text:
|Publication number
|Publication type
|Application number
|Publication date
|Apr 14, 1992
|Filing date
|Nov 20, 1990
|Priority date
|Jun 18, 1990
|Fee status
|Also published as
|Publication number
|John H. Shaw, Jr., Robert Mermelstein
|Original Assignee
|The Procter & Gamble Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (21), Referenced by (13), Classifications (16), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
This is a continuation-in-part of application Ser. No. 07/539,650, filed on June 18, 1990.
The present invention relates to granular laundry detergent compositions and to methods for their manufacture. More specifically, the invention relates to methods of overcoming hygroscopicity problems of 2,2'-oxodisuccinate detergency builders, especially tetrasodium 2,2'-oxodisuccinate; and to the builder agglomerate and granular laundry detergent compositions achieved by solving such problems.
2,2'-oxodisuccinate builder salts, e.g., tetrasodium 2,2'-oxodisuccinate, are attractive and efficient nonphosphorus detergency builders which despite being known since the 1960's have apparently eluded large-scale commercialization.
2,2'-oxodisuccinates are believed to have been first disclosed in U.S. Pat. No. 3,128,287, Berg, issued Apr. 7, 1964. Detergent compositions comprising 2,2'-oxodisuccinate as builder are disclosed in U.S. Pat. No. 3,635,830, Lamberti et al, issued Jan. 18, 1972. 2,2'-oxodisuccinic acid and the tetrasodium salt are freely water-soluble and are understood to act as a builder at least in part by complexing in aqueous solution with the calcium and/or magnesium ions which constitute a major fraction of ions found in wash-water, these latter ions being termed "water hardness".
Another well-known class of laundry detergent ingredients are the zeolites. Zeolite A, especially the sodium-exchanged form (Na-A) is an established laundry detergent builder. See U.S. Pat. No. 4,605,509, Corkill et al, issued Aug. 12, 1986. Zeolite A is substantially insoluble in water, at least by comparison with 2,2'-oxodisuccinate, and is understood to act as a builder, at least in part by trapping water hardness, especially calcium ions, in the unusual "cages" of its molecular structure.
Zeolite A is readily available in industry and is especially useful for detergency building purposes when it is in the 1-10 micron size range.
Recently, it has also become possible to synthesize 2,2'-oxodisuccinate using the attractive method of U.S. Pat. No. 4,798,907, MacBrair, Jr., et al, issued Jan.17, 1989.
The terms "2,2'-oxodisuccinate" and "oxydisuccinate" (apparently synonymous for literature search purposes) also appear with frequency in the literature, especially in recitals of builders for laundry detergent formulae. Exhaustive recital of these references (in excess of one hundred) is not possible here. See, for example U.S. Pat. No. 4,689,167, Collins et al, issued Aug. 25, 1987; U.S. Pat. No. 4,131,558, Bailey et al, issued Dec. 26, 1978; U.S. Pat. No. 4,116,852, Bailey et al, issued Sept. 26, 1978; U.S. Pat. No. 4,089,795, Bailey et al, issued May 16, 1978; U.S. Pat. No. 4,019,998, Benson et al, issued Apr. 26, 1977 and U.S. Pat. No. 3,939,100, Hau et al, issued Feb. 17, 1976. Likewise, there is a great number of disclosures of the use of Zeolite A in laundry detergent compositions.
In light of the extensive literature, it is remarkable that 2,2'-oxodisuccinate is still not actively being used in commerce, especially as a detergency builder.
A significant problem not previously believed to have been reported in the 2,2'-oxodisuccinate literature is that when 2,2'-oxodisuccinate builders are conventionally spray-dried to make a granular laundry detergent with other detergent ingredients such as zeolite builders, detergent surfactants and the like, they produce hygroscopic detergent granules which tend to "cake" or become sticky on storage, especially at high humidity. The severe hygroscopicity of tetrasodium 2,2'-oxodisuccinate can be graphically illustrated simply by overnight exposure of freeze-dried solid tetrasodium 2,2'-oxodisuccinate to a humid atmosphere, when a paste or even a liquid is formed owing to the high water absorption from the atmosphere.
The present invention is therefore directed at providing the granular laundry detergent formulator with a practical and useful solution to the 2,2'-oxodisuccinate hygroscopicity problem.
More specifically, it is an object herein to provide a process for making a built granular laundry detergent wherein at least a portion of the builder component is 2,2'-oxodisuccinate, especially in agglomerated form.
It is a further object to provide novel 2,2'-oxodisuccinate-containing agglomerates generally to the detergent formulator.
A third object is the provision of granular laundry detergent compositions formulated with the agglomerates of the invention.
Other objects, such as the provision of useful fully-formulated granular detergent products, are also secured, as will be seen from the following disclosure.
All percentages and proportions herein are by weight unless otherwise indicated.
Succinctly stated, this invention improves a granular built laundry detergent composition wherein the builder comprises 2,2'-oxodisuccinate (e.g, tetrasodium 2,2'-oxodisuccinate, typical of what is hereinafter intended by the abbreviation "ODS" and zeolite A. Such compositions tend, as noted, to cake by virtue of the hygroscopicity of the ODS.
The present invention provides the improvement which comprises: preparing said laundry detergent composition by a process characterized by the steps of: (a) coagglomerating the ODS with zeolite A separately from the making of the balance of the granular built laundry detergent composition; and (b) mixing the ODS/zeolite agglomerate particles produced in step (a) with the balance of said granular built laundry detergent composition.
Without intending to be limited by theory, at the heart of this invention is the surprising finding that although there are conditions under which zeolite A can apparently be mixed with 2,2'-oxodisuccinate without significantly improving the hygroscopicity of the latter (e.g., when the detergent ingredients are all conventionally spray-dried), if the ODS and zeolite are brought together under agglomerating, as distinct from spray-drying or simple solids mixing conditions, a new and useful ODS/zeolite composition with significantly reduced hygroscopicity and numerous other advantageous properties is produced.
The above-identified "balance" of the granular laundry detergent is the sum of all the components of the detergent composition other than the ODS/zeolite agglomerate, and is generally comprised of particulate detergent ingredients. It is typically a spray-dried detergent powder although alternate processes for making it, such as flaking, extrusion or the like may be equally practical; and it generally comprises from about 5% to about 95%, preferably from about 40% to about 80%, more preferably still from about 65% to about 85% of the detergent composition as a whole. For best results, the balance is of course preferably substantially free from ODS. In certain preferred embodiments of the invention, it is also substantially free from zeolite; that is to say, all the ODS and zeolite of the granular laundry detergent are found in the ODS/zeolite agglomerate.
Conveniently, agglomeration according to the method of the invention requires only water, zeolite A and ODS; and it can be carried out in a conventional pan agglomerator. The content of agglomerate in the granular laundry detergent composition is generally from about 5% to about 95%, more preferably from about 15% to about 60%, more preferably still, from about 15% to about 35%.
In its composition embodiments, the invention also provides a composition of matter adapted for use as a builder for granular laundry detergents, in the form of agglomerates which are the product of water-agglomerating zeolite A and ODS: these generally comprise: (i) from about 5% to about 35%, preferably from about 15% to about 25% by weight ODS (preferably consisting essentially of tetrasodium 2,2'-oxodisuccinate); (ii) from about 35% to about 70% zeolite A (preferably from about 50% to about 70%, most preferably from about 55% to about 65% zeolite A: very preferably this component consists essentially of 1-10 micron zeolite Na-A, dry basis) and (iii) water, preferably no more than about 30%, more preferably from about 10% to about 20%, with the water being wholly or largely in the bound state.
Adding flexibility for the detergent formulator, it is also possible to have present in the agglomerate-making a water-crystallizable inorganic salt, such as sodium carbonate. Sodium carbonate can be present at low levels, e.g., about 1% to about 5%, with little impact on the properties of the agglomerate. This is fortunate since low levels of sodium carbonate sometimes contaminate technical grades of zeolite and/or ODS. If sodium carbonate is used at an appreciable level, satisfactory agglomerates can still be made which will typically contain from about 25% to about 35% zeolite A and from about 25% to about 35% sodium carbonate, provided that the sum of zeolite A plus water-crystallizable inorganic salt is from about 50% to about 70%. Such embodiments do, however, tend to absorb water to a greater extent than low-carbonate-level or carbonate-free embodiments of the agglomerates of this invention.
Although it is not intended to generally exclude embodiments of the invention wherein the water-crystallizable inorganic salt is other than sodium carbonate (sodium sulfate, for example, being a conceivable substitute) it should be noted that salts known to adversely affect the calcium sequestration capacity or calcium sequestration rate of zeolite Na-A are preferably avoided, or their presence minimized herein. Such salts are typically highly alkaline as illustrated by sodium hydroxide and the water-soluble sodium silicates. Impurity levels of such salts, e.g., the normally analyzable impurity levels of such salts in detergent-grade zeolite Na-A are, of course, tolerable; but for optimum results, the zeolite is water-washed before agglomerating with ODS.
ODS agglomerates in accordance with the invention are generally spheroidal, glassy, free-flowing and low in hygroscopicity; these agglomerates are visually pleasing, have high density (e.g., about 1000 grams/liter which is desirable for the formulator of compact granular detergents), possess outstanding resistance to compression, are not friable to the extent that they can freely be pneumatically transported in the detergent plant without breaking up, dissolve freely to leave equal or less residue on laundered fabrics as compared with otherwise processed mixtures of the components, are readily dry-mixed with the balance of the granular detergent composition and have numerous other advantages.
Although as noted the invention includes water-crystallizable salt-containing embodiments, the ODS agglomerates of this invention in their most unusual and preferred form contain only ODS builder salts, zeolite A and water: such agglomerates have the advantage of simplicity in not requiring any inorganic salts or indeed any separate organic binder whatever. Conventional agglomeration of detergent ingredients in contrast usually requires crystal-forming inorganic salts such as sodium carbonate to be present.
In view of the hygroscopicity of ODS when incorporated in the art-disclosed fashion into a conventionally spray-dried granule (even when zeolite A is present), it is remarkable that it has now proved possible, as taught herein, to agglomerate this combination of ingredients to form particles with such highly desirable handling characteristics. It is further remarkable that the resistance to water-pickup, both of the agglomerates and of detergent compositions into which they are dry-mixed, is significantly improved. Thus in one especially preferred embodiment made simply from ODS, zeolite and water, the invention encompasses a composition consisting essentially of agglomerates having a mean particle size in the range from about 500 micron to about 1100 micron comprising the aforementioned levels of 2,2'-oxodisuccinate builder salts (preferably consisting essentially of tetrasodium 2,2'-oxodisuccinate) and the aforementioned levels of zeolite A (preferably consisting essentially of 1-10 micron zeolite Na-A); said agglomerates having a hygroscopicity, determined (typically, gravimetrically) by net water gain after equilibration at a temperature of 21� C. for a period of 7 days at two humidity levels, namely 50% and 80% relative humidity (RH), of about 10% or less (50% RH) and about 60% or less (under the very severe condition of 80% RH).
Although the hygroscopicity advantages of the latter embodiment can be matched when up to about half of the zeolite is substituted by sodium carbonate, only an agglomerate having relatively high zeolite levels and relatively low sodium carbonate levels (typically about 5% or less, more preferably 1% or less) will approach the excellently low hygroscopicity of an even more highly preferred embodiment of the invention consisting essentially of agglomerates comprising: (i) from about 15% to about 25% tetrasodium 2,2'-oxodisuccinate and (ii) from about 55% to about 65% 1-10 micron zeolite Na-A provided that the sum of said components (i) and (ii) is from about 75% to about 85% and (iii) from about 10% to about 20% water (water contents of agglomerates herein being generally specified on a "freshly made" basis); such agglomerates have a hygroscopicity, determined (typically, gravimetrically) by net water gain after equilibration at a temperature of 21� C. for a period of 7 days at 50% and 80% relative humidity (RH), of about 1% or less (50% RH) and about 30% or less (80% RH).
In its detergent composition embodiments, the present invention also encompasses the desirable substantially non-hygroscopic granular detergent compositions made possible by the invention. These generally comprise (i) at least 5%, preferably from about 15% to about 25% detersive surfactant (this component typically being selected from the group consisting of anionic and nonionic detersive surfactants) and (ii) at least 5%, preferably from about 15% to about 35%, of detergency builder in the form of ODS agglomerates according to the invention. Such fully-formulated granular laundry detergents may also contain other conventional detergent ingredients, such as optical brighteners, peroxygen bleaches e.g., perborate and percarbonate, bleach activators e.g., tetraacetylethylenediamine and the like. The formulator may choose to substitute detergency builders of the art, such as phosphate builders, for a portion of the ODS agglomerate of the invention.
As noted, the laundry detergent compositions of this invention comprise, in major part, conventional ingredients that are quite familiar to detergent formulators. Advantages of the granular detergent compositions of this invention include that they, like the ODS agglomerates of the invention, are substantially non-hygroscopic. They can include but do not require special binders or crispeners such as sodium silicate, clays or the like, and perform excellently for their intended purpose of laundering fabrics in an aqueous laundry bath.
As explained above, the present invention resides in the finding that when ODS is water-agglomerated with zeolite A (or, if the formulator desires, is water-agglomerated with Zeolite A and water-crystallizable inorganic salts) separately from the making of the balance of the detergent composition, unique detergency builder particles (ODS agglomerates) are formed, which in turn makes it possible to provide new and improved granular laundry detergents simply by admixing the agglomerates and conventional particulate detergent ingredients.
Suitable zeolites for use herein are 1-10 micron size zeolites of the kind which form roughly equidimensional crystallites (See for example Breck, "Zeolite Molecular Sieves", Wiley-Interscience, New York, N.Y, 1974. It is very preferable to have an effective builder as the zeolite component: zeolites known to be useful detergency builders and preferred for use herein include the calcium-binding zeolites, e.g., the Na-form zeolites of group 3 especially "zeolite A", for example as disclosed in German Pat. No. 2 422 655 or U.S. Pat. No. 4,605,609, Corkill et al. Conventional detergent-grade zeolite A, sodium-form (Na-A) is readily available in industry or can be synthesized as described by Breck supra. Although for purposes of clarity, weights herein are given on a dry basis, the formulator should be aware that commercially available detergent-grade zeolites generally contain about 20% water as delivered. This water does not need to be removed before making ODS agglomerates according to the invention. Detergent-grade zeolites may be highly pure, which is of course preferable, or may contain impurities provided that their level is not such as to interfere with the working of the invention.
The ODS builder starting-material is typically that of U.S. Pat. No. 4,798,907 MacBrair et al. Although it is highly preferred to use highly pure, e.g., recrystallized or methanol-washed tetrasodium 2,2'-oxodisuccinate, it is also possible to use technical grades comprising about 85% by weight, or more, dry basis, of tetrasodium ODS. Impurities when present are usually from the synthesis, such as maleate, fumarate or malate salts.
In more detail, the term "ODS" (acronym "ODS") herein refers to a known class of materials, namely ODS builder salts of quality satisfactory for laundry detergent uses. Most simply and very preferably, ODS builders are illustrated by tetrasodium ODS, although tetrapotassium ODS and tetralithium ODS can be substituted for the sodium salt. 2,2'-oxodisuccinic acid is also usable but is not as suitable. Preferably when using the acid, pH correction or neutralization, e.g. with NaOH, is carried out in an additional pre-processing step, prior to agglomeration.
Most generally, ODS builder salts comprise anions (the predominant anion being 2,2'-oxodisuccinate) and cations (the predominant cation, especially in the preferred embodiments, being sodium). To be fit for the intended purpose, the fraction of all anions representing organic anion impurities and the fraction of all cations representing multivalent cation impurities will each generally be low, e.g., the total of all such impurities is typically less than 20% by weight dry basis of the ODS builder salt composition. In practice, this generally means that 60% or more of the anions, preferably 80% or more, are 2,2'-oxodisuccinate and 75% or more of the cations, preferably 99% or more, are water-soluble monovalent cations, preferably sodium, potassium or lithium, most preferably sodium. Organic anions other than 2,2'-oxodisuccinate, when present, should comprise 15% by weight or less, dry basis, of the ODS. Non-ODS anions are typically comprised of the anions of simple organic carboxylate salts as noted, usually nonether carboxylates such as fumarate salts, maleate salts and malate salts.
Although as noted for purposes of clarity, weights herein are given on a dry basis, the formulator should be aware that according to the present invention, it is preferred to work with the ODS component as an aqueous solution or as a concentrated aqueous slurry. Typical water contents of ODS starting-materials as received, e.g., as made using the above-referenced Mc. Brair et al process, are in the range from about 60% to about 70% (the corresponding ODS content typically being from about 30% to about 40%). It is not essential that the water in such ODS starting-materials should be removed before making agglomerates according to the invention, a significant advantage when one considers the energy costs and technical difficulty of drying ODS builder salts. However, both with transportation costs and with the best possible agglomerate compositions in mind, it is preferred to further concentrate the ODS starting-material solutions, e.g., by evaporation, to an ODS concentration in the range from about 30% to about 60%, preferably from about 50% to about 60%, prior to agglomerating with zeolite according to the invention.
Interestingly in this connection, it has been found (counter to often-observed tendencies) that ODS solubility apparently increases with increasing purity. As the ODS impurity content (see discussion hereinabove) increases, it becomes increasingly difficult to achieve a pumpable ODS solution or slurry at the highest concentrations of the above ranges. This gives yet another reason for which the agglomerate manufacturer should seek to obtain the best possible grade of ODS.
On the other hand, a remarkable finding in connection with the instant invention is that concentrated aqueous solutions of technical-grade ODS indeed tend to "gel" over a period of storage. Although pumping is difficult, such gels can in fact successfully be used as a starting-material for the preparation of ODS agglomerates which have a relatively high (e.g., 20%, or higher) ODS content.
Whether one is concerned with technical or purer grades of ODS, there is little doubt that this builder has unique properties, e.g., forming unique glassy phases during the instant agglomeration, which as is here demonstrated impact significantly on its chemical engineering.
The agglomerates of the invention can additionally contain various optional ingredients. Agglomeration can, for example be conducted in the presence of limited amounts of sodium linear alkylbenzenesulfonates (although exclusion of this and other detersive surfactants is preferable) or of water-crystallizable inorganic salts such as sodium carbonate at levels specified in the summary hereinabove. On the other hand, it is an advantage that certain highly alkaline salts sometimes used as binders in conventional agglomeration, such as sodium silicate, do not have to be present. In the preferred embodiments, no sodium silicate is added in the agglomeration according to the invention. Sodium silicate has on occasion been implicated in diminishing the calcium sequestration rate of zeolite A, thus it is particularly advantageous that it is not a necessary component of the ODS agglomerates. In general, especially in connection with optional ingredients in preferred embodiments of the instant ODS agglomerates containing such salts, the expression "water-crystallizable inorganic salts" refers to compounds selected from sodium carbonate (soda ash), potassium carbonate and the like, as well as mixtures thereof. The preferred form of optional ingredient is anhydrous, fine powder with particle size closely matching the zeolite.
The ODS agglomerates herein generally contain water at levels specified in the summary hereinabove. Water contents of the freshly prepared ODS agglomerates are best determined by material balance, more specifically, the water content of the agglomerate can be measured by subtracting water lost during agglomeration from the water content of the starting-materials. After hygroscopicity testing, water may also be determined gravimetrically or by any other conventional water-determination method. Care will generally be exercised to ensure that thermal decomposition of ODS does not occur to any significant extent during water content determinations.
Essential to the practice of this invention is the provision of agglomerates of ODS and zeolite A, which are made separately from the remainder (balance) of the granular detergent composition. The agglomeration process of the invention is remarkable in its apparent lack of reliance on salt hydration to a stable state for agglomerate particle formation. In detail, the process can be illustrated as follows. Note that there does not have to be any water-crystallizable inorganic salt. In a typical preparation of an ODS agglomerate from an aqueous slurry of tetrasodium 2,2'-oxodisuccinate (Na4 ODS), 1-10 micron zeolite Na-A and water, the slurry consisting essentially of Na4 ODS and water is first concentrated if needed, so that the water content is about 40% to about 50%. This can be done using any convenient evaporative means, such as a vacuum drum dryer. Preferably, temperatures during such pre-agglomeration evaporation are above ambient, for speed, but to avoid any ODS decomposition tendency are below about 100� C., more preferably below about 60� C.
The zeolite A (or optionally but less desirably a mixture of zeolite A with water-crystallizable inorganic salts) is loaded into an agglomerator. Any conventional agglomerator can be used, such as an inclined pan agglomerator (sometimes known as an inclined disk agglomerator), a rotary drum agglomerator, or a vertical blender/agglomerator.
Suitable agglomerating equipment is more extensively illustrated and discussed in standard works such as "Handbook of Powder Technology", by C. E. Capes, edited by J. C. Williams and T. Allen, Elsevier, 1980. See especially pages 63-96, incorporated herein by reference.
Agglomerating machines (agglomerators) are often referred to by engineers by the name of the corporation which manufactures them. Suitable agglomerator types on this basis are Eirich agglomerators, Schugi agglomerators and Lodige agglomerators. See also "Handbook of Powder Technology" supra, at page 72.
In a preferred embodiment, the agglomerates according to the present invention are made in an Eirich mixer, Machinenfabrik Gustav Eirich.
The entirety of the zeolite (or zeolite-containing solid mixture as noted) is loaded in one batch into a suitably sized Eirich agglomerator. Is should be emphasized that staged addition of zeolite during the agglomeration can lead to inferior results.
The agglomerator is set in motion, thereby forming a free-flowing moving bed "stirred bed" of zeolite A (or zeolite-containing particulate solid) in the agglomerator. The concentrated aqueous mixture of 2,2'-oxodisuccinate builder and water ("ODS slurry"), prepared as described above, is now added. The agglomeration process temperature can be mild, e.g., ambient, slightly below ambient, or above ambient. A temperature elevated above ambient provides for greater drying of the ODS agglomerate during the agglomeration process, which in turn provides particles having improved long-term physical properties and a higher ODS content than obtainable without the elevated process temperature. Excellent results are obtained at temperatures in the range from about 100� C. to about 300� C., more preferably from about 50� C. to about 150� C., even more preferably from about 100� C. to about 150� C.
The ODS slurry addition can in general be done by pouring, by spraying through a spray nozzle or (especially when the ODS slurry is very thick) by pumping it through a large orifice. Whatever precise addition method is used, it is preferred to spread the ODS slurry evenly over the stirred zeolite bed. In general, the ODS addition can be done "in one shot", can be staged or (most conveniently and preferably) can be accomplished in a single continuous addition to a zeolite bed which is being stirred at high shear. High-shear stirring of the zeolite speeds the process, allowing more rapid throughput. It also has the advantage of forming more uniform, relatively small ODS agglomerates, which are well-matched for dry-mixing with conventional detergent granules to make fully-formulated detergent products quite resistant to segregation. (The terms "dry-mixing", "admixing" and "mixing" as used in connection with mixing solid materials herein are equivalent, the term "dry-mixing" often being used by preference by engineers in the granular detergency field.)
In a preferred mode, a stream of air which can be at ambient temperature, cooled to below ambient temperature, or more preferably heated to above ambient temperature (typically about 100� C., preferably about 150� C. and relatively dry), is passed over the surface of the moving ODS/zeolite mixture during the agglomeration process. Although in general there may be passage of air throughout the process, the stage at which the air-stream produces the greatest improvement occurs when the stirred bed has already started to form discrete agglomerate particles. Apparently, the air-stream assists "detachment" of the particles. Whether by evaporation of water or by some other mechanism, the air stream thus improves the already excellent results. Regardless of how the process is carried out in terms of air-stream, stirring of the zeolite bed with its associated wet ODS is continued until substantially complete detachment of the resulting agglomerate into discrete particles. Agglomerates are secured which are spheroidal, glassy, free-flowing and low in hygroscopicity, which have outstanding resistance to compression and are not friable; the two latter characteristics are especially advantageous in view of the subsequent dry-mixing of the agglomerates with the remainder of the granular detergent composition.
If the ODS/zeolite agglomerates are not sufficiently dried during the agglomeration process, it is preferred that an additional post-drying operation, such as fluidized bed drying or aging, follow the agglomeration process. However, such steps are not essential.
While not intending to be bound by theory, it is believed that drying the agglomerated particles following the agglomeration process provides particles having improved long-term physical properties, particularly after high humidity storage. It is further believed that if the agglomerated particles are dried sufficiently during the agglomeration process through the use of heat or some other drying mechanism, the particles will possess the aforementioned improved long-term physical properties, and will have the additional benefit of having an increased ODS concentration, up to about 35% by weight, preferably from about 15% to about 25% by weight, as compared to agglomerated particles prepared without drying during agglomeration.
The agglomeration step of the granular detergent-making process of the present invention is advantageously carried out in the presence of heating, with any necessary post-drying of the agglomerate, and in the absence of added binders. In a preferred embodiment the process is completed by mixing the above-prepared agglomerate with a balance of said granular laundry detergent composition consisting of a granular detergent powder (this can be spray-dried in the conventional manner) comprising at least one detersive surfactant.
The ODS agglomeration process, and thus the overall granular laundry detergent-making process of the invention, has several advantages, including simplicity, convenience, the ability to operate (in the agglomeration stage at least) without added heating (although heating is preferred), and the ability to make excellent agglomerates without using sodium silicate as an agglomerating aid (see for comparison U.S. Pat. No. 4,528,276, Cambell et al., issued July 9, 1985 which apparently requires both sodium silicate and heat). Evidently, the major advantage as already noted, is the preparation of a conveniently handled substantially non-hygroscopic ODS builder composition, and thereby, of improved fully-formulated detergent granules.
Apart from the agglomerates described hereinabove, the granular laundry detergent compositions of this invention comprise various conventional ingredients such as detersive surfactants, and adjuncts such as detersive enzymes, bleaches, bleach activators, detergency (non-ODS) builders and the like, all well-known in the art and in commercial practice. These conventional ingredients (with the exception of perfumes and colorants which can be sprayed on and are generally low-level additives) are solids, at least when they are to be mixed with the instant agglomerates or as found the final form of granular detergent compositions according to the invention, and can take the form of spray-dried "base granules", "noodles" or other extrudates, flakes, powders, or conventionally made non-ODS agglomerates.
The granular laundry detergent compositions of this invention will typically contain organic surface-active agents ("surfactants") to provide the usual cleaning benefits associated with the use of such materials. Detersive surfactants (sometimes also called "detergent surfactants") useful therein include well-known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical of these are the alkyl benzene sulfonates, alkyl- and alkylether sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, amine oxides, alpha -sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known from the detergency art. In general, such detersive surfactants contain an alkyl group in the C9 -C18 range; the anionic detersive surfactants can be used in the form of their sodium, potassium or triethanolammonium salts; the nonionics generally contain from about 5 to about 17 ethylene oxide groups. U.S. Pat. Nos. 4,111,855 and 3,995,669 contain detailed listings of such typical detersive surfactants. C11 -C16 alkyl benzene sulfonates, C12 -C18 paraffin-sulfonates and alkyl sulfates, and the ethoxylated alcohols and alkyl phenols are especially preferred in the compositions of the present type. Also useful as the surfactant are the water-soluble soaps, e.g. the common sodium and potassium coconut or tallow soaps well-known in the art.
The detersive surfactant component of the instant granular laundry detergent compositions can comprise as little as 1% of the fully-formulated detergent compositions herein, but preferably such compositions will contain 5% to 40%, even more preferably 10% to 30%, of surfactant. Mixtures of anionic surfactants such as the alkyl benzene sulfonates, alkyl sulfates and paraffin sulfonates are preferred, especially in conjunction with nonionic polyethoxylates for through-the-wash cleansing of a broad spectrum of soils and stains from fabrics.
The granular laundry detergent compositions herein can contain other ingredients which aid in their cleaning performance. For example, the invention encompasses preferred embodiments in the form of granular laundry detergent compositions containing non-ODS, non-zeolite builder/metal ion sequestrant as illustrated by one or more of ethylenediaminetetraacetate, ethylenediaminedisuccinate (EDDS), 1,2-oxoethanediylbis(aspartate) (OEDBA), citrate, or polyacrylate. Such materials can be used as their art-disclosed levels. See for example U.S. Pat. No. 3,579,454 or application Ser. No. 07/392,168 filed Aug. 10, 1989, now U.S. Pat. No. 4,983,315, Glogowski et al, issued Jan. 8, 1991, incorporated by reference, for typical examples of the use of such materials in various cleaning compositions.
If sodium silicates are desired for use as builders or sequestrants, as washing machine anti-corrosion agents or even as granule crispeners in the instant detergent compositions, they will be included in the portion of the detergent composition other than the ODS/zeolite agglomerate, i.e., in the "balance" of the fully-formulated granular laundry detergent.
The fully-formulated granular laundry compositions herein also preferably contain enzymes to enhance their through-the-wash cleaning performance on a variety of soils and stains. Amylase and protease enzymes suitable for use in detergents are well-known in the art and in commercially available liquid and granular detergents. Commercial detersive enzymes (e.g., mixtures of amylase and protease) are typically used at levels of 0.001% to 2%, and higher, in the present compositions. Enzymes are generally added to the instant compositions in the form of particulate solids, which can simply be mixed with the agglomerate and other components of the detergent balance.
Moreover, the detergent compositions herein can contain, in addition to ingredients already mentioned, various other optional ingredients typically used in commercial products to provide aesthetic or additional product performance benefits. Typical ingredients include pH regulants, perfumes, dyes, bleach, optical brighteners, soil suspending agents, bactericides, preservatives, suds control agents, soil release agents such as those of U.S. Pat. No. 4,877,896, Maldonado, Trinh and Gosselink, issued Oct. 31,1989, and the like. As known in the art, certain such ingredients can be used to advantage at very low levels but more typically, they comprise 0.5% to 30% of granular laundry detergents in the fully-formulated form.
The portion of the instant granular detergent compositions other than the ODS-containing agglomerate can be prepared by any of the several well-known procedures for preparing commercial detergent compositions, provided that the ODS agglomerate is prepared separately and is dry mixed with the balance to complete the fully-formulated detergent composition.
Suitable manufacturing techniques include spray-drying, extrusion, rolling/flaking, and agglomeration. Particles of various ingredients can be dry-mixed in solid form. See, for example, "Detergents and textile washing: principles and practice", G. Jakobi and A. Lohr, 1987, Library of Congress Card Number 87-25299 or similar standard texts on detergent-making. In connection with processing and general handling of solid detergent ingredients, the following references are additionally instructive: Handbook of Powder Technology (publication details supra); see in particular Volume 1 entitled "Particle Size Enlargement"; and "Handbook of Powder Science and Technology", Eds. M. E. Fayed and L. Otten, Van Nostrand Reinhold, 1984, Library of Congress Card Number 83-6828.
One preferred approach useful herein is to spray-dry a slurry of detersive surfactants, non-ODS builders, and certain detersive adjuncts such as brighteners thereby forming a base granule, ODS agglomerate and enzyme particles are admixed to the base granule, forming the final granular detergent composition.
A quite different approach also capable of producing a granular laundry detergent in accordance with the invention is to form a dry-neutralized agglomerate between the acid form of an anionic detersive surfactant, alkaline inorganic salts and zeolite A and to blend the resulting composition with the ODS agglomerates of the invention, optionally adding particulate enzyme and, if desired, particulate sodium perborate.
Although mixing dry particulate materials with the ODS agglomerates to form the fully-formulated laundry detergent is the general practice, some exceptions, such ass spray-on of perfumes and dyes, have been noted hereinabove: another example of a spray-on to complete a fully formulated granular laundry detergent in accordance with the invention is to spray a molten or organic solvent-borne nonionic detersive surfactant, polyester soil release agent or the like, e.g., onto the mixture of agglomerates and other solid-form detersive ingredients, or onto the ODS/zeolite agglomerates. However, especially when the material sprayed on is relatively low-melting or has poor water-solubility, this practice is not preferred on account of the possibility either of producing a "tacky" detergent product, or of impairing the overall solubility of the granular laundry detergent.
In general, as noted supra, the practitioner will match the particle size ranges of the various dry-mixed components of the granular laundry detergent composition. It is an advantage of the ODS agglomeration process herein that it is readily adjusted by the practitioner to prepare a range of differently sized ODS agglomerate particles.
Particle size ranges of granular laundry detergents according to the invention generally range from about 50 micron to about 450 micron (mean about 200 micron) when the granular laundry detergent is to have compact form, and from about 150 micron to about 1000 micron (mean about 325 micron) for typical "one-cup" dosage products.
Without limiting the invention, the ODS agglomerates, process and granular laundry detergent compositions are further illustrated by the following examples.
Commercial detergent-grade sodium zeolite A (6.3 lb., water content 20%; a fine particulate in the size range 1-10 micron, obtainable from various manufacturers including W. R. Grace, Ethyl Corp., PQ Corp., --U.S; Birac Co. --Yugoslavia, Degussa G.m.b.H. --Germany; Ausidet, Mia Lanza, Laviosa, --Europe and Tosoh --Japan) is loaded into an inclined pan agglomerator (Eirich mixer, model RV-02).
The pan of the Eirich mixer is set in motion at 33 revolutions per minute (clockwise) and the rotor blade, a high-shear element, is set in motion counterclockwise at 1750 revolutions per minute.
An aqueous solution of tetrasodium 2,2'-oxodisuccinate (1.8 lbs., concentration 33%) is poured evenly over the moving bed of zeolite.
After about 3 minutes of continued stirring, high-pressure air is passed over the surface of the moving mixture for about 2 minutes while the Eirich continues in motion. Shortly thereafter, a rattling noise is heard as the product ODS agglomerates reach substantially complete detachment.
The resulting free-flowing ODS agglomerate is stable and ready for use without any further aging or conditioning. It contains about 7.5% ODS builder, about 65% zeolite A builder, about 26.5% water and about 1% impurities. On one hand, the agglomerate is quite stable to moisture pickup when stored outside a detergent carton and in equilibrium with a humid atmosphere at 50% RH (Relative Humidity). Even when the relative humidity is as high as 80%, the moisture pickup is judged significantly better relative to simple mixtures (non-agglomerated) of the ODS and zeolite components, or relative to the spray-dried ingredients in a laundry detergent granule. On the other hand, the agglomerate disperses readily when placed in water along with the balance of a granular laundry detergent composition to form an aqueous laundry bath. This efficient dispersion is important in that it avoids leaving residues on laundered fabrics.
A. ODS agglomerates are prepared as in Example 1.
B. Separately, a spray-dried detergent base powder is made by spray-drying conventional detersive ingredients. (Alone or with enzymes--see infra-this component serves to illustrate what is referred to elsewhere herein as "the balance of the granular laundry detergent composition.)
C. ODS agglomerates (40 parts), the base powder (59.5 parts) and particles of enzyme (0.5 parts) are mixed, thereby forming fully-formulated granular laundry detergent having the following composition:
______________________________________Ingredients Percent______________________________________(These components come from the ODS agglomerate):Tetrasodium 2,2'-oxodisuccinate 3.0Zeolite Na-A 1-10 micron (dry basis) 26.0(These components come from the base powder):C11-13 alkylbenzene sulfonate 12.0(neutralized, dry basis)C12 -C13 alcohol ethoxylate EO 6.5 1.0Tallow alcohol sulfate 7.5Zeolite Na-A 1-10 micron (dry basis) 3.0Optical brightener 0.23Sodium carbonate (dry basis) 14.0Perfume/minors 0.5Sodium silicate (1.6 ratio Na2 O:SiO2) 2.0Enzymes (Savinase, 6T) 0.5Water to 100______________________________________
In use, the composition of Example 2 efficiently launders fabrics in an automatic clothes washing machine. It performs well and leaves little or no residue on the laundered fabrics.
An aqueous solution of tetrasodium 2,2'-oxodisuccinate is quality checked by proton nuclear magnetic resonance spectroscopy (n.m.r) and high performance liquid chromatography (h.p.l.c) which shows that the impurity levels are no more than about 5% by weight. The solution is evaporatively concentrated to form an ODS slurry which is again n.m.r and h.p.l.c analyzed and found to have a total solids content of about 60%. 50.0 grams of this slurry are weighed Zeolite Na-A, as used in Example 1, about 100 g, is placed in the bowl of a Cuisinart BASIC or DLC-7 SUPER PRO model food processor having a steel high-shear cutting blade.
With the blade in motion, the ODS slurry is poured onto the moving zeolite solids. Over a period of a few minutes, the food processor is switched off intermittently so as to allow the operator to scrape any material sticking on the sides back into the agitated zone of the processor. Agglomerate beads having smooth outer surfaces and a roughly spherical appearance are formed. As mixing continues, air is passed over the surface of the agglomerates and they dry out or age over a few minutes to the point that they begin to rattle about in the processor. After about 3 minutes there is good detachment (the agglomerates do not stick to the walls of the processor or to each other to any significant extent). The processor is switched off and the ODS agglomerates are recovered.
The resulting free-flowing ODS agglomerate is stable and ready for use without any further aging or conditioning. It contains about 21% ODS builder, about 57% zeolite A builder, about 18.3% water and about 3.7% impurities.
ODS agglomerates having proportions of components in accordance with Example 3 are prepared using equipment, and process details as in Example 1.
The resulting free-flowing ODS agglomerate is stable and ready for use without any further aging or conditioning. The agglomerate is sieved and the fraction having size in the range 50 to 450 microns is retained. The agglomerate contains about 21% ODS builder, about 57% zeolite A builder, about 18.3% water and about 3.7% impurities.
A. ODS agglomerates are prepared as in Example 4.
B. Separately, a spray-dried detergent base powder is made by spray-drying conventional detersive ingredients.
C. ODS agglomerates (29 parts), the base powder (70.5 parts) and particles of enzyme (0.5 parts) are mixed, thereby forming fully-formulated granular laundry detergent having the following composition:
______________________________________Ingredients Percent______________________________________(These components come from the ODS agglomerate):tetrasodium 2,2'-oxodisuccinate 6.0Zeolite Na-A 1-10 micron (dry basis) 16.5(These components come from the base powder):C12.3 alkylbenzene sulfonate 13.0(neutralized, dry basis)C14 -C15 alkyl sulfate 5.0Zeolite Na-A 1-10 micron (dry basis) 4.5Optical brightener 0.3Sodium carbonate (dry basis) 23.0Sodium silicate (1.6 ratio Na2 O:SiO2) 2.3Sodium polyacrylate, m.w. 4500 (dry basis) 2.0PEG 8000 1.4DC-544 (Dow Corning) silicone/process aid 0.1Sodium sulfate 10.0(Additional Dry-mix)Enzymes (Savinase, 6T) 0.5(These components are sprayed on to the final product)Perfume 0.5______________________________________
In use, the composition of Example 5 efficiently launders fabrics in an automatic clothes washing machine. It performs well and leaves little or no residue on the laundered fabrics.
The procedure of Example 3 is repeated except that the zeolite is substituted by a 50:50 mixture (both components expressed on an anhydrous basis) of the identical zeolite with anhydrous sodium carbonate, a water-crystallizable inorganic salt.
The results are similar except that a distinct "dough" stage occurs between the initial mixing of the components and the final detachment of the ODS agglomerate particles from each other.
The resulting free-flowing ODS agglomerate contains about 22% ODS builder, about 30.7% zeolite A builder, about 30.7% sodium carbonate, about 12.7% water and about 3.9% impurities.
In the following examples, the granular detergent compositions are prepared as follows:
A. ODS agglomerates are prepared as in Example 5.
B. Other detergent ingredients with the except of perfume are solids with granulometry similar to the ODS agglomerate. A variety of suitable ingredients can be identified from Mc Cutcheon's. The ODS agglomerates and the balance of the detergent composition are dry-mixed. Perfume is sprayed on to form the final product.
The resulting detergent compositions are as follows:
______________________________________Example No. 7 8______________________________________Tetrasodium 2,2-oxodisuccinate 10 15Zeolite Na-A (1-10 micron) 21 31.5sodium silicate Na2 O:SiO2 ratio 2.0 2 3C12.3 Linear Alkylbenzenesulfonic acid, 20 15sodium saltSodium carbonate 20 20sodium sulfate 20 10sodium polyacrylate, m.w 4500 2 0Savinase, 6.0 T 0.5 0.5Perfume 0.3 0.5Water, impurities, minors . . . to 100 100______________________________________
In use, the compositions of the foregoing Examples efficiently launder fabrics in an automatic clothes washing machine. They perform well and leave little or no residue on fabrics.
An aqueous solution of tetrasodium 2,2'-oxodisuccinate is evaporatively concentrated to form an ODS slurry comprising 60% ODS solids.
Separately, 202.9 grams of Zeolite Na-A, as used in Example 1, are placed in the bowl of a Cuisinart DLC-7 SUPER PRO Model food processor having a steel, high-shear cutting blade.
With the blade in motion, 100.0 grams of the ODS slurry are poured onto the moving zeolite solids. Over a period of a few minutes, gummy spherical particles are formed. As mixing continues, air heated to 150� C. by a heat gun is blown into the food processor for about 30 seconds. The particles become free-flowing, detached spheres, which are recovered and ready for immediate use. A material balance on the composition indicates that all water not associated with the zeolite crystal structure is evaporated. The agglomerates contain 22% ODS builder, 59% zeolite A builder, 16% water, and 3% impurities.
A granular detergent composition is prepared as follows:
A. ODS agglomerates are prepared as in Example 9.
B. Separately, a spray-dried detergent base powder is prepared from conventional detersive ingredients.
C. ODS agglomerates (27.3 parts), base powder (70.4 parts), enzymes (0.3 parts), and citric acid (1.5 parts) are combined in conventional powder mixing equipment, while perfume (0.5 parts) is sprayed onto the powder.
The resulting fully-formulated laundry detergent is of the following composition:
______________________________________Ingredients Wt. Percent______________________________________(These components come from the ODS agglomerate):Tetrasodium 2,2'-oxodisuccinate 6.0Zeolite Na-A 1-10 micron (dry basis) 16.1(These components come from the base powder):C12 alkyl benzene sulfonate (neutralized) 15.0C14-15 alkyl sulfate 3.0Zeolite Na-A 1-10 micron (dry basis) 3.0Optical fluorescer 0.5Sodium carbonate 20.0Sodium silicate (1.6 ratio Na2 O:SiO2) 2.0Sodium polyacrylate, MW 4500 (dry basis) 1.0PEG 8000 2.0Sodium sulfate 12.0DC-544 silicone 0.1(Additional Dry-Mix)Citric Acid 1.5Enzymes (Savinase, 6T) 0.5(Spray-on to finished product)Perfume 0.5Water/misc. from all sources to 100%______________________________________
In use, the composition of Example 10 launders fabrics well in an automatic clothes washing machine, leaves little or no residue on the laundered fabrics, and has acceptable physical properties under high humidity storage testing.
In addition to the embodiments of the invention illustrated hereinabove, it is believed possible to provide alternate embodiments without departing from the spirit and scope of the invention. In such embodiments, alternate materials might for example be substituted for the zeolite A component of the ODS agglomerate. Such alternate materials should be generally be water-insoluble silicates, aluminosilicates or similar, provided that they are in the form of roughly equidimensional (that is to say "chunky" or near-spherical) crystallites in the 1-10 micron size range. Clays, such as layer aluminosilicates e.g., bentonite or montmorillonite, would in contrast not be considered suitable for substituting the zeolite component. In other alternate embodiments, the ODS agglomerates may be colored with non-staining blue or green dyes, or can be sprayed with perfumes for aesthetic appeal.
ODS agglomerates according to the invention have no known utility outside the detergency arts, e.g., they are not useful as petroleum industry-type zeolite catalyst particles etc. However, they are excellent for their detergency purpose, and very appealing to the detergent formulator even without further aesthetics modification, since they are quite white, uniquely strong and non-dusting, are free from clays, do not require hot-pressing manufacturing techniques, and do not contain amorphous silica or sodium silicate that would interfere with free dispersion in water or form residues on laundered fabrics.
|Cited Patent
|Filing date
|Publication date
|Jan 31, 1963
|Apr 7, 1964
|Pfizer & Co C
|2,2'-oxodisuccinic acid, derivatives thereof, and process for preparing
|Nov 24, 1969
|Jan 18, 1972
|Lever Brothers Ltd
|Detergent compositions containing oxydisuccing acid salts as builders
|Feb 14, 1975
|Feb 17, 1976
|The Procter & Gamble Company
|Combination alkali metal pyrophosphate-alkaline earth metal pyrophosphate detergent builder
|Jun 17, 1974
|Oct 12, 1976
|The Procter & Gamble Company
|Detergent compositions
|Sep 29, 1975
|Apr 26, 1977
|The Procter & Gamble Company
|Process for preparing a pyrophosphate-silicate detergent product
|Feb 13, 1976
|Mar 7, 1978
|The Procter & Gamble Company
|Process for preparing detergent compositions
|Feb 12, 1976
|May 16, 1978
|The Procter & Gamble Company
|Orthophosphate and silica-containing composition
|Aug 24, 1977
|Sep 26, 1978
|The Procter & Gamble Company
|Builders and built detergent compositions
|Nov 15, 1976
|Oct 31, 1978
|Union Carbide Corporation
|Zeolite agglomerates having controlled pore structure
|Feb 12, 1976
|Dec 26, 1978
|The Procter & Gamble Company
|Process for preparing an orthophosphate-silicate detergent product
|Nov 2, 1977
|Dec 25, 1979
|The Procter & Gamble Company
|Spray-dried detergent compositions
|Nov 2, 1978
|Nov 4, 1980
|Kao Soap Co., Ltd.
|Bleaching composition causing no color change or fading of colored and figured cloths
|Sep 23, 1980
|Dec 1, 1981
|The Procter & Gamble Company
|Abrasion resistant spray dried aluminosilicate detergent composition
|Nov 21, 1980
|Nov 8, 1983
|Colgate Palmolive Company
|Readily disintegrable agglomerates of insoluble detergent builders and detergent compositions containing them
|Mar 27, 1984
|Aug 13, 1985
|Dow Corning Corporation
|Detergent composition with siliconate-zeolite and silicate builder
|Mar 11, 1974
|Aug 12, 1986
|The Procter & Gamble Company
|Detergent compositions containing sodium aluminosilicate builders
|Jan 30, 1986
|May 5, 1987
|The Procter & Gamble Company
|Ether carboxylate detergent builders and process for their preparation
|Jan 30, 1986
|Aug 25, 1987
|The Procter & Gamble Company
|Detergency builder system
|Feb 26, 1988
|Jan 17, 1989
|The Procter & Gamble Company
|Controlled temperature process for making 2,2'-oxodisuccinates useful as laundry detergent builders
|Aug 28, 1987
|Apr 4, 1989
|Lever Brothers Company
|Antifoam ingredient for detergent compositions
|Jan 14, 1988
|Sep 25, 1990
|The Procter & Gamble Company
|Amino-functional compounds as builder/dispersants in detergent compositions
|Citing Patent
|Filing date
|Publication date
|Oct 14, 1994
|Nov 14, 1995
|Lever Brothers Company, Division Of Conopco, Inc.
|Process for the preparation of an enriched 2,2'-oxydisuccinate reaction mixture by removal of calcium malate
|Oct 14, 1994
|Nov 14, 1995
|Lever Brothers Company, Division Of Conopco, Inc.
|Process for the purification of alkaline earth metal salts of 2,2'-oxydisuccinate by acidification
|Dec 22, 1994
|Dec 5, 1995
|Lever Brothers Company, Division Of Conopco Inc.
|Diaminoalkyl di(sulfosuccinates) and their use as builders
|Mar 3, 1994
|Jul 23, 1996
|The Procter & Gamble Company
|Detergent compositions with builder system comprising aluminosilicates and polyaspartate
|Jun 20, 1995
|Oct 8, 1996
|Albemarle Corporation
|Formulated branched chain alcohol ether sulfate compounds
|Jun 20, 1996
|Jan 27, 1998
|Lever Berothers Company, Division Of Conopco, Inc.
|Intimate admixtures of salts of 2,2'-oxydisuccinate (ODS) with selected glycolipid based surfactants to improve the flow and handling characteristics of the (ODS) salt
|Jun 20, 1996
|Feb 3, 1998
|Lever Brothers Company, Division Of Conopco, Inc.
|Intimate admixtures of salts of sulfo carboxymethyloxy succinate (SCOMS) with selected glycolipid based surfactants to improve the flow and handling
|Mar 21, 1997
|Sep 28, 1999
|The Procter & Gamble Company
|Spray-dried component comprising chelant
|Oct 10, 2006
|Sep 8, 2009
|Henkel Ag & Co. Kgaa
|Scented solid substances comprising a non-ionic surfactant-impregnated carrier
|Jul 26, 2006
|May 8, 2012
|Nippon Shokubai Co., Ltd.
|Iminocarboxylic acid salt-containing solid composition and production method thereof
|Jul 26, 2006
|Feb 1, 2007
|Nippon Shokubai Co., Ltd.
|Iminocarboxylic acid salt-containing solid composition and production method thereof
|Oct 10, 2006
|May 17, 2007
|Rene-Andres Artiga Gonzalez
|Scented solid substances
|Feb 12, 2009
|Aug 20, 2009
|Nigel Patrick Somerville Roberts
|Delivery particle
|U.S. Classification
|510/361, 510/532, 510/507, 510/443, 510/506, 510/323, 510/444
|International Classification
|Cooperative Classification
|European Classification
|Feb 19, 1991
Owner name: PROCTER & GAMBLE COMPANY, THE
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:SHAW, JOHN H. JR.;MERMELSTEIN, ROBERT;REEL/FRAME:005612/0130
Effective date: 19901120
|Sep 26, 1995
|Fee payment
Year of fee payment: 4
|Nov 9, 1999
|Maintenance fee reminder mailed
|Apr 16, 2000
|Lapse for failure to pay maintenance fees
|Jun 27, 2000
|Expired due to failure to pay maintenance fee
Effective date: 20000414


text:
Pop star Justin Bieber was arrested early this morning in Miami Beach, FL with TMZ.com listing his charges as including driving under the influence, drag racing, resisting arrest and driving on an expired license. TMZ says that Bieber was stopped for street racing his Lamborghini Gallardo, then failing a field sobriety test, and is being charged with resisting arrest for "refusing to take his hands out of his pockets."
Justin Bieber Dui
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Megan and Rob's Tofino wedding brings a little bit of long beach's winter storm season to the dryer than average summer we have been having. This was our first chance to capture a wedding in Tofino and it was such a beautifully planned and love filled event that we are thrilled we got to be the ones to photograph all the great moments. They chose a Tofino wedding so their guests could get away for a weekend and enjoy all the things they loved about storm season getaways on the west coast. This day started at Long Beach Lodge with all the preparations then portraits in the lodge and on the beach. There is a saying t0 never turn your back on the sea and this lesson was well learned that day! We were all gathered for wedding party photos just steps from the stairs to the beach right in front of the resort lodge. The tide seemed a ways out with a lot of sandy beach but I noticed a wave broke and just kept coming up the beach. As it got closer I realized it wasn't slowing and yelled run at which point I grabbed Megan's train of her dress, Megan grabbed her little niece, Aaron grabbed our bags and after the wave broke we were all accounted for with me wet from the knees down and shoes full of sand and a bridesmaid who was glad her dress was black and of a material that dried quickly! The first thing out of Megan's mouth wasn't alarm over whether her dress was dry but"Did anyone get that?!" I was saving the dress, Aaron our gear and the videographers were in between shots but we did get the laughter afterwards. We learned a Tofino lesson to always ahve a dry pair of shoes in the car and that if the sand doesn't have many footprints on it new ones are likely to be washed away very soon! The rest of the day went seamlessly with the ceremony at St. Columba Church with cocktails at the Ice House Oyster Bar in the harbour. Guests were then transported by school bus to one of our favourite spots in Tofino – Shelter Restaurant for delicious food, drinks, toasts, hugs and warm wishes. Every detail of this day was filled with love – not just the love between Megan and Rob but the love they wanted to pour out on all the people most precious to them who were in attendance. From the incredible stationary and invites with vintage stamps – all custom made by Megan!! (she provided the lovely images of the invites below before she mailed them out) – the welcome packages with wine from favourite BC wineries, custom designed maps with favourite Tofino spots marked, monogramed buttons, custom stick on tattoos, individual bags for the wedding party and Coach umbrellas in case of rain this was all about making every single guest feel so loved and their attendance appreciated. Together they collected vintage pieces for the tablescapes and crafted their Love marquis light, the table numbers and wooden signs by hand. Megan's dress was hand made with french lace and silk by Alida's Gowns and her accessories were sourced from local BC artists. The orchestration of the day was flawless thanks to Tofino wedding planner Rare Earth Wedding Event Productions. We can't thank Rob and Megan enough for letting us in on their day to create these images for them. Our favourite moment of the day was watching Rob and Megan exit the church with bells chiming, friends and family waving streamers and the two of them with huge smiles on their faces. It's what the whole day is all about. For our first Tofino wedding this was a fantastic day that will be hard to beat!
Venues: Long Beach Lodge, The Ice House Oyster Bar, Shelter Restaurant | Bride's Attire: Custom gown by Alida's Gowns, Crystal hair band by David & Chiyo, Jewelry by BHLDN, Shoes John Fluevog Groom's Attire: Suit by Perry Ellis, The Tie Bar, NHL cufflinks | Wedding Planner: Rare Earth Wedding Event Production | Florist: Flowers to You | Hair Stylist: Salty Dolls | Makeup Stylist: Emmy Humber | Decor – DIY | Stationary DIY | favours: Homemade Jam with berries from Ruby Red Farms | Bridal Party gifts: Coach | Videographers: On The Beach Tofino Wedding Videos


text:
SANTA CLARA, Calif. -- Quinton Dial may soon be healthy enough to play for the San Francisco 49ers, who need the depth on the defensive line.
Dial, a fifth-round pick from Alabama, is practicing this week after coming off the physically unable to perform list. He may not have to wait long for playing time due to a need at nose tackle. He also can play defensive end.
I reached out to draft expert Steve Muench of Scouts Inc. to get his thoughts on Dial when he came out of school. Muench said Dial has ability and fits the 49ers' scheme. But there are concerns.
Here's Muench: "The first thing I think about is his blindside block on Georgia quarterback Aaron Murray in last year's SEC championship. His greatest strength as a player is defending the run. He's tough to move off the ball and he has the upper-body strength to control blockers. He fits well in San Francisco's scheme because he can line up on the inside or the outside in that scheme, plus he can help free up those talented linebackers by occupying blockers. If he stays healthy and they can get him to consistently play at a high level, he could prove to be a valuable role player. Those are big ifs based on his history and tape, though. We gave him a seventh-round grade. Injury concerns played a role and we may have moved him into the late fifth-round range if he was healthy, but they aren't the only reason he didn't grade out as an earlier pick. He's not much of a threat to get to the quarterback himself and, more importantly, we had concerns about his motor."
Still, Dial has a chance in San Francisco because of coaching and the talent around him. He should be able to get up to speed.


text:
The New York Times in reviewing Jennifer Jordan's book about the first five women who climbed K2 (and had unhappy ends) notes the women also had unhappy lifes. The book is entitled "Savage Summit : The True Stories of the First Five Women Who Climbed K2, the World's Most Feared Mountain." For instance there's Wanda Rutkiewicz who climbed 8 of the world's 14 peak over 8,00 meters. She had three husbands, few friends and fellow climbers stole her sleeping bag on Everest and her fellow male climbers claimed she never summited Annapurna until she produced the pictures to prove it. Chantal Mauduit was derided for using sherpas –which most climbers use. There was Alison Hargreaves who is believed to have perished on K2 as an attempt to safe her flagging fortunes. There other woman are Julie Tullis and Liliane Barrard .
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Inner Dharma
Welcome to Inner Dharma, a website focused on classical and traditional martial arts.
I have been training in martial arts since 1980, first in a hard style of Japanese Karate and then for sixteen years in a modern form of jujutsu focused on self-defense. I have always been interested in internal martial arts, and in 2004 began concentrating my effort in that direction. I have also been fortunate to learn two styles of classical Japanese swordsmanship.
My personal practice is currently focused on improving my skill at:
- Bagua, Xingyi, and Taiji under Shifu Zhang Yun as part of the Yin Cheng Gong Fa organization.
- Kashima Shinden Jiki Shinkage-ryu Kenjutsu under Dr. David Hall as part of the Hobyokan.
I am grateful to have learned elements of Katori Shinto-ryu between 2006 and 2014.
For information on my current teaching activities, please visit the Gassankan website or contact me via the email address below. A set of links to recommended resources can be found on the navigation bar above.


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I have really been loving the 'designer' toast craze! Putting all kinds of great ingredients on a good piece of toasted bread just can't be beat! It is also a wonderful way to use favorite leftovers.
Because of this, I decided to make the July giveaway book one that will inspire you to create your own yummy toasts! The book is called Posh Toast with recipes by Emily Kydd and photography by Louise Hagger. This book is sure to inspire some great toast creations. Use one of the 70+ recipes in the book to create your toast, or be inspired to come up with your own!
Just leave a comment during the month of July to be entered into the drawing to win this great recipe book!
Thank you to everyone that entered to win the June book selection and congratulations to the winner, Diane S. I know this book will come in handy for you Diane! To read more about the book, Rising to the Occasion by Paul Dickson, click here.
Instagram users, please read on! Why don't we share 'posh toast' photos for the month of July! Share photos of the ingredients you use for your toast creations using hashtag #pleasuregram. Can't wait to get some new toast ideas!
Thanks for stopping by! Have a wonderful weekend and remember to take pleasure in simple things, Jackie


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PE, PS, etc. This stock should be in the 20s
After 2 weeks o oversold S&P....Markets Begin to Bounce
Iraq RAISED Oil Price to Asia as did Saudi Arabia (Bloomberg News)
Jobs overtime hours at the highest level since before 2007 for Durable Goods and Non Durable Goods workers.
The jobs hours nearly at maximum. Rising hiring will be higher soon, over 300K jobs/month.
Total Hours of Overtime for Durable Goods and the Non-durable Goods Workers Are at the Highest Levels Since 2007.
Good growth of Jobs Working Hours...
Jobs Overtime Strength: Hours for Durable & Non-durable Goods Workers at Highest Levels Since Before 2007
I think it's a Technology Upturn Begun. HPQ Beat and Reaffirmed 2015. MU Beat the past 5 times by increasing amounts the past six months including the wider GPM%.
Would be surprised if it were DRAMs the only segment with rising earnings. INTC EPS and GPM% rise is likely as well.
Maktoob News on Yahoo:
Saudi Arabia and Venezuela Have Agreed to Work to Recover Oil Price and the Oil Market
XOM Long
I think earnings are turning the corner in general. Especially in Olipoly DRAM vendors...
Recovery also begun in MSFT, HPQ, and others. Some buzz in the cool products and acceptance & likeability of Win8.
INTC Earnings will provide an interesting insight:
Micron (ticker: MU) From DRAM chips Beat Earnings EPS with Expanded GPM Rise up 3% to 36%.
Samsung from DRAM chips also beat earnings.
If Intel does similarly this is a Technology Profit Upcycle.
If not then it is a DRAM Chip Upturn (chip shortage) lifting MU and Samsung.
falling into 16s.............Nasdaq climing
Even more important than 5 Earnings Beats in a row. GPM says moving from commodity to higher margin pricing and profit mix.
after initial "head fake" from all the Strong Jobs Growth
Total Beats and Revsions Upward by 80K for all three months.... Broad Based Growth
WMT Long
Beat plus Beat REVISIONS UP BY 50K for Prior two months so Total Beat is Significant
Indicates that Intel may also be reporting Higher EPS and Enlargement GPM% in similar fashion.
1 Beat good... 2 Beat would be Better.... 3 Beats and Revising Upward the Prior two months is STRONG.
This is a Clear Sgn of Rising Jobs Growth
per Bloomberg site...as the recovery gains strength
"highest paying jobs" grew the fastest said Bloomberg news site
OCT - NOV - DECEMBER per Bloomberg News articles.
Oct, Nov Beat by Total 50K
Dec Beat with Strong 252K Jobs Gains
Bloomberg News reports "HIGH WAGE JOBS' were one of the strongest growing
QCOM Long
per Bloomberg. "High Wage Jobs" grew the most


text:
Category: "Selena Gomez"
Selena Gomez feels 'defeated' when asked about her personal life
Did Orlando Bloom cheat on Katy Perry with Selena Gomez in Las Vegas?
Taylor Swift & Selena Gomez in Louis Vuitton at the Met Gala: cute or tragic?
Selena Gomez on child stars: 'We're easy targets… it's disgusting.'
Selena Gomez in Mugler at the iHeartRadio awards: budget or hot?
Justin Bieber fans who paid $2k to meet him had to pose with a cardboard cutout
Justin Bieber & Selena Gomez may get back together: aww or give it up?
Who had the best street style during PFW: Selena, Gigi or Zendaya?
Kate Hudson in Maria Lucia Hohan at the VF Oscar party: under-styled or fine?
Taylor Swift in Versace at the Grammys: boring, budget or fabulous?


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It only takes a minute to get started. Fill out our uncomplicated sign up form and login to the site.
This step is discretionary but will seriously raise your chances of having members look at your profile. Let people know a bit about yourself, your hobbies and upload some good photographs of yourself.
Utilise our website's sophisticated search to uncover members who satisfy your requirements. Or just browse through listings and uncover members that you find interesting.
Found someone who is attractive to you? Send them a few words or just a wink and see how you get along. With a little luck you'll be on your way to finding that special someone for you.
You won't regret it


text:
Updated: This program presents an original way of the famous Rubik's Cube by an assembly of 27 multi-colored cubies isolated in the space. Even during its deformations, it allows a 3D vision of the cube thanks to the basic MFC graphic functions. This simulation can also rapidly calculate a solution to reordering the Cube.
Latest GDI Articles
C++ Programming: Easy Screen Capture Using MFC/ATL
Learn to use CScreenImage, an MFC/ATL extension class for screen image captures.
Tip: Detect if a Language Font is Installed (Such as East Asian)
Check if any language (such as East Asian) is Installed on a user's computer.
Outline Text, Part 2
Display outline text with a translucent shadow and display a cached outline text for video rendering.
Outline Text, Part 1
How to draw outlined text with GDI/GDI+.
How to Use a Font Without Installing It
How to use a font without installing it first on user systems.
Latest Developer VideosMore...
Latest CodeGuru Developer Columns
Comparing the stdio and iostream C++ Libraries
It's essential to know the differences in these libraries and use them correctly. This brief tutorial will guide you.
A Tipple with a Tuple
Fear not, Tuple lovers. This much-maligned data type is still in use today.
Creating a Tic Tac Toe Game in Visual Basic
Create a Tic Tac Toe game with Visual Basic. I hope you will agree on how easy it is to do.
The Value of APIs
Application Programming Interfaces (APIs) are where you have to be. It's not a matter of if as much as a matter of which.


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Modeling and Simulation of Biological Agent Response to Combustion Effects
Award Information
Small Business Information
24 Thorndike St., Cambridge, MA, 02141
Principal Investigator:
N. Albert Moussa
(617) 661-0700
(617) 661-0700
Business Contact:
Venkat Devarakonda
Vice President
(617) 661-0700
Vice President
(617) 661-0700
Research Institution:
AbstractWeapons directed at enemy stores of chemical and biological agents can cause extreme collateral damage by venting live agents from broken containers into the surrounding area. This is severely hazardous for friendly forces, noncombatants, and the surrounding environment. An Agent Defeat weapon (such as HTIs) is specifically designed to cause substantial damage to the target, while minimizing collateral damage. In response to the environment created by the weapon in the facility, the agent may get neutralized through pyrolysis/thermal inactivation or combustion or may remain viable. Most of the research thus far has focused on the pyrolysis and combustion of chemical agents and thermal inactivation of biological agents. However, the combustion of biological agents has not been examined and even the most fundamental properties such as the ignition temperature are currently not available. The objective of the proposed Phase II SBIR project is to investigate combustion neutralization technologies for biological agents and develop a model compatible with existing lethality assessment codes. This objective will be accomplished through a combination of carefully controlled sub-system level bench scale tests on live agents and simulants and modeling. In addition to measuring combustion properties such as the ignition temperature, flammability limits, and the products of combustion, the study also will yield a fundamental understanding of combustion mechanism. The models and data from this study can be used to predict the extent of combustion and fractional viability of spores in a real life combustion event.
* information listed above is at the time of submission.
An Official Website of the United States Government


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roveverb [ I + adv/prep, T ]uk /rəʊv/ us /roʊv/ literary
Thesaurus: synonyms and related words
(Definition of "rove" from the Cambridge Advanced Learner's Dictionary & Thesaurus © Cambridge University Press)
(Definition of "rove" from the Cambridge Academic Content Dictionary © Cambridge University Press)
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Word of the Day
a type of heavy cloth that has a pattern woven into it that is the same colour as the cloth


text:
Fleet Foxes – Helplessness Blues Music Video
I was raised up believing I was somehow unique
Like a snowflake distinct among snowflakes, unique in each way you can see
And now after some thinking, I'd say I'd rather be
A functioning cog in some great machinery serving something beyond me
But I don't, I don't know what that will be
I'll get back to you someday soon you will see
What's my name, what's my station, oh, just tell me what I should do
I don't need to be kind to the armies of night that would do such injustice to you
Or bow down and be grateful and say "sure, take all that you see"
To the men who move only in dimly-lit halls and determine my future for me
And I don't, I don't know who to believe
I'll get back to you someday soon you will see
If I know only one thing, it's that everything that I see
Of the world outside is so inconceivable often I barely can speak
Yeah I'm tongue-tied and dizzy and I can't keep it to myself
What good is it to sing helplessness blues, why should I wait for anyone else?
And I know, I know you will keep me on the shelf
I'll come back to you someday soon myself
If I had an orchard, I'd work till I'm raw
If I had an orchard, I'd work till I'm sore
And you would wait tables and soon run the store
Gold hair in the sunlight, my light in the dawn
If I had an orchard, I'd work till I'm sore
If I had an orchard, I'd work till I'm sore
Someday I'll be like the man on the screen
Helplessness Blues, the latest album from Fleet Foxes, is available on May 2nd in the UK, and May 3rd in the US.
This footage was shot over a 5 month span in different parts of Arizona. Some of the footage includes some rare events including the snow in Scottsdale this year, snow clouds on the San Francisco Peaks in Flagstaff, and the lunar eclipse.
hot on elephant
The 4 Stages of a Good Divorce. A Letter to my Children: You do not come from a Broken Home. These People are Rare Gems—Keep Them, Fight for Them, don't Give Up on Them. Mom, can I Call her Mom, Too? Jon Stewart makes first appearance since retiring—"it's not your country." Waylon shares 10 transformingly beautiful Quotes about Love. 40 Things I've Learned in 40 Years. My Marriage had to End—for my Life to Begin. Why your Yoga Goals are (Probably) Irrelevant, if not Downright Dangerous. Dear Woman in the White Car at Margaritas Mexican Grill in West Memphis, Arkansas on July 15th, 2012.


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25% off lightweight hoodies? Heavy. Use HOODSRGOOD.
Kung fu master kicks the #@!% out of invisible ninjas!
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great work. you should add it to the Martial Arts group
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text:
Printing Fresno
310 results for Printing in Fresno
Mail Boxes Etc438 East Shaw Avenue93710 Fresno (559) 225-6155
MBE, the worlds largest franchisor of retail postal and business services, provides convenient, value-added business services to general consumers, road warriors and the small-office/home-office ... printing, packing, domestic shipping, international shipping, luggage logistics, moving supplies,...
Postnet6083 North Figarden Drive93722 Fresno (559) 277-5423
PostNet offers high quality, affordable printing, copying and shipping services
Request for Quotation
Are you looking for Printing Services & Supplies ?Use our "Request for Quotation" service to get customized offers from companies in Fresno, tailored for your exact needs!
Allied Graphic Sales & Service4545 N Brawley Ave #11093722 Fresno (559) 271-7740ClosedCall us today
In business since 1981, Allied Graphic Sales & Services is a professional quality graphic equipment store. We specialize in graphic sales, machine repair, and more. A large part of our success has...
AlphaGraphics Fresno3950 N. Chestnut Diagonalsuite 10793726 Fresno Mclane (559) 476-2900Closed
AlphaGraphics is specialized in offering marketing services. AlphaGraphics is focused on offering high quality marketing services and helping the customers achieve their own goals. The services ... marketing services, printing services, business cards
Ups Store438 East Shaw Avenue93710 Fresno (559) 225-6153Closed
printing needs. The company offers the possibility of uploading the necessary documents online and picking them up at a nearby location. The UPS Store FRESNO can also offer services regarding the...
Unisource2325 S. Cedar Ave.93725 Fresno (559) 291-0226
printing business imaging papers, packaging systems, and facility supplies and equipment in North America We offer the widest product selection in our industry, allowing customers to reduce suppliers...
California Surveying & Drafting Supply4753 W. Jennifer Ave93722 Fresno 559-275-0513
For printing and imaging solutions, Fresno, CA clients trust California Surveying & Drafting Supply.
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Binding Unlimited2140 N Fine Ave93727 Fresno Mclane (559) 255-7527Closed
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Avante Print & Copy370 West Fallbrook Avenue Suite 10493711 Fresno (559) 224-8285Closed
Avante Print and Copy offers printing, bindery, and copying services to the Fresno, CA area. Advertising Specialties available. Call 559-224-8285.
Advance Forms Management2930 N. Maroa Ave93704 Fresno (559) 227-1192Closed
Promotional items, promotions, custom t shirts and promotional products available here. ... product dealers, printing, supply, continuou individual forms, form printing, continuous, product,...
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Boot camp workouts: Ready to feel the burn, soldier?
D.I. McSweeny on BOOT CAMP on FOX. Photograph by: Anthony Neste/FOX, National Post It has been 10 years since boot camp classes made their debut on the fitness scene.
Start the conversation, or Read more at Canada.com.
Copyright © 2016 Topix LLC


text:
We have some great new wines for you to enjoy this season! Order soon online or come visit our new Wine Gems store at 495 New Rochelle Road, Bronxville, NY 10708 (in Chester Heights) to shop for wines and spirits!
Come join us for a free in-store tasting! Our next event is Saturday, July 30, 5:30-7:30pm. Importer José Castellano from Palette of Wines will be at Wine Gems to pour sparkling, white, rosé and red wines from Spain. Once you select some winning wines, take them across the street to Elia Taverna to enjoy with the best Greek food in Westchester. No corkage Monday thru Wednesday and just $10 per bottle on other days!
On Friday, Jan 29, Wine Gems hosted a wine tasting at the Winter Antiques Show in NYC to benefit East Side House Settlement. It's not too late to place an online order! Just type "WAS" in the Comments section of your order and we will make the donation.
Have something to celebrate? Here are three great wines perfect for a special occasion or holiday gift:
Orin Swift Abstract 2013 is an affordable indulgence for lovers of big, rich red wines. Dave Phinney has crafted a blend of Grenache, Petite Sirah, and Syrah from hillside California vineyards. Lush flavors of sweet boysenberries, kirsch, licorice, dark cherries, and exotic floral notes. 15.7% alcohol and a very stylish label!
If you love a creamy, buttery, oaky Chardonnay, we have the perfect white wine gem for you! Dutton Goldfield Dutton Ranch Chardonnay 2012 is a classic Russian River Valley Chardonnay!
From Piedmont, we have a gorgeous red wine gem for a special gift or a splurge! Cantina del Pino Barbaresco Albesani 2009 was rated 93 points in Wine Spectator and 92 by Antonio Galloni for Parker's Wine Advocate. In Galloni's words, "Proprietor Renato Vacca continues to show he has the magic touch. I would be thrilled to drink any of these magnificent wines."
We have a new Facebook page! Like us at WineGemsShop. We regularly update it with images of new wines, in-store tastings and special events. You can also use it to let us know about your experience with our wines and service.
You're invited to join our wine club and you may also order anytime a la carte! To place your order for these and other wines, simply reply directly to this e-mail, come in to our store in Chester Heights or visit our website,www.winegems.net. If you need any help or additional information, just send an e-mail or call us for quick expert advice: email@example.com, or 914-954-7481.
Have you heard about the Wineberry Box? It's a box made of Bordelais oak holding 3 liters of wine (that's 4 bottles) and the wines inside are really good! Le Garrigon Cotes du Rhone 2010 was the top-rated wine in the New York Times panel's review of wines-in-a-box in August 2011! Click here to order the current vintage. 2014 Le Garrigon Cotes du Rhone 3L Box
Our retail store is located at 495 New Rochelle Road in the Chester Heights neighborhood of lower Westchester County just off Exit 10 of the Cross County Parkway. We're at the corner of New Rochelle Road and Parkway Plaza, directly opposite Elia Taverna and J&G Deli & Market.
Site last updated July 24, 2016
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Terminally Ill Boy, Dog Fetch a Wave for Surfing Wish
Caleb Acosta was granted his wish to ride the waves with Ricochet the surfing dog.
Instant Index: Pod of Dolphins Interrupts a Surfing Competition to Catch Some Waves
Diane Sawyer reveals the stories people have been buzzing about all week.
Hot Dogs Hang 10
A new surfing competition for the dogs.
Now Playing: Terminally Ill Boy, Dog Fetch a Wave for Surfing Wish
Now Playing: Instant Index: Pod of Dolphins Interrupts a Surfing Competition to Catch Some Waves
Now Playing: Hot Dogs Hang 10
Now Playing: Goatee the Surfing Goat
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It has been a while (a decade) since I was last employed with Data Projections, but I had a great experience there, save for the last few months, when new local management was brought in.
I originally came on board as an Administrative Assistant in charge of helping with Educational Bids and Tradeshows, also assisting the Executive Office Manager. Profits were not where the owners wanted them to be, and they were forced to consolidate some positions, and I was moved to the Front Office (while still maintaining many of my former responsibilities). My supervisor and the owner expected much, but were not overbearing.
When my husband was transferred from Houston (where I was - at the corporate office) to Dallas, they were able to transfer me, much to my delight. The owner expressed her displeasure for me leaving, but I took that as a sign that I had performed my duties well.
When I went to the Dallas branch, it was much smaller, and I was in charge of the front office, while also handling Inside Sales and rentals. Everything went very well, and the branch was like a family. Much of that changed when a new branch manager was hired, and soon after most of the employees at that branch were either laid off or they quit. I had just had a baby, so I used my layoff as an opportunity to become a full-time caregiver.


text: Doctor, Patient Exchange Gunfire in Deadly Penn. Hospital ShootingAdam Weinstein7/25/14 10:00amFiled to: darby shootingguns guns gunsgunspennsylvaniaphiladelphia2036EditInvite manuallyPromoteDismissUndismissHideShare to KinjaToggle Conversation toolsGo to permalink The quiet of a hospital in the Philadelphia-area suburbs was broken yesterday when an armed mental patient killed a caseworker and got into a gunfight with his armed psychiatrist.Authorities say the afternoon incident at Mercy Fitzgerald Hospital's wellness center might have been worse, if not for quick action on the part of the pistol-packing doctor and several of his unarmed colleagues: Delaware County District Attorney Jack Whelan said a mentally troubled Richard Plotts walked into the Psychiatric Unit on the third floor of the building with his caseworker, 53-year-old Theresa Hunt of Philadelphia. Plotts and Hunt went into Dr. Lee Silverman's office, and an argument erupted. Hunt shut the door and called police. Seconds later there was gunfire. When it was over, Hunt was dead and Plotts and Silverman wounded.Investigators believe Plotts shot Silverman in the head, inflicting a graze wound. They believe the doctor then pulled out his own gun, firing several times. Plotts was critically injured, hit twice in the torso and once in the arm. After the shooting, another doctor and caseworker reportedly burst into the office to find "Silverman holding his bloody face and Plotts still holding his weapon." They proceeded to wrestle Plotts down and take his weapon. He is currently in critical condition; Dr. Silverman was treated and released. Advertisement If he pulls through, Plotts will be charged with first degree murder for Hunt's death, authorities say. Silverman faces no charges and was praised for his action in the shootout, in which one of Plotts' bullets narrowly missed him. It was unclear how long Silverman had been armed at work or whether he'd begun carrying as a result of his experience with Potts, though the district attorney said he "did receive information that there were incidents involving Mr. Plotts and hospital personnel including the doctor's staff in the past." Also unclear was why Plotts had the means to fatally shoot his caseworker in the first place. Upper Darby Police Superintendent Michael Chitwood told a local paper that Plotts had been committed for psychiatric evaluation in that town "on at least three occasions" and had been banned from at least one facility for his aggression. Sponsored "He's got a long history of guns and mental illness," Chitwood said. [Image via AP]Reply203 repliesLeave a reply


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The face mask I ordered were just wonderful and made my daughter's birthday party a big success!!!!! The person who took care of me on the phone was very helpful and kind. Thank you.
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More creativity, less toil.
From design to production, YuGen is the ultimate
management platform for the apparel industry.
From design to production, YuGen is the ultimate
management platform for the apparel industry.
Harness the power of automation to organize all your product data,
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Collaborate with factories, vendors and your internal team where the data lives.
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YuGen allowed us to quadruple our style count without increasing our resources and headaches. Its a win-win for everybody!
We are teaching our students to become the next generation of Sports Product Experts. YuGen is an excellent fit and we are excited to implement this forward facing solution it in our inaugural year.
Ellen Schmidt Devlin, University of Oregon, Head of Sport Product Management
I am a passionate entrepreneur but I literally drowned in spread sheets and email. YuGen simplifies my tasks tremendously!
Summer Kramer, SummerSkin
President and Founder.
No credit card required. No obligation. We know you'll love it!
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text:
- Miss Florida 2017 stripped of crown days after win - US Weekly
- Lindsay Lohan steps out amid relationship drama - TMZ
- Was Taylor Swift snubbed by the VMAs? - Gossip Cop
- Rachel Platten sings "Fight Song" with lots of stars - Just Jared Jr
- Farrah Abraham sizzles in a revealing bikini - Radar
- New pics from the Clooneys' Italian summer - Lainey Gossip
- Fox News snubs major DNC moment - The Hollywood Reporter
16 January 2013 at 5:07 PM
Daniel Day-Lewis Promotes 'Lincoln' After Golden Globe Win!
About this photo set: Daniel Day-Lewis steps out at the photo call for Lincoln alongside his co-star Sally Field and director Steven Spielberg at the Casa de America on Wednesday (January… Read More Here
Photo #: 2793210
Posted to Daniel Day-Lewis, Sally Field, Steven Spielberg
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