crystalline calcium carbonate builder used in the compositions described in the present invention is illustrated below. 1. Add to 750 ml of distilled water at 35 ° C, enough concentrated water hardness material to produce 172 ppm of CaCOs; 2. Shake and maintain the water teature at 35 ° C during the experiment; 3. Add 1 ml of 8.76% KOH to water; 4. Add 0.1085 g of KCl; 5. Add 0.188 g of glycine; 6. Shake 0.15 g of NaCO3 in the solution; 7. Adjust the pH to 10.0 using 2N HCl and keep it throughout the test; 8. Shake 0.15 g of a detergency builder according to the invention in the solution and turn on the time meter; 9. Collect an aliquot of the solution every 30 seconds, filter it quickly through a 0.22 micron filter, acidify quickly to a pH of 2.0-3.5 and seal the container; 10. Repeat step 9 at intervals of 1 minute, 2 minutes, 4 minutes, 8 minutes and 16 minutes; 1 1. Analyze all 6 aliquots for the CaCO3 content by means of an ion selective electrode, titration, quantitative ICP or other appropriate technique; 12. The sedation rate in ppm of CaCO3 sequestered per 200 ppm of builder is 171 minus the concentration of CaCO3 at one minute; 13. The amount of sequestration (in ppm of CaCO3 per gram / liter of builder) is 171 minus the concentration of CaC? 3 at 16 minutes by five. For the particle sizes of the builder material in accordance with the present invention which are in the lower portion of the average particle size range, a reference sample that runs without hardness is needed to properly determine how much of the builder Detergency passes through the filter. The above calculations should then be corrected to eliminate the contribution of the builder to the apparent calcium concentration.

EXAMPLES ll-IV In the following, various detergent compositions prepared according to the invention and specifically for washing machines that are loaded on the upper part are exemplified. The base granule is prepared by a conventional spray-drying process in which the starting ingredients are formed in a suspension and passed through a spray-drying tower having a flow against hot air flow (200-). 300 ° C) which results in the formation of porous granules. The mixed agglomerates are formed from two supply streams of some starting detergent ingredients which are supplied continuously at a rate of 1400 kg / hr, in a Lodige CB-30 mixer / densifier, one of which consists of a paste of surfactant containing the surfactant and water and the other stream contains the dry starting detergent material containing aluminosilicate and sodium carbonate. The rotational speed of the rod in the Lódige CB-30 mixer / densifier is approximately 1400 rpm and the average residence time is approximately 1-10 seconds. The contents from the Lddige CB-30 mixer / densifier are supplied continuously to a Mixer KM-600 mixer / densifier for further agglomeration during which the average residence time is approximately 6 minutes. The resulting detergent agglomerate is then supplied to a fluidized bed dryer and to a fluidized bed cooler before being mixed with the spray dried granules. The remaining auxiliary detergent ingredients are sprinkled on, or added in dry, to the mixture of agglomerates and granules.

II lll IV Base granule Calcite (rhombohedral { 1.0-1.1.}.) 3.0 16.0 11.0 Aluminosilicate 15.0 2.0 1 1.0 Sodium sulphate 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 C12-C13 Sodium alkylbenzenesulfonate linear 6.0 6.0 7.0 C14-C16 secondary sodium alkyl sulfate 3.0 3.0 3.0 Sodium alkylsuiphate of C14-C15 ethoxylated 3.0 3.0 9.0 Sodium silicate - 0.1 0.2 Rinse aid 246 0.3 0.3 0.3 Sodium carbonate 7.0 7.0 25.7 DTPA1 0.5 0.5 - Mixed agglomerates C 4-C15 alkyl sulfate, Na 5.0 5.0 _ C12-C13 Sodium Alkylbenzene sulfonate 2.0 2.0 - NaKCa (C03) 2 - 7.0 - Sodium carbonate 4.0 4.0 - Polyethylene glycol (MP = 4000) 1.0 1.0 - Mix C12.15 ethoxylated alkyl (EO = 7) 2.0 2.0 0.5 Perfume 0.3 0.3 1.0 Polyvinylpyrrolidone 0.5 0.5 - Polyvinylpyridine N-oxide 0.5 0.5 - Polyvinylpyrrolidone-polyvinylimidazole 0.5 0.5 - Distearylamine and Cumenosulfonic acid 2.0 2.0 - Dirt release polymer 0.5 0.5 - Lipolase Lipase (100,000 LU / I.). 4 0.5 0.5 - Termamil amylase (60 KNU / g) 4 0.3 0.3 - CAREZYMER cellulase (1000 CEVU / g) 4 0.3 0.3 - Protease (40 mg / g) 5 0.5 0.5 0.5 NOBS3 5.0 5.0 - Sodium percarbonate 12.0 12.0 - Polydimethylsiloxane 0.3 0.3 - Various (water, etc) the remainder the rest the rest Total 100 100 100 1 Diethylenetriaminpentaacetic acid 2 Prepared in accordance with the patent E.U.A. 5,415,807, issued on May 16, 1995 for Gosselink and other 3 Nonanoiloxibencensulfonate 4 Acquired at Novo Nordisk A / S 5 Acquired at Genencor 6 Acquired at Ciba-Geigy EXAMPLES V-XVl The following detergent compositions according to the invention are especially suitable for scrubbers that are loaded from the front. The compositions are made in the same manner as examples 11-IV. (% weight) V VI Vil Base granule Na2Ca2 (C03) 3 24.0 - 8.0 Calcite (rhombohedral {1, 0-1, 1.}.) - 24.0 8.0 Aluminosilicate - - 8.0 Sodium Sulfate 6.0 6.0 6.0 Acrylic acid copolymer / maleic acid 4.0 4.0 4.0 C12-C13 linear sodium alkylbenzenesulfonate 8.0 8.0 8.0 Sodium silicate - 0.1 0.2 Carboxymethylcellulose 1.0 1.0 1.0 Brightener 47 0.3 0.3 0.3 Silicone based antifoam 1.0 1.0 1.0 DTPMPA1 0.5 0.5 0.5 Mixed Alkyl of C12.l5 ethoxylated (EO = 7) 2.0 2.0 2.0 Alkyl of C12.1 ethoxylated (EO = 3) 2.0 2.0 2.0 Perfume 0.3 0.3 0.3 Sodium carbonate 13.0 13.0 13.0 Sodium perborate 18.0 18.0 18.0 Sodium perborate 4.0 4.0 4.0 TAED2 3.0 3.0 3.0 Savinasa protease (4.0 KNPU / a) 3 1.0 1.0 1.0 Lipolase lipase (100,000 LU / I- 0.5 0.5 0.5 Termamil amylase (60 KNU / g) 3 0.3 0.3 0.3 Sodium sulfate 3.0 3.0 5.0 Miscellaneous (water, etc) the rest the rest the rest Total 100 100 100 Diethylene triamine pentamethylene phosphonic acid • Tetra acetyl ethylene diamine 'Acquired at Novo Nordisk A / S (% weight) VIII IX X Base granules Aluminosilicate 14.0 - - Calcite (rhombohedral {1, 0-1, 1.}.) 1.0 15.0 - Sodium sulfate 2.0 2.0 - Sodium alkyl-benzenesulfonate of C12-C-? 3 linear 3.0 3.0 - DTPMPA1 0.5 0.5 - Carboxymethylcellulose 0.5 0.5 - Acrylic acid / maleic acid copolymer 4.0 4.0 - Mixed agglomerates C14-C sodium alkylsulfate? 5 _ _ 11.0 Sodium alkylbenzene sulfonate of C12-C13line! 5.0 5.0 - Tallow Alkyl Sulfate 2.0 2.0 - Sodium Silicate - 0.1 - Aluminosilicate 11.0 12.0 6.0 Calcite (rhombohedral {1, 0-1, 1.}.) 1.0 - 7.0 Carboxymethylcellulose - - 0.5 Acrylic acid / maleic acid copolymer - 2.0 Sodium carbonate 8.0 8.0 7.0 Mixed Perfume 0.3 0.3 0.5 Alkyl of C12.15 ethoxylate (EO = 7) 4.0 4.0 4.0 Alkylated C12_? S ethoxylate (EO = 3) 2.0 2.0 2.0 Acrylic acid / maleic acid copolymer - 3.0 Stratified crystalline silicate2 - - 12.0 Sodium Citrate 5.0 5.0 8.0 Baking soda 5.0 5.0 5.0 Sodium carbonate 6.0 6.0 15.0 Polyvinylpyrrolidone (PVP) 0.5 0.5 0.5 Alcalase Protease (3.0 AU / g) 0.5 0.5 1.0 LipaseLipolase 3 (100,000 LU / I) 0.5 0.5 0.5 Termamil amylase3 (60KNU / g) 0.5 0.5 0.5 CellulasaCAREZYMÉ R 3 (1000CEVU / g) 0.5 0.5 0.5 Sodium sulfate 4.0 4.0 0.0 Miscellaneous (water, etc) the rest the rest the rest Total 100 100 100 Diethylene triamine pentamethylene phosphonic acid SKS 6 commercially available in Hoechst 'Acquired in Novo Nordisk A / S (% weight) XI XII XIII Base granules Aluminosilicate - 8.0 7.0 Calcite (rhombohedral {1, 0-1, 1.}.) 15.0 7.0 8.0 Sodium Sulfate 2.0 2.0 0.0 Sodium Alkylbenzenesulfonate of C12-C13 linear 3.0 3.0 3.0 Cationic surfactant1 1.0 1.0 1.0 DTPMPA2 0.5 0.5 0.5 Carboxymethylcellulose 0.5 0.5 0.5 Acrylic acid copolymer / maleic acid 3.0 3.0 2.0 Mixed agglomerates C12-C13 linear sodium alkylbenzenesulfonate 5.0 5.0 5.0 Tallow Alkyl Sulfate 2.0 2.0 2.0 Sodium silicate - 0.1 0.2 Aluminosilicate 8.0 8.0 8.0 Sodium carbonate 8.0 8.0 4.0 Mix Perfume 0.3 0.3 0.3 Alkyl of C12.15 ethoxylated (EO = 7) 2.0 2.0 2.0 Alkyl of C12. 5 ethoxylated (EO = 3) 1.0 - 1.0 Sodium Citrate 2.0 2.0 2.0 Sodium bicarbonate 1.0 1.0 - Sodium carbonate 11.0 11.0 10.0 TAED3 4.0 4.0 5.0 Sodium perborate 10.0 10.0 10.0 Polyethylene oxide - - 0.3 Bentonite - - 10.0 Savinasa Protease (4.0 KNPU / g) 4 1.0 1.0 1.0 Lipase Lipolase 3 (100,000 LU / I) 0.5 0.5 0.5 Termamil amylase (60KNU / g) 0.5 0.5 0.5 Cellulase CAREZYMER 3 (1000CEVU / g) 0.5 0.5 0.5 Sodium Sulfate 1.0 1.0 - Miscellaneous (water, etc) the rest the rest the rest Total 100 100 100 Compound of C12.14 dimethyl hydroxyethyl quaternary ammonium; Diethylenetriamine pentamethylene phosphonic acid 'Tetraacetyldiethylene diamine Acquired at Novo Nordisk A / S (% weight) XIV XV XVI Agglomerates C12-C13 linear sodium alkylbenzenesulfonate 5.0 5.0 5.0 C14-C16 secondary sodium alkyl sulfate 3.0 3.0 3.0 Sodium alkylsulfate of C14-C15 9.0 9.0 9.0 Aluminosilicate 1.0 - 9.0 Calcite (rhombohedral {1, 0-1, 1.}.) 9.0 10.0 1.0 Sodium carbonate 6.0 6.0 6.0 Acrylic acid / maleic acid copolymer 3.0 3.0 3.0 Carboxymethylcellulose 0.5 0.5 0.5 DTPMPA1 0.5 0.5 0.5 Mix Alkyl of C12.15 Ethoxylate (EO = 7) 5.0 5.0 5.0 Perfume 0.5 0.5 0.5 Stratified crystalline silicate2 5.0 - 10.0 Calcite (rhombohedral {1, 0-1, 1.}.) 5.0 10.0 - HEDP3 0.5 0.5 0.5 Sodium Citrate 2.0 2.0 3.0 TAED4 6.0 6.0 6.0 Sodium percarbonate 20.0 20.0 20.0 Dirt-free polymer5 0.3 0.3 0.3 Savinasa Protease (4 KNPU / g) 6 1.5 1.5 1.5 Lipase Lipolase (100,000 LU / g) 6 0.5 0.5 0.5 CAREZYMER Cellulase (1000CEVU / g) 6 0.5 0.5 0.5 Termamil amylase (60KNU / g) 6 0.5 0.5 0.5 Silicone / Silicone based foam suppressor 5.0 5.0 5.0 Polisher 497 0.3 0.3 0.3 Rinse aid 477 0.3 0.3 0.3 Various (water, etc) the rest the rest the rest Total 100 100 100 1 Diethylenetriamine pentamethylene phosphonic acid 2 SKS 6 commercially available from Hoechst 3 Hydroxy ethylidene 1,1-dysphonic acid 4 Tetra acetyl ethylene diamine Prepared in accordance with US Pat. 5,415,807, issued May 16, 1995 for Gosselink and others 6 Acquired at Novo Nordisk A / S 7 Acquired at Ciba-Geigy EXAMPLES XVII-XVIH The following detergent compositions according to the invention are suitable for washing machines that are loaded on top with low wash volume. The compositions are worked up in the same manner as in Examples II-IV. '% Weight) XVII XVIII Granules with a rhombohedral base. { 1, 0, -1, 1} ) 7.0 3.0 Aluminosilicate - 4.0 Sodium Sulfate 3.0 3.0 Polyethylene glycol (MW = 4000) 0.5 0.5 Co-polymer acrylic acid / maleic acid 6.0 6.0 0.5 0.5 cationic surfactant Secondary sodium alkyl sulfate of C14-16 7.0 7.0 Sodium linear alkylbenzene sulfonate of C12-13 13.0 13.0 Sodium alkylsulfate of C14-15"ethoxylate 6.0 6.0 Stratified crystalline silicate 6.0 6.0 Sodium silicate - 0.1 Oily fatty acid, Na 1.0 1.0 Polisher 497 0.3 0.3 Sodium carbonate 28.0 28.0 DPTA3 0.3 0.3 Mix C12-1 alkyl ethoxylate (EO-07) 1.0 1.0 Perfume 1.0 1.0 Rhombohedral Calcite. { 1, 0, -1, 1} 2.0 3.0 Dirt-free polymer 4 0.5 0.5 Polyvinylpyrrolidone 0.3 0.3 N-oxide polyvinylpyridine 0.1 0.1 Polyvinylpyrrolidone-polyvinylimidazole 0.1 0.1 Lipase Lipolase (100,000 LU / I) 6 0.3 0.3 Termamil amylase (60 KNU / g) 6 0.1 0.1 CAREZYME® cellulase (1000 CEVU / g) 6 0.1 0.1 Savinasa (4.0 KNPU / g) 6 1.0 1.0 NOBS5 4.0 4.0 Sodium Perborate Monohydrate 5.0 5.0 Various (water, etc). the rest the rest Total 100.0 100.0 1 Compound of dimethyl hydroxyethyl ammonium of C12.14 quaternary 2 SKS6 commercially available from Hoescht 'Diethylene triamine pentaacetic acid 4 Prepared in accordance with the Patent E: U: A: 5,415,807, issued May 16, 1995, for Gosselink and others. 5 Nonanoyloxybenzenesulfonate * Acquired at Novo Norkisk A / S 7 Acquired at Ciba-Geigy EXAMPLES XIX-XXI The following detergent compositions in accordance with The invention is especially suitable for hand washing operations. (% in weigh) * *. fifteen twenty composed of dimethyl hydroethyl ammonium of C12.14 quaternary 2 diethylene triamine pentaiacetic acid 3 Prepared in accordance with Patent E: U: A: 5,415,807, issued May 16, 1995, for Gosselink et al. 4 Nonanoiloxinbencensulfonato 5 Acquired at Novo Norkisk A / S 6 Acquired at Ciba-Geigy EXAMPLE XXII The following detergent composition according to the invention is in the form of a laundry bar which is especially suitable for hand washing operations.

(% Weight) XXII Coconut Fatty Alkyl Sulfate 30.0 Sodium tripolyphosphate 1.0 Tetrasodium pyrophosphate 1.0 Sodium carbonate 20.0 Sodium Sulfate 5.0 Rhombohedral Calcite. { 1, 0, -1, 1} 20.0 Aluminosilicate 10.0 Coconut fatty alcohol 2.0 Perfume 1.0 Various (water etc) 1.0 Total 100.00 EXAMPLES XIII-XXIV The following detergent compositions according to the invention are especially suitable for automatic dishwashing machines, exemplified herein 'Tetraacetyl ethylene diamine Acquired at Novo Nordisk A / S 4 Acquired at Genencor EXAMPLES XXV-XXVI These examples present liquid detergent compositions according to the invention. * i fifteen Acquired in Ciba-Geigy 2 Acquired in Novo Nordisk A / S 20 3 Acquired in Genencor 4 Prepared in accordance with the patent E: U.A. 5,415,807, issued May 16, 1995, Gosselink et al.

EXAMPLE XXVII This example illustrates the process of making the builder of the present invention. 2.5 kg / hr of calcite commercially purchased from Omya, Inc., is continuously fed into the chamber of an 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 an Alpine air classifier (Model 50ATP air classifier commercially available from Hosokawa Micron-Alpine, Germany) mounted therein. The Fluid Bed Jet Mill and the air classifier are operated with the valve (E12) open, the throttle butterfly valve adjusted to accommodate the pressure at 0 air pressure, the air classifier speed adjusted to 8,000 RPM , the grinding valve set at a pressure of 5 bar and the product supply screw set at 35% of the maximum speed. The air pressure of the rinsing air in the Fluid Bed Jet Mill are adjusted to 0.5 and 0.6 bars, after which the desired crystalline calcium carbonate builder is obtained having a rhombohedral crystalline structure with. { 1, 0, .1, 1} ). Having thus described the invention in detail, it will be clear to those skilled in the art that various changes can be made without departing from the essence of the invention and the invention should not be considered limited to what is described in the specification.

Claims (10)

NOVELTY OF THE INVENTION CLAIMS t%

1. A detergent composition characterized in that: (a) it has an effective amount of crystalline calcium carbonate, said crystalline calcium carbonate having a substantially rhombohedral crystal structure with crystallographic indices (1.0, -1.1); and (b) at least 1% by weight of a detersive surfactant.

2. A detergent composition according to claim 1, further characterized in that said detergent composition is substantially free of phosphates. *

3. A detergent composition according to claims 1-2, further characterized in that said detergent composition is substantially free of soluble silicates.

4. A detergent composition according to claims 1-3, further characterized in that it contains sodium sulfate and sodium carbonate in a weight ratio of 1: 20 to 2: 1.

5. A detergent composition according to claims 1-4, further characterized in that said detergent composition is substantially free of polycarboxylates.

6. - A detergent composition according to claims 1-5, further characterized in that it has a premix containing polycarboxylate and said detersive surfactant.

7. A detergent composition according to claims 1-6, further characterized in that said crystalline calcium carbonate is calcite.

8. A detergent composition according to claims 1-7, further characterized in that it contains from 0.01% to 5% of potassium salts.

9. A detergent composition according to claims 1-8, further characterized in that said crystalline calcium carbonate has an average particle size of 0.2 microns at 20 microns.

10. A method for removing calcium hardness ions from an aqueous solution characterized in that it comprises the step of dispersing the crystalline calcium carbonate having a substantially rhombohedral crystal structure with crystallographic indices (1.0-1.1) in said aqueous solution, said calcium hardness ions crystallizing on said crystalline calcium carbonate which results in the removal of said calcium hardness ions from said aqueous solution.