Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – Clay or inorganic aluminosilicate salt component
Reexamination Certificate
2001-07-19
2004-04-06
Boyer, Charles (Department: 1751)
Cleaning compositions for solid surfaces, auxiliary compositions
Cleaning compositions or processes of preparing
Clay or inorganic aluminosilicate salt component
C510S315000, C510S323000, C510S377000, C423S700000
Reexamination Certificate
active
06716808
ABSTRACT:
TECHNICAL FIELD
This invention relates to built detergents for domestic use, especially having granular, tablet or syndet bar form. The compositions contain particular aluminosilicate builders, preferably hybrids of aluminosilicate and specific occluded materials such as silicate, carbonate, sulfate, phosphate, borate, nitrate, nitrite, Na
2
O, or mixtures thereof. The builder can be surface-modified or can be processed in a particular manner. The compositions further contain selected detergent adjuncts, such as certain surfactants, enzymes, polymers and/or bleaches. Other adjuncts, e.g., conventional surfactants, enzymes, builders or bleaches can also be present.
BACKGROUND OF THE INVENTION
The formulation of zeolite builders into detergents is technically difficult. Zeolites hitherto formulated in detergents lack an ideal combination of low cost, ease of manufacture, high equilibrium binding of both Ca and Mg, rapid kinetics of binding for Ca and Mg, and ability to hold large amounts of surfactant. Zeolites or aluminosilicates, when added to laundry detergents, can interact adversely with numerous laundry detergent adjuncts, e.g. bleaches, bleach catalysts, enzymes, brighteners and other additives, and/or produce unacceptable harshness and/or give other major problems, such as redeposition onto textiles.
Another significant technical problem is a strong tendency for low-level adjuncts or differently charged additives such as cationic surfactants, catalysts or enzymes to adsorb onto relatively large, anionically charged surfaces of insoluble inorganic builders. Since such adjuncts are often expensive and tend to be used at relatively low levels in detergent compositions, their loss by any mechanism, such as interaction with the builder, can have dramatic effects on overall cleaning performance.
Accordingly, substantial and costly research and experimentation are needed to integrate a synthetic inorganic builder material with other detergent ingredients so as to benefit from its properties and at the same time avoid negating or reducing the desirable effect(s) of the adjuncts with which it is formulated. Such experimentation often results in failure. There is, therefore, an ongoing unmet need for fully formulated detergent compositions acceptably, incorporating synthetic inorganic builders, especially certain types for which synthesis methods have only recently been described.
BACKGROUND ART
WO 98/42622, to Englehard Corporation, published Oct. 1, 1998, provides processes for preparing certain hybrid zeolite-silicate compositions. These materials do not contain hydroxysodalite, indeed a comparison is given to demonstrate the absence thereof. Also described are some detergent formulations using, the hybrid aluminosilicates. Solving the problems of formulating these hybrid builders, especially with certain potentially interacting low-level, high cost ingredients, are not, however specifically addressed. It appears to be assumed that the hybrid zeolite-silicate can simply be formulated as a replacement for current zeolites, and the formulation teaching is to conventional zeolite detergents. However, according to the theory of operation described in WO 98/42622, the hybrid material has a higher charge. Whether for this reason or due to some other theory of operation, it has now been discovered that the WO 98/42622 hybrid materials do not have the same properties for purposes of formulation into detergents as do the conventional detergent zeolite, zeolite A.
While WO 98/42622 provides apparently useful synthesis methods, and the evidence provided in WO 98/42622 strongly suggests that the WO 98/42622 hybrid material is different from zeolite MAP, whether this hybrid or silicate-occluded material is in fact novel may, or may not, be the case. There exists a substantial body of old prior art on zeolite manufacture which is not in computer-readable form and as such is relatively difficult to find and/or search. An accessible fraction of this art includes disclosure of occluded, or hybrid-type (to use the WO 98/42622 language) zeolites or hybrid aluminosilicates having occluded salts of various kinds, and hints that occlusion is well-known to zeolite manufacturers. For example, occluded zeolites are described in “Zeolite Chemistry and Catalysts”. Ed. J. A. Rabo, ACS Monograph Series. Vol. 171, American Chemical Society, Washington D.C. 1976. See more particularly Chapter 5. “Salt Occlusion in Zeolite Crystals”, pages 33-349 and references cited therein, see also Chapter 1 of the same reference. Thus, such materials include, for example, sodium nitrate-occluded or other nitrate salt-occluded zeolite A, see the work referenced by Liquomik and Marcus. See also Chapter 1, pages 58-63 of the same ACS monograph, which discloses, for example, NaAlO
2
occluded zeolite A; other occluded aluminosilicates, such as borate-occluded sodalite, NaOH-occluded sodalite, Na
2
CO
3
-occluded cancrinite, halide- or nitrate-occluded zeolite Y, and yet other salt-occluded zeolites. In Chapter 4 of the ACS monograph, it is noted “Another consequence of the Donnan equilibrium is that electrolyte invasion can occur. In this process, anions from the aqueous phase enter into the zeolite phase with a correspondingly equivalent number of additional cations.” See also Chapter 4 of the same ACS monograph at pages 310-111, for example the statement “Modified varieties of many zeolites can be prepared by occluding extraneous species within the zeolite crystal either during or after synthesis.” Reference is made to the work of Barrer and others. In Chapter 5 at page 338, reference is made to borate-occluded zeolite A. In short, a wealth of occluded aluminosilicate materials appear to be disclosed in the art.
Surprisingly, in contrast, other than in WO 98/42622, there appears to be no specific disclosure whatever of the use of occluded or hybrid-type zeolites or other occluded aluminosilicates in detergent compositions.
It is therefore against a background of (a) an apparent plurality of occlusions in zeolites coupled with (b) a lack of teaching on how to formulate occluded or hybrid-type aluminosilicate materials in detergents other than as a mere substitute for zeolite A or P as taught in WO 98/42622, that the present invention is provided.
Additionally by way of background on zeolites and occluded zeolites, the practitioner is referred to D. W. Breck, “Zeolite Molecular Sieves”, Wiley, New York. 1974 and to Kirk Othmer's Encycopedia of Chemical Technology, 4th Edition, 1995, Wiley, New York, see Vol. 16, “Molecular Sieves”.
Builders in general are described in many patents issued to Procter & Gamble, Unilever, Hoechst/Clariant, Kao, Lion, Crosfield, PQ Corp., and others. One recent review in the context of detergents is in Surfactant Science Series, Marcel Dekker, New York, see Vol. 71, Ed. M. S. Showell, published 1998. See more particularly Chapter 3, “Builders: The Backbone of Powdered Detergents” by Hans-Peter Rieck of Hoechst/Clariant.
All percentages herein are by weight of the detergent composition unless otherwise noted. All references cited are incorporated by reference in their entirety,. Ratios and proportions are by weight unless otherwise specifically indicated.
SUMMARY OF THE INVENTION
In a first aspect or embodiment of the invention, it has now been discovered that improved detergent compositions beyond those described in WO 98/42622 can be formulated by combining the hybrid zeolite-silicates of WO98/42622 with particular detergent ingredients.
In a second aspect or embodiment of the invention, improved detergent compositions are formed by combining detergent ingredients with certain hybrid zeolite-cobuilders not specifically described in WO98/42622. In these materials, the hybrid builder has an occluded material other than silicate, such as sulfate, borate, nitrate, nitrite, phosphate, or Na
2
O.
In a third aspect or embodiment of the invention, improved detergent compositions are formed by combining detergent ingredients with combinations of hybrid zeolite-silicate and hybrid zeolite-cobuilder s
Pancheri Eugene Joseph
Roger St. Laurent James Charles Theophile
Rohrbaugh Robert Henry
Boyer Charles
Corstanje Brahm J.
Dressman Marianne
Glazer Julia A.
The Procter & Gamble & Company
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