Shot peening coverage is confirmed by mounting a test strip having surface irregularities of graduated depth on a surface of a component undergoing peening for which peening coverage is to be confirmed. The component, with the test strip attached thereto, is exposed to the shot stream under production conditions. The strip, which is selected according to a procedure described herein such that some, but not all, of the surface irregularities are removed when proper peening coverage is attained, is then removed and examined.

This invention relates to method and apparatus for confirming shot peening coverage.
Shot peening has been common practice in the treatment of metal components to increase surface hardness and fatigue life. In shot peening, spherical shot is impacted on the surface of a component, thereby forming very small spherical dents on the surface. However, the process must be carefully controlled, because shot peening above and below a critical intensity results in a component having less than optimal properties.
Two critical shot peening perimeters are intensity and coverage. Peening intensity is a function of the kinetic energy of the shot impacted upon the surface of the component, which is a function of shot velocity and shot size. Commonly, shot is accelerated by using air pressure to force the shot through a peening nozzle which is directed at the surface undergoing peening. In order to confirm shot peening intensity, the almen strip process has been used for many years. Thin metal strips which deflect when undergoing peening are mounted in a special holder in which a critical section of the strip is unsupported. The strip thus installed on the holder is exposed to the shot stream under (as closely as possible) the same conditions as the component undergoing peening. After the strip has undergone peening for a predetermined time period, the strip is removed from the holder and the deflection measured, all according to known procedures. Accordingly, a series of almen strips are exposed to the shot stream for increasing time periods. When the deflection of the strips increases by no more than ten percent (10%) when the time is doubled, the intensity is said to be at saturation, and peening of the component parts may begin at this saturation intensity.
Peening coverage of a component is a factor of intensity, but may be affected by other factors. For example, since the goal of peening is to cover the surface being peened by small dents or dimples formed by the impact of the shot, the hardness of the component will affect the size of the dimples and hence coverage is also a factor of hardness. The peening nozzle which directs shot to the component is usually automatically moved at a predetermined stroke rate. If the nozzle becomes out of adjustment, or the stroke rate is somehow changed either through a machine malfunction or otherwise, coverage may also be affected, even though the common almen strip procedure indicates no change in intensity. Therefore, coverage can only be confirmed by an extremely laborious and highly skilled method of physically observing the surface of the article being peened, usually with the aid of a microscope, in order to confirm that the entire surface has been covered with the aforementioned dimples or dents. In mass production, the intensity of the peening equipment is periodically checked by the almen strip method, but no convenient method of determining coverage, other than the aforementioned manual examination, has been available.
One prior art method of establishing peening coverage is disclosed in US. Pat. No. 3,950,642, which discloses a test strip coated with a fluorescent dye which is peened and then compared to a control strip to determine coverage, since a greater percentage of the fluorescent dye will be removed from the strip as coverage increases. Another prior art method in common use is to mount a test strip on a component undergoing peening and then microscopically examine the test strip to establish coverage, by examining for dimples or dents or changes in physical characteristics of the strip.
According to one embodiment of the invention, a test strip having surface irregularities distributed over the surface of the strip is mounted on the surface of a component undergoing peening, which is then peened. The test strip is then removed and the surface compared with a standard to determine coverage. This may be done by physically comparing the test strip with an archived standard test strip, comparing the test strip with a paper copy of the test surface of a test strip, or (if the examiner has had sufficient experience) by an examiner viewing the test strip and making a judgment as to whether coverage is sufficient.
According to another embodiment of the invention, a test strip having multiple regions of surface irregularities of graduated depth is mounted on a surface of the component undergoing peening for which peening coverage is to be confirmed. The component, with the test strip attached thereto, then is exposed to the shot stream under production conditions. The strip is then removed and examined. Since the surface irregularities are of graduating depth, and since the strip has been selected according to a procedure hereinafter described, when the test strip has been exposed to shot at the desired coverage level, some of the irregularities will be obliterated while the deeper irregularities will remain. The test strip may also be compared with an archived standard test strip or a copy of an archived standard test strip.
Accordingly, coverage of shot peening is confirmed without the laborious inspection process of the prior art. It is contemplated that only a representative sample of the components undergoing peening will have coverage confirmed. (For example, one out of every one hundred parts undergoing peening).

Test strip and method for confirming shot peening coverage


Disclosed are compositions of a novel astringent and keratolytic topical pharmaceutical base into which drugs can be incorporated such as for example an anti-pruritic drug and/or an anti-inflammatory drug.

The present invention relates to a novel astringent and keratolytic (urea containing) topical pharmaceutical base composition to which other drugs can be added, for example, an anti-pruritic drug like lidocaine, a corticosteroid like hydrocortisone or a combination thereof.
Urea has been long recognized as a cosmetic ingredient in formulations acting as a humectant and moisturizer. There have been reports of keratolytic activity attributed to urea with the ability at high concentrations to solubilize and denature protein. High concentrations of urea are also known to have a mild, antimicrobial effect.
Astringents are locally applied compounds which precipitate proteins and shrink mucous membranes. Typically used are aluminum sulfate and calcium acetate. Astringents add significant value to topical cream products and in the healing of damaged skin.
The pH of normal skin is about 4.5-5.5. This acidic pH of the skin provides a natural protection and is referred to as the xe2x80x9cAcid Mantlexe2x80x9d of the skin. Microorganisms prefer a pH in the range 6-7 to thrive and are therefore held in check by the acidic pH of the skin.
There is a need in the industry for improving on compositions for treating inflamed and pruritic conditions more effectively. A need also exists for a topical pharmaceutical base into which other drugs can be incorporated to provide better efficacy and improved healing of the dermal condition.
The present invention concerns the finding that the use of topical keratolytics, such as urea, improve drug penetration and the efficacy of traditional anesthetic agents, such as, for example, lidocaine and corticosteroid action.
Accordingly, as one embodiment, the present invention includes a novel topical pharmaceutical base containing astringents and urea which base can be used to incorporate drugs, such as anesthetics and corticosteroids or a mixture thereof. The topical base includes about 1 to about 40 wt % urea; about 0.01 to about 1 wt % of an astringent, and dermatologically acceptable excipients.
The present invention includes as a second embodiment a dermatological composition for treating pruritus conditions containing about 1 to about 40 wt % urea; about 0.01 to about 1 wt % of an astringent; about 0.01 to about 10 wt % of an anesthetic agent, and dermatologically acceptable excipients.
In a third embodiment, the present invention includes a dermatological composition for treating pruritic and inflamed conditions containing about 1 to about 40 wt % urea; about 0.01 to about 1 wt % of an astringent; about 0.01 to about 10 wt % of an anesthetic agent; about 0.001 to about 10 wt % of a corticosteroid, and dermatologically acceptable excipients.
The above dermatological compositions may preferably include one or more non-ionic surfactants. The compositions are preferably creams and have a pH between about 3.0 and 6.5.
The present invention first includes a novel pharmaceutical base which drugs can be incorporated into such as anesthetics and corticosteroids or mixtures thereof.
The pharmaceutical base contains urea and an astringent. The urea is contained in an amount from about 1 to about 40 wt % of the total composition. Preferably compositions contain from about 5 to about 35 wt % . The astringent ranges from about 0.01 to about 1 wt % of the composition. Combining astringents and urea in a pharmaceutically acceptable topical base at an acidic pH provides a unique combination of factors for applying topical drugs to the skin and for skin healing.
Astringents precipitate proteins and shrink mucous membrane. Commonly used astringents include salts of cations, including aluminum, zinc, manganese, iron and bismuth; other salts that contain the afore-mentioned metals, such as permanganates; and tannins and related polyphenolic compounds. Examples of specific astringents include aluminum chlorohydrates including hydrate of aluminum chloride hydroxide, aluminum chloride, aluminum sulfate, calcium acetate, zinc sulfate, aluminum ammonium sulfate, aluminum potassium sulfate, aluminum acetate, calamine (iron oxide mixed with zinc oxide), zinc sulfate, zinc caprylate, zinc chloride, zinc oxide, and tannic acid. Preferred astringents include aluminum sulfate, calcium acetate or a mixture thereof.
Examples of drugs incorporated in this topical base include the compositions of the present invention which include about 0.001 to about 10 percent by weight of a corticosteroid, e.g. hydrocortisone or hydrocortisone acetate, or about 0.01 to about 10 percent by weight of an anesthetic agent, e.g. lidocaine or a pharmaceutically acceptable salt thereof. In one embodiment, the weight ratio of anesthetic to corticosteroid is between about 6:1 to about 3:1.
Local anesthetics include, for example, benzocaine, bupivacaine, cocaine, etidocaine, lidocaine, mepivacaine, paroximine, prilocaine, procaine, proparacaine, ropivicaine, and tetracaine.
Corticosteroids include, for example, alclometasone dipropionate, amcinonide, augmented betamethasone dipropionate, beclomethasone dipropionate, betamethasone, betamethasone benzoate, betamethasone dipropionate, betamethasone sodium phosphate, betamethasone valerate, clobetasol propionate, clocortolone pivalate, cortisone, desonide, desoximetasone, dexamethasone, dexamethasone acetate, dexamethasone sodium phosphate, diflorasone acetonide, diflorasone diacetate, fluocinolone acetonide, flucinonide, flunisolide, fluocinolone acetonide, flurandrenolide, fluticasone propionate, halcinonide, halobetasol propionate, hydrocortisone, hydrocortisone acetate, hydrocortisone butyrate, hydrocortisone sodium phosphate, hydrocortisone valerate, methylprednisolone, methylprednisolone acetate, methylprednisolone sodium succinate, mometasone furoate, prednisolone acetate, prednisolone sodium phosphate, prednisolone tebutate, prednisone, triamcinolone, triamcinolone acetonide, triamcinolone diacetate, and triamcinolone hexacetonide. Topical corticosteroids are typically applied as creams, ointments or gels.
Glucocorticoids that are commonly applied topically include betamethasone dipropionate, clobetasol propionate, diflorasone diacetate, halobetasol propionate, amcinodide, flucinonide, halcinonide, betamethasone valerate, diflorasone diacetate, triamcinolone acetonide, flurandrenolide, hydrocortisone valerate, mometasone furoate, hydrocortisone butyrate, aclometasone dipropionate, flucinonolone acetonide, and dexamethasone sodium phosphate.
Preferably, the compositions of the present invention include about 0.01 to about 2.0 percent by weight hydrocortisone and about 1.0 to about 5.0 percent by weight lidocaine and 15 percent urea. In the compositions of the present invention, the ratio of lidocaine to hydrocortisone ranges from about 1.0 to 00.01 to about 5.0 to 2.5. A particularly preferred composition comprises about 3.0 percent by weight lidocaine and about 0.5 percent by weight hydrocortisone with 10 percent urea.
Further, the vehicle used to deliver topical drug products can play an important role in the efficacy and stability of product. This is of particular importance in the development of these formulations.
Generally topical cream formulations are oil in water emulsions (o/w) which allow easy application of the product on the skin without leaving an oily residue. Most o/w cream formulations use anionic surfactants (e.g. sodium lauryl sulfate) in their emulsion system to provide a physically and chemically stable product. Long term stability is an important consideration in the commercialization of a product. Attempts to make formulations with anionic surfactants and lidocaine hydrochloride, caused physical and chemical instability problems. The use of non-ionic surface active agents in the formulations unexpectedly overcome these stability problems and provide an elegant stable topical cream product. The amount of non-ionic surfactant in the above compositions range from about 0.1 to about 10 wt % of the total composition.
Non-ionic surfactants may be relatively water insoluble or quite water soluble.
The water insoluble non-ionic surfactants are the long-chain fatty acids and their water-insoluble derivatives. These include (1) fatty alcohols such as lauryl, cetyl (16 carbons), and stearyl alcohols; (2) glyceryl esters such as the naturally occurring mono-, di-, and triglycerides; and (3) fatty acid esters of fatty alcohols and other alcohols such as propylene glycol, polyethylene glycol, sorbitan, sucrose, and cholesterol. Included also in this general class of nonionic water-insoluble compounds are the free steroidal alcohols such as cholesterol.
To increase the water solubility of these compounds and to form the second group of nonionic agents, polyoxyethylene groups are added through an ether linkage with one of their alcohol groups. The list of derivatives available is much too long to cover completely, but a few general categories will be given.
The most widely used compounds are the polyoxyethylene sorbitan fatty acid esters. Closely related compounds include polyoxyethylene glyceryl, and steroidal esters, as well as the comparable polyoxypropylene esters. It is also possible to have a direct ether linkage with the hydrophobic group as with a polyoxyethylene-stearyl ether or a polyoxyethylene-alkyl phenol. These ethers offer advantages since, unlike the esters, they are quite resistant to acidic or alkaline hydrolysis.
Other suitable combinations from these examples can also be used to serve as the emulsifying system for this invention.
Any dermatologically acceptable carrier can be used in the compositions of the invention. As used herein, xe2x80x9cdermatologically acceptable carrierxe2x80x9d refers to vehicles, diluents, carriers, which can include adjuvants, additives, or excipients, known for use in dermatological compositions. The compositions of the invention include, but are not limited to, creams, ointments, solutions, lacquers, sticks, pledgets, wipes, cleansers and/or gels.
The topical composition may be a semi-solid at room temperature but is easily absorbed into the stratum corneum. The semi-solid composition can be a cream. Such a composition can include petroleum-based liquids and solid fractions as skin protectants. The solid skin protectant can be semi-solid. The solid skin protectant can be present in about 5.5% to about 20% in the composition and includes petrolatum or a synthetic or semi-synthetic hydrocarbon of the same nature as petrolatum. Mixtures of such ingredients can also be used. Liquid skin protectants can be petrolatum and contained in the composition in about 10% to about 20% and include any synthetic or semi-synthetic oleaginous liquid fraction. The liquid skin protectant can be mineral oil, which is a liquid mixture of hydrocarbons obtained from petroleum.
The compositions of the invention can include propylene glycol. Propylene glycol can be present in the composition up to about 10%. In one embodiment, propylene glycol is present in the composition at about 1% to about 5%.
The compositions can contain conventional preservatives, such as methyl paraben, propyl and butyl imidazolidinylurea, diazolidinylurea, methylchloroiso-thiazolinone and methylisothiazolinone. Although not to be held by theory, it is believed that the antimicrobial properties of the urea and antimicrobial agents and propylene glycol allow the composition of the present invention to be free of conventional preservatives.
The present compositions can also contain dermatologically acceptable excipients, such as for example emulsifiers and thickeners. Among these are for example C16 to C18 straight or branched chain fatty alcohols or fatty acids or mixtures thereof. Examples of emulsifiers and thickeners include cetyl alcohol, stearyl alcohol, stearic acid, palmitic acid, or mixtures thereof. Fatty acids or fatty alcohols may be present in from about 0.25 to 10 wt-%.
Another ingredient useful in the composition of the present invention may be glyceryl stearate, which is a monoester of glycerine and stearic acid, or other suitable forms of glyceryl stearate for example glyceryl stearate SE, which is a commercially available self-emulsifying grade of glycerol stearate that contains some sodium and/or potassium stearate. Glyceryl stearate may be in the composition anywhere from about 1 to about 10% by weight.
The composition can be an emulsion. The emulsion can contain a fatty phase in the range of about 5% to about 60% by weight. Typically, the fatty phase will range from about 5% to about 40% by weight, with respect to the total weight of the composition. Known oils, waxes, emulsifiers and coemulsifiers can be used in compositions in the emulsion form. The emulsifier and the coemulsifier can be present, in the composition, in a proportion ranging from about 0.3% to about 30% by weight. Typically the emulsifier and the coemulsifier are present in a proportion ranging from about 0.5 to about 20% by weight. The emulsion can also contain lipid vesicles.
In one embodiment, the composition can include thickeners which provide a high viscosity cream designed to remain in place upon application to the skin. By way of example, thickeners can include a mixture of a carbomer and triethanolamine. The mixture can be combined together and added to the composition in an amount totaling anywhere from about 0.05 to 30% by weight. Triethanolamine can be purchased as Trolamine NF from BASF. Carbomers come in various molecular weights and are identified by numbers. These are otherwise known as Carbopol. Exemplary Carbopols include is Carbopol 940, 910, 2984, 5984, 954, 980, 981, 941 and 934. Carbopol ETD 2001, 2020, and 2050 and Ultrez 20 are also commercially available and can be used. The carbomer or Carbopols are resins which are known thickening agents. They are homopolymers of acrylic acid crosslinked with an allyl ether of pentaerythritol, an allyl ether of sucrose or an allyl ether of propylene. The carbomer can be present in the composition as a thickener and also can be used to suspend and stabilize the emulsion.
The composition can also contain known adjuvants and additives, such as bactericides, fungicides, virucides, light filter substances, active ingredients with a cooling action, antioxidants, plant extracts, antiinflammatories, substances which promote wound healing, skin-lightening agents, screening agents, odor absorbers, skin-coloring agents, perfumes, antifoams, dyes, pigments which have a coloring action, thickeners, surface-active substances, emulsifiers, emollients, moisturizers and/or humectants, fats, oils, waxes, alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents, silicone derivatives or chelating agents. These additives and adjuvants, depending on their nature, can be introduced into the fatty phase, into the aqueous phase and/or into the lipid spherules.
Exemplary oils or waxes suitable for use in the compositions include mineral oils (liquid petrolatum), vegetable oils (liquid fraction of karite butter, sunflower oil), animal oils (perhydrosqualene), synthetic oils (purcellin oil), silicone oils or waxes (cyclomethicone) and fluorinated oils (perfluoropolyethers), beeswax, carnauba wax or paraffin wax. Fatty alcohols and fatty acids (stearic acid) can be added to these oils.
Exemplary emulsifiers which are suitable include glyceryl stearate, polysorbate 60, sorbitan monostearate, and the PEG-6/PEG-32/glycol stearate mixture marketed under the trademark Tefose.RTM. 63 by Gattefosse.
Exemplary solvents which can be used in the compositions include the lower alcohols, such as ethanol, isopropanol and propylene glycol.
Exemplary hydrophilic gelling agents suitable for use in the compositions include carboxyvinyl polymers (carbomer), acrylic copolymers such as acrylate/alkyl acrylate copolymers, polyacrylamides, polysaccharides such as hydroxypropylcellulose, natural gums and clays. And exemplary lipophilic gelling agents include modified clays such as bentones, metal salts of fatty acids such as aluminum stearates, and hydrophobic silica, ethylcellulose or polyethylene.
The compositions of the present invention containing drugs may be used in the topical treatment of the following derma, vaginal and anal conditions: pain, itching and irritation, pruritus ani, anal fissures, hemorrhoids, pruritus, insect bites, abrasions, minor bums, pruritus vulvae, pruritic eczemas and similar conditions of the skin and mucous membranes. The compositions of the present invention are particularly useful when these conditions are accompanied by moderate to severe inflammation.
The following Examples give illustrative formulations, of the compositions of the present invention. The following ingredients are combined and packaged by standard techniques, well-known to those skilled in the art. Other topical dosage forms may also be used e.g. Gels, Lotions, solutions, aerosol sprays and the like as required.

Topical pharmaceutical base with anti-pruritic and/or anti-inflammatory drugs


Disclosed is a nonaqueous liquid detergent composition comprising an enzyme particle, said composition having an average particle size of the enzyme particle of less than 600 microns.

This invention relates to liquid laundry detergent products which are nonaqueous in nature and which contain enzyme particles having reduced average particle size.
Liquid nonaqueous detergents are well known in the art. This class of detergents is particularly interesting for enhancing the chemical compatibility of detergent composition components, in particular enzyme particles.
In such nonaqueous products, these enzyme particles are less reactive than if they had been dissolved in the liquid aqueous matrix.
A problem associated with the use of enzyme particles is that there is a tendency for such products to phase separate as dispersed insoluble solid particulate material drops from suspension and settles at the bottom of the container holding the liquid detergent product. Phase stabilizers such as thickeners or viscosity control agents can be added to such products to enhance the physical stability thereof. Such materials, however, can add cost and bulk to the product without contributing to the laundering/cleaning performance of such detergent compositions.
A further problem associated with enzyme particles is that it has been observed that enzyme particles can induce visual inhomogenities in the final product. This represents a problem as composition aesthetics is a key element in terms of consumer acceptance.
Accordingly, the formulator of a nonaqueous liquid detergent composition is faced with the challenge of formulating a physically stable non-aqueous detergent composition which provides effective enzyme activity in the wash.
The Applicant has now surprisingly found that enzyme particles of reduced size within a liquid non-aqueous detergent composition do meet the above objectives.
It is therefore an advantage of the invention to provide enzyme particles containing non-aqueous liquid-detergent compositions which produce efficient enzyme activity in the wash, which are physically stable and which have improved visual appearance.
EP 0 541 610 discloses the preparation of nonaqueous liquid detergents containing more than 8% anionic surfactants by wet grinding of a mixture comprising a peroxygen bleach. The average particle size obtained after grinding is in the preferred range of 1-5 microns. This document does not disclose or suggest that utilizing enzyme particles of reduced particles do provide the benefits of the present invention.
The present invention relates to a liquid nonaqueous detergent composition comprising a enzyme particles characterized in that the average particle size of said enzyme particles is less than 600 microns.
Enzyme Particles
The enzyme particles suitable for the present invention comprise comprise one or more enzymes which provide cleaning performance and/or fabric care benefits.
Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, xylanases, lipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, xcex2-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof.
A preferred combination is a cleaning composition having cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes.
The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800. Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50 KDa, an isoelectric point of 5.5 and containing 415 amino acids. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed Nov. 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also WO91/17243.
Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for xe2x80x9csolution bleachingxe2x80x9d, i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, laccase and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, WO89/09813 and in European Patent application EP No. 91202882.6, filed on Nov. 6, 1991 and EP No. 96870013.8, filed Feb. 20, 1996.
Preferred enhancers are substitued phenthiazine and phenoxasine 10-Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substitued syringates (C3-C5 substitued alkyl syringates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
Said cellulases and/or peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P xe2x80x9cAmano,xe2x80x9d hereinafter referred to as xe2x80x9cAmano-Pxe2x80x9d. Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable lipases are lipases such as M1 LipaseR and LipomaxR (Gist-Brocades) and LipolaseR and Lipolase UltraR(Novo) which have found to be very effective when used in combination with the compositions of the present invention.
Also suitable are cutinases [EC 188.8.131.52] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor). The lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPNxe2x80x2). One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE(copyright) by Novo Industries A/S of Denmark, hereinafter xe2x80x9cNovoxe2x80x9d. The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE(copyright), DURAZYM(copyright) and SAVINASE(copyright) from Novo and MAXATASE(copyright), MAXACAL(copyright), PROPEPASE(copyright) and MAXAPEM(copyright) (protein engineered Maxacal) from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, Jan. 9, 1985 and Protease B as disclosed in EP 303,761 A, Apr. 28, 1987 and EP 130,756 A, Jan. 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. Other preferred proteases include those of WO 95/10591 A to Procter and Gamble. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter and Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo.
In more detail, protease referred to as xe2x80x9cProtease Dxe2x80x9d is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 and in the patent application of C. Ghosh, et al, xe2x80x9cBleaching Compositions Comprising Protease Enzymesxe2x80x9d having U.S. Ser. No. 08/322,677, filed Oct. 13, 1994. Also suitable for the present invention are proteases described in patent applications EP 251 446 and WO91/06637.
Preferred protease for use in the present invention are SAVINASE(copyright) and the proteases described in EP 215 446 and WO95/10591 at a level of from 0.001% to 0.5%, preferably from 0.003% to 0.2%, more preferably from 0.01% to 0.1% pure enzyme by weight of total composition for liquid detergent compositions and; SAVINASE(copyright), ALCALASE(copyright) and the proteases described in WO91/06637 and WO95/10591 at a level of from 0.0001% to 0.2%, preferably from 0.001% to 0.1%, more preferably 0.005% to 0.05% pure enzyme by weight of total composition in granular detergent compositions.
Amylases (xcex1 and/or xcex2) can be included for removal of carbohydrate-based stains. WO/94/02597, Novo Nordisk A/S published Feb. 3, 1994, describes cleaning compositions which incorporate mutant amylases. See also WO/94/18314, Genencor, published Aug. 18, 1994 and WO/95/10603, Novo Nordisk A/S, published Apr. 20, 1995. Other amylases known for use in cleaning compositions include both xcex1- and xcex2-amylases. xcex1-Amylases are known in the art and include those disclosed in U.S. Pat. No. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent specification no. 1,296,839 (Novo). Other suitable amylase are stability-enhanced amylases including Purafact Ox AMR described in WO 94/18314, published Aug. 18, 1994 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Examples of commercial xcex1-amylases products are Termamyl(copyright), Ban(copyright), Fungamyl(copyright) and Duramyl(copyright), all available from Novo Nordisk A/S Denmark. WO95/26397 describes other suitable amylases : xcex1-amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl(copyright) at a temperature range of 25xc2x0 C. to 55xc2x0 C. and at a pH value in the range of 8 to 10, measured by the Phadebas(copyright) xcex1-amylase activity assay. Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in WO95/35382.
The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Said enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition. The enzymes can be added as separate single ingredients (prills, granulatescontaining one enzyme) or as mixtures of two or more enzymes (e.g. cogranulates).
Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Copending European Patent application 92870018.6 filed on Jan. 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
A range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. Pat. No. 3,553,139, Jan. 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Pat. No. 4,101,457, Place et al, Jul. 18, 1978, and in U.S. Pat. No. 4,507,219, Hughes, Mar. 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. Pat. No. 4,261,868, Hora et al, Apr. 14, 1981. Enzymes for use in detergents can be stabilised by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. Pat. No. 3,600,319, Aug. 17, 1971, Gedge et al, EP 199,405 and EP 200,586, Oct. 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. Pat. No. 3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.
The enzyme particles according to the present invention are characterized by having a reduced average particle size less than 600 microns, preferably between 50 and 500 microns, most preferred between 100 and 400 microns. Stated particle sizes are the diameters of particles of equal volume. Desirably, the particle size distribution is relatively narrow so that average particle sizes expressed as number average or weight average sizes are similar. Particle sizes can be measured, for example, using Coulter counters or laser particle size measuring equipment such as that sold under the Malvern name. The enzyme particles are prepared by grinding in a mill which will break down the particles to diameters below 600 microns. The enzyme particles will generally be supplied as much larger particles of above about 600 microns diameter. If desired, the enzyme particle may be premixed with other solids (e.g. builders, enzymes). Preferred mills are colloid mills.
Surprisingly, it has now been found that the enzyme particles of reduced particle size, are physically and chemically stable in the concentrate, while at the same time being more effective in the wash liquor.
The present invention also relates to a process for the production of a nonaqueous liquid detergent having the composition and properties described above. In this process, the liquid constituents are thoroughly mixed in a first mixing step and the suspension obtained is subjected to wet grinding so that the average particle diameter of the solid constituents in the suspension obtained after grinding is 5-200 microns. In a second process step, the enzyme particles are mixed with the ground suspension from the first mixing step in a second mixing step. This mixture is then subjected to wet grinding so that the average particle size of the enzyme particle is less than 600 microns, preferably between 50 and 500 microns, most preferred between 100 and 400 microns. Other compounds, such as bleach compounds are then added to the resulting mixture.
The nonaqueous detergent compositions of this invention may further comprise a surfactant- and low-polarity solvent-containing liquid gel phase having dispersed therein the enzyme particles. The components of the liquid and solid phases of the detergent compositions herein, as well as composition form, preparation and use, are described in greater detail as follows: All concentrations and ratios are on a weight basis unless otherwise specified.
Surfactant
The amount of the surfactant mixture component of the detergent compositions herein can vary depending upon the nature and amount of other composition components and depending upon the desired rheological properties of the ultimately formed composition. Generally, this surfactant mixture will be used in an amount comprising from about 10% to 90% by weight of the composition. More preferably, the surfactant mixture will comprise from about 15% to 50% by weight of the composition.
A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in U.S. Pat. No. 3,664,961 issued to Norris on May 23, 1972.
Highly anionic preferred surfactants are the linear alkyl benzene sulfonate (LAS) materials. Such surfactants and their preparation are described for example in U.S. Pat. Nos. 2,220,099 and 2,477,383, incorporated herein by reference. Especially preferred are the sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14. Sodium C11-C14, e.g., C12, LAS is especially preferred.
Other suitable surfactants include the alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C18 alkyl component, more preferably a C12-C15 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations).
Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)mSO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C18 alkyl or hydroxyalkyl, more preferably C12-C15 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations Exemplary surfactants are C12-C15 alkyl polyethoxylate (1.0) sulfate (C12-C15E(1.0)M), C12-C15 alkyl polyethoxylate (2.25) sulfate (C12-C15E(2.25)M), C12-C15 alkyl polyethoxylate (3.0) sulfate (C12-C15E(3.0)M), and C12-C15 alkyl polyethoxylate (4.0) sulfate (C12-C15E(4.0)M), wherein M is conveniently selected from sodium and potassium.
Other suitable anionic surfactants to be used are alkyl ester sulfonate surfactants including linear esters of C8-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to xe2x80x9cThe Journal of the American Oil Chemists Societyxe2x80x9d, 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula:
wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations. Preferably, R3 is C10-C16 alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is C10-C16 alkyl.
Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C9-C20 linear alkylbenzenesulfonates, C8-C22 primary of secondary alkanesulfonates, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, C8-C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6-C12 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2O)kxe2x80x94CH2COOxe2x80x94M+ wherein R is a C8-C22 alkyl, k is an integer from 1 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in xe2x80x9cSurface Active Agents and Detergentsxe2x80x9d (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
When included therein, the detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 5% to about 25% by weight of such anionic surfactants.
One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 14, more preferably from 12 to 14. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C12-C15 primary alcohols containing 5-8 moles of ethylene oxide per mole of alcohol.
Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula
RO (CnH2nO)tZx
wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less. than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula
wherein R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight C11-15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
Nonaqueous Liquid Diluent
To form the liquid phase of the detergent compositions, the hereinbefore described surfactant (mixture) may be combined with a nonaqueous liquid diluent such as a liquid alcohol alkoxylate material or a nonaqueous, low-polarity organic solvent.
Alcohol Alkoxylates
One component of the liquid diluent suitable to form the compositions herein comprises an alkoxylated fatty alcohol material. Such materials are themselves also nonionic surfactants. Such materials correspond to the general formula:
R1(CmH2mO)nOH
wherein R1 is a C8-C16 alkyl group, m is from 2 to 4, and n ranges from about 2 to 12. Preferably R1 is an alkyl group, which may be primary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms. Preferably also the alkoxylated fatty alcohols will be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
The alkoxylated fatty alcohol component of the liquid diluent will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15.
Examples of fatty alcohol alkoxylates useful as one of the essential components of the nonaqueous liquid diluent in the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials have been commercially marketed under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company. Other useful Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C12-C13 alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated C9-C11 primary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanol tradename. Dobanol 91-5 is an ethoxylated C9-C11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15-S-9 both of which are linear secondary alcohol ethoxylates that have been commercially marketed by Union Carbide Corporation. The former is a mixed ethoxylation product of C11 to C15 linear secondary alkanol with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide being reacted.
Other types of alcohol ethoxylates useful in the present compositions are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14-15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products have also been commercially marketed by Shell Chemical Company.
The alcohol alkoxylate component when utilized as part of the liquid diluent in the nonaqueous compositions herein will generally be present to the extent of from about 1% to 60% by weight of the composition. More preferably, the alcohol alkoxylate component will comprise about 5% to 40% by weight of the compositions herein. Most preferably, the alcohol alkoxylate component will comprise from about 10% to 25% by weight of the detergent compositions herein.
Nonaqueous Low-Polarity Organic Solvent
Another component of the liquid diluent which may form part of the detergent compositions herein comprises nonaqueous, low-polarity organic solvent(s). The term xe2x80x9csolventxe2x80x9d is used herein to connote the non-surface active carrier or diluent portion of the liquid phase of the composition. While some of the essential and/or optional components of the compositions herein may actually dissolve in the xe2x80x9csolventxe2x80x9d-containing phase, other components will be present as particulate material dispersed within the xe2x80x9csolventxe2x80x9d-containing phase. Thus the term xe2x80x9csolventxe2x80x9d is not meant to require that the solvent material be capable of actually dissolving all of the detergent composition components added thereto.
The nonaqueous organic materials which are employed as solvents herein are those which are liquids of low polarity. For purposes of this invention, xe2x80x9clow-polarityxe2x80x9d liquids are those which have little, if any, tendency to dissolve one of the preferred types of particulate material used in the compositions herein, i.e., the peroxygen bleaching agents, sodium perborate or sodium percarbonate. Thus relatively polar solvents such as ethanol should not be utilized. Suitable types of low-polarity solvents useful in the nonaqueous liquid detergent compositions herein do include alkylene glycol mono lower alkyl ethers, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides, and the like.
A preferred type of nonaqueous, low-polarity solvent for use herein comprises the mono-, di-, tri-, or tetra-C2-C3 alkylene glycol mono C2-C6 alkyl ethers. The specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropolyene glycol monoethyl ether, and dipropylene glycol monobutyl ether. Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are especially preferred. Compounds of the type have been commercially marketed under the tradenames Dowanol, Carbitol, and Cellosolve.
Another preferred type of nonaqueous, low-polarity organic solvent useful herein comprises the lower molecular weight polyethylene glycols (PEGs). Such materials are those having molecular weights of at least about 150. PEGs of molecular weight ranging from about 200 to 600 are most preferred.
Yet another preferred type of non-polar, nonaqueous solvent comprises lower molecular weight methyl esters. Such materials are those of the general formula: R1xe2x80x94C(O)xe2x80x94OCH3 wherein R1 ranges from 1 to about 18. Examples of suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.
The nonaqueous, low-polarity organic solvent(s) employed should, of course, be compatible and non-reactive with other composition components, e.g., bleach and/or activators, used in the liquid detergent compositions herein. Such a solvent component will generally be utilized in an amount of from about 1% to 60% by weight of the composition. More preferably, the nonaqueous, low-polarity organic solvent will comprise from about 5% to 40% by weight of the composition, most preferably from about 10% to 25% by weight of the composition.
Liquid Diluent Concentration
As with the concentration of the surfactant mixture, the amount of total liquid diluent in the compositions herein will be determined by the type and amounts of other composition components and by the desired composition properties. Generally, the liquid diluent will comprise from about 20% to 95% by weight of the compositions herein. More preferably, the liquid diluent will comprise from about 50% to 70% by weight of the composition.
Solid Phase
The nonaqueous detergent compositions herein may further comprise a solid phase of particulate material which is dispersed and suspended within the liquid phase. Generally such particulate material will range in size from about 0.1 to 1500 microns. More preferably such material will range in size from about 5 to 500 microns.
The particulate material utilized herein can comprise one or more types of detergent composition components which in particulate form are substantially insoluble in the nonaqueous liquid phase of the composition. The types of particulate materials which can be utilized are described in detail as follows:
Peroxygen Bleaching Agent with Optional Bleach Activators
The most preferred type of particulate material useful for forming the solid phase of the detergent compositions herein comprises particles of a peroxygen bleaching agent. Such peroxygen bleaching agents may be organic or inorganic in nature. Inorganic peroxygen bleaching agents are frequently utilized in combination with a bleach activator.
Useful organic peroxygen bleaching agents include percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, Hartman, Issued Nov. 20, 1984; European Patent Application EP-A-133,354, Banks et al., Published Feb. 20, 1985; and U.S. Pat. No. 4,412,934, Chung et al., Issued Nov. 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in U.S. Pat. No. 4,634,551, Issued Jan. 6, 1987 to Burns et al.
Inorganic peroxygen bleaching agents may also be used in particulate form in the detergent compositions herein. Inorganic bleaching agents are in fact preferred. Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials, most preferably the percarbonates. For example, sodium perborate (e.g. mono- or tetra-hydrate) can be used. Suitable inorganic bleaching agents can also include sodium or potassium carbonate peroxyhydrate and equivalent xe2x80x9cpercarbonatexe2x80x9d bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used. Frequently inorganic peroxygen bleaches will be coated with silicate, borate, sulfate or water-soluble surfactants. For example, coated percarbonate particles are available from various commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.
Inorganic peroxygen bleaching agents, e.g., the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during use of the compositions herein for fabric laundering/bleaching) of the peroxy acid corresponding to the bleach activator. Various non-limiting examples of activators are disclosed in U.S. Pat. No. 4,915,854, Issued Apr. 10, 1990 to Mao et al.; and U.S. Pat. No. 4,412,934 Issued Nov. 1, 1983 to Chung et al. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical. Mixtures thereof can also be used. See also the hereinbefore referenced U.S. Pat. No. 4,634,551 for other typical bleaches and activators useful herein.
Other useful amido-derived bleach activators are those of the formulae:
R1N(R5)C(O)R2C(O)L or R1C(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenol sulfonate.
Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate and mixtures thereof as described in the hereinbefore referenced U.S. Pat. No. 4,634,551. Such mixtures are characterized herein as (6-C8-C10 alkamido-caproyl)oxybenzenesulfonate.
Another class of useful bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al. in U.S. Pat. No. 4,966, 723, Issued Oct. 30, 1990, incorporated herein by reference. A highly preferred activator of the benzoxazin-type is:
Still another class of useful bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Pat. No. 4,545,784, Issued to Sanderson, Oct. 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
If peroxygen bleaching agents are used as all or part of the essentially present particulate material, they will generally comprise from about 1% to 30% by weight of the composition. More preferably, peroxygen bleaching agent will comprise from about 1% to 20% by weight of the composition. Most preferably, peroxygen bleaching agent will be present to the extent of from about 3% to 15% by weight of the composition. If utilized, bleach activators can comprise from about 0.5% to 20%, more preferably from about 1% to 10%, by weight of the composition. Frequently, activators are employed such that the molar ratio of bleaching agent to activator ranges from about 1:1 to 10:1, more preferably from about 1.5:1 to 5:1.
In addition, it has been found that bleach activators, when agglomerated with certain acids such as citric acid, are more chemically stable.
Surfactants
A type of particulate material which can be suspended in the nonaqueous liquid detergent compositions herein includes ancillary anionic surfactants which are fully or partially insoluble in the nonaqueous liquid phase. The most common type of anionic surfactant with such solubility properties comprises primary or secondary alkyl sulfate anionic surfactants. Such surfactants are those produced by the sulfation of higher C8-C20 fatty alcohols.
Conventional primary alkyl sulfate surfactants have the general formula
ROSO3xe2x88x92M+
wherein R is typically a linear C8-C20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation. Preferably R is a C10-C14 alkyl, and M is alkali metal. Most preferably R is about C12 and M is sodium.
Conventional secondary alkyl sulfates may also be utilized as the essential anionic surfactant component of the solid phase of the compositions herein. Conventional secondary alkyl sulfate surfactants are those materials which have the sulfate moiety distributed randomly along the hydrocarbyl xe2x80x9cbackbonexe2x80x9d of the molecule. Such materials may be depicted by the structure
CH3(CH2)n(CHOSO3xe2x88x92M+) (CH2)mCH3
wherein m and n are integers of 2 or greater and the sum of m+n is typically about 9 to 15, and M is a water-solubilizing cation.
If utilized as all or part of the requisite particulate material, ancillary anionic surfactants such as alkyl sulfates will generally comprise from about 1% to 10% by weight of the composition, more preferably from about 1% to 5% by weight of the composition. Alkyl sulfate used as all or part of the particulate material is prepared and added to the compositions herein separately from the unalkoxylated alkyl sulfate material which may form part of the alkyl ether sulfate surfactant component essentially utilized as part of the liquid phase herein.
Organic Builder Material
Another possible type of particulate material which can be suspended in the nonaqueous liquid detergent compositions herein comprises an organic detergent builder material which serves to counteract the effects of calcium, or other ion, water hardness encountered during laundering/bleaching use of the compositions herein. Examples of such materials include the alkali metal, citrates, succinates, malonates, fatty acids, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids and citric acid. Other examples of organic phosphonate type sequestering agents such as those which have been sold by Monsanto under the Dequest tradename and alkanehydroxy phosphonates. Citrate salts are highly preferred.
Other suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For example, such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, such as those sold by BASF under the Sokalan trademark.
Another suitable type of organic builder comprises the water-soluble salts of higher fatty acids, i.e., xe2x80x9csoapsxe2x80x9d. These include alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
If utilized as all or part of the requisite particulate material, insoluble organic detergent builders can generally comprise from about 1% to 20% by weight of the compositions herein. More preferably, such builder material can comprise from about 4% to 10% by weight of the composition.
Inorganic Alkalinity Sources
Another possible type of particulate material which can be suspended in the nonaqueous liquid detergent compositions herein can comprise a material which serves to render aqueous washing solutions formed from such compositions generally alkaline in nature. Such materials may or may not also act as detergent builders, i.e., as materials which counteract the adverse effect of water hardness on detergency performance.
Examples of suitable alkalinity sources include water-soluble alkali metal carbonates, bicarbonates, borates, silicates and metasilicates. Although not preferred for ecological reasons, water-soluble phosphate salts may also be utilized as alkalinity sources. These include alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Of all of these alkalinity sources, alkali metal carbonates such as sodium carbonate are the most preferred.
The alkalinity source, if in the form of a hydratable salt, may also serve as a desiccant in the nonaqueous liquid detergent compositions herein. The presence of an alkalinity source which is also a desiccant may provide benefits in terms of chemically stabilizing those composition components such as the peroxygen bleaching agent which may be susceptible to deactivation by water.
If utilized as all or part of the particulate material component, the alkalinity source will generally comprise from about 1% to 15% by weight of the compositions herein. More preferably, the alkalinity source can comprise from about 2% to 10% by weight of the composition. Such materials, while water-soluble, will generally be insoluble in the nonaqueous detergent compositions herein. Thus such materials will generally be dispersed in the nonaqueous liquid phase in the form of discrete particles.
Optional Composition Components
In addition to the composition liquid and solid phase components as hereinbefore described, the detergent compositions herein can, and preferably will, contain various optional components. Such optional components may be in either liquid or solid form. The optional components may either dissolve in the liquid phase or may be dispersed within the liquid phase in the form of fine particles or droplets. Some of the materials which may optionally be utilized in the compositions herein are described in greater detail as follows:
Optiona Inorganic Detergent Builders
The detergent compositions herein may also optionally contain one or more types of inorganic detergent builders beyond those listed hereinbefore that also function as alkalinity sources. Such optional inorganic builders can include, for example, aluminosilicates such as zeolites. Aluminosilicate zeolites, and their use as detergent builders are more fully discussed in Corkill et al., U.S. Pat. No. 4,605,509; Issued Aug. 12, 1986, the disclosure of which is incorporated herein by reference. Also crystalline layered silicates, such as those discussed in this ""509 U.S. patent, are also suitable for use in the detergent compositions herein. If utilized, optional inorganic detergent builders can comprise from about 2% to 15% by weight of the compositions herein.
Optional Chelating Agents
The detergent compositions herein may also optionally contain a chelating agent which serves to chelate metal ions, e.g., iron and/or manganese, within the nonaqueous detergent compositions herein. Such chelating agents thus serve to form complexes with metal impurities in the composition which would otherwise tend to deactivate composition components such as the peroxygen bleaching agent. Useful chelating agents can include amino carboxylates, phosphonates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof.
Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethyl-ethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, ethylenediaminedi-succinates and ethanoldiglycines. The alkali metal salts of these materials are preferred.
Amino phosphonates are also suitable for use as chelating agents in the compositions of this invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylene-phosphonates) as DEQUEST. Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Preferred chelating agents include hydroxyethyl-diphosphonic acid (HEDP), diethylene triamine penta acetic acid (DTPA), ethylenediamine disuccinic acid (EDDS) and dipicolinic acid (DPA) and salts thereof. The chelating agent may, of course, also act as a detergent builder during use of the compositions herein for fabric laundering/ bleaching. The chelating agent, if employed, can comprise from about 0.1% to 4% by weight of the compositions herein. More preferably, the chelating agent will comprise from about 0.2% to 2% by weight of the detergent compositions herein.
Optional Thickening, Viscosity Control and/or Dispersing Agents
The detergent compositions herein may also optionally contain a polymeric material which serves to enhance the ability of the composition to maintain its solid particulate components in suspension. Such materials may thus act as thickeners, viscosity control agents and/or dispersing agents. Such materials are frequently polymeric polycarboxylates but can include other polymeric materials such as polyvinylpyrrolidone (PVP) and polymeric amine derivatives such as quaternized, ethoxylated hexamethylene diamines.
Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight of the polymer.
Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000, and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, Diehl, U.S. Pat. No. 3,308,067, issued Mar. 7, 1967. Such materials may also perform a builder function.
If utilized, the optional thickening, viscosity control and/or dispersing agents should be present in the compositions herein to the extent of from about 0.1% to 4% by weight. More preferably, such materials can comprise from about 0.5% to 2% by weight of the detergents compositions herein.
Optional Brighteners, Suds Suppressors and/or Perfumes
The detergent compositions herein may also optionally contain conventional brighteners, suds suppressors, silicone oils, bleach catalysts, and/or perfume materials. Such brighteners, suds suppressors, silicone oils, bleach catalysts, and perfumes must, of course, be compatible and non-reactive with the other composition components in a nonaqueous environment. If present, brighteners suds suppressors and/or perfumes will typically comprise from about 0.01% to 2% by weight of the compositions herein.
Suitable bleach catalysts include the manganese based complexes disclosed in U.S. Pat. Nos. 5,246,621, 5,244,594, 5,114,606 and 5,114,611.
Composition Form
The particulate-containing liquid detergent compositions of this invention are substantially nonaqueous (or anhydrous) in character. While very small amounts of water may be incorporated into such compositions as an impurity in the essential or optional components, the amount of water should in no event exceed about 5% by weight of the compositions herein. More preferably, water content of the nonaqueous detergent compositions herein will comprise less than about 1% by weight.
The particulate-containing nonaqueous detergent compositions herein will be in the form of a liquid.
Composition Preparation and Use
The non-aqueous liquid detergent compositions herein can be prepared by first forming the surfactant-containing non-aqueous liquid phase and by thereafter adding to this phase the additional particulate components in any convenient order and by mixing, e.g., agitating, the resulting component combination to form the phase stable compositions herein. In a typical process for preparing such compositions, essential and certain preferred optional components will be combined in a particular order and under certain conditions.
In a first step of a preferred preparation process, the anionic surfactant-containing powder used to form the surfactant-containing liquid phase is prepared. This pre-preparation step involves the formation of an aqueous slurry containing from 40% to 50% of one or more alkali metal salts of linear C10-16 alkyl benzene sulfonic acid and from 3% to 15% of one or more diluent non-surfactant salts. In a subsequent step, this slurry is dried to the extent necessary to form a solid material containing less than 5% by weight of residual water.
After preparation of this solid anionic surfactant-containing material, this material can be combined with one or more of the non-aqueous organic solvents to form the surfactant-containing liquid phase of the detergent compositions herein. This is done by reducing the anionic surfactant-containing material formed in the previously described pre-preparation step to powdered form and by combining such powdered material with an agitated liquid medium comprising one or more of the non-aqueous organic solvents, either surfactant or non-surfactant or both, as hereinbefore described. This combination is carried out under agitation conditions which are sufficient to form a thoroughly mixed dispersion of the LAS/salt material throughout a non-aqueous organic liquid.
In a subsequent processing step, the non-aqueous liquid dispersion so prepared can then be subjected to milling or high shear agitation under conditions which are sufficient to provide the structured, surfactant-containing liquid phase of the detergent compositions herein. Such milling or high shear agitation conditions will generally include maintenance of a temperature between 20xc2x0 C. and 50xc2x0 C. and a processing time that is sufficient to form a network of aggregated small particles of the insoluble fraction of the anionic surfactant-containing powdered material. Such small particles will generally range in size from about 10 to 200 microns. Milling and high shear agitation of this combination will generally provide an increase in the yield value of the structured liquid phase to within the range of from 1 Pa to 5 Pa.
After formation of the dispersion of LAS/salt co-dried material in the non-aqueous liquid, either before or after such dispersion is milled or agitated to increase its yield value, the additional particulate material to be used in the detergent compositions herein can be added. Such components which can be added under high shear agitation include any optional surfactant particles, particles of substantially all of an organic builder, e.g., citrate and/or fatty acid, and/or an alkalinity source, e.g., sodium carbonate, can be added while continuing to maintain this admixture of composition components under shear agitation. Agitation of the mixture is continued, and if necessary, can be increased at this point to form a uniform dispersion of insoluble solid phase particulates within the liquid phase.
In a second process step, the enzyme particles are mixed with the ground suspension from the first mixing step in a second mixing step. This mixture is then subjected to wet grinding so that the average particle size of the enzyme particles is less than 600 microns, preferably between 50 and 500 microns, most preferred between 100 and 400 microns. Other compounds, such as bleach precursors and bleach compounds are then added to the resulting mixture.
After some or all of the foregoing solid materials have been added to this agitated mixture, the particles of the highly preferred peroxygen bleaching agent can be added to the composition, again while the mixture is maintained under shear agitation. By adding the peroxygen bleaching agent material last, or after all or most of the other components, and especially after alkalinity source particles, have been added, desirable stability benefits for the peroxygen bleach can be realized.
As a final process step, after addition of all of the particulate material, agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity, yield value and phase stability characteristics. Frequently this will involve agitation for a period of from about 1 to 30 minutes.
In adding solid components to non-aqueous liquids in accordance with the foregoing procedure, it is advantageous to maintain the free, unbound moisture content of these solid materials below certain limits. Free moisture in such solid materials is frequently present at levels of 0.8% or greater. By reducing free moisture content, e.g., by fluid bed drying, of solid particulate materials to a free moisture level of 0.5% or lower prior to their incorporation into the detergent composition matrix, significant stability advantages for the resulting composition can be realized.
The compositions of this invention, prepared as hereinbefore described, can be used to form aqueous washing solutions for use in the laundering and bleaching of fabrics. Generally, an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering/bleaching solutions. The aqueous washing/bleaching solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered and bleached therewith.
An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering/bleaching solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous solution. More preferably, from about 800 to 5,000 ppm of the detergent compositions herein will be provided in aqueous washing/bleaching solution.
The following examples illustrate the preparation and performance advantages of non-aqueous liquid detergent compositions of the instant invention. Such examples, however, are not necessarily meant to limit or otherwise define the scope of the invention herein.

Nonaqueous detergent compositions containing enzymes


An active satellite dispenser is preferably attachable to a reusable launch vehicle for deployment of one or more satellites into one or more desired orbits. The active satellite dispenser includes a center mast that releasably receives the satellite(s), a liquid propellant rocket, and an orbital control system on an avionics pallet. In the preferred embodiment, a pressurized gas selectively pressurizes the propellant tanks (which may include fuel and oxidizer tanks), to provide propellant to the rocket. In operation, the launch vehicle releases the satellite dispenser in a first deployment orbit. The active dispenser rocket and orbital control system then transport the active dispenser and satellite(s) into the final deployment orbit. In the preferred embodiment the active dispenser can operate multiple times to place individual satellites in different orbits.

The present invention relates to hardware for the launch, transportation, transfer, and release of satellites, cargo, and other payloads in earth orbit. More particularly, the present invention relates to a satellite dispenser providing propulsion and avionics systems for the controlled release of multiple satellites
The transportation of cargo to space is expensive. The high cost is partially attributable to the aggregation of multiple, costly individual operations that are needed to transport and deploy satellites and other cargo to orbit. The latter part of the orbital transportation operation, i.e., transporting the payload from low earth orbit to the desired final higher orbit, is typically accomplished by an upper, or final, stage. This stage is ignited and transports the payload to the final orbit. Sometimes this stage remains attached to the payload, satellite, or cargo; but it is usually discarded in orbit. Upper stages vary in their capability of independent actions from a passive, simple, small, solid rocket motor just providing additional propulsion capability, which goes in the direction it is pointed when ignited, to very capable, restartable, liquid rocket engines capable of multiple restarts and significant maneuvering using thruster(s) and related avionics. Some active upper stages are able to dispense multiple satellites.
Launch vehicles used to deploy satellites in a predetermined orbit are evolving from expendable, and partially expendable rockets, toward fully reusable launch vehicles (RLVs) capable of multiple reuse. The primary advantage of RLVs is the potential for significant cost savings. RLVs frequently utilize active satellite dispensers and upper stages. Satellite launch systems still include a device that couples the satellite to the launch vehicle; but in today""s world, this dispensing hardware takes on a more active role than the simple release of the satellite in response to a control signal. Recent reusable vehicle advances, technological improvements, and commercial market forces are moving the satellite industry toward smaller, more sophisticated commercial networks of communications satellites requiring multiple satellites in various orbital planes around earth.
The increased demand for communication satellite networks and higher orbits has given rise to active, more capable, customer-sensitive satellite dispensers that satisfy the new privately-financed communication network markets. The new commercial networks require innovative satellites of different size, weight, and transportation requirements. Existing satellite dispensers lack the flexibility and cost effectiveness of reusable vehicles. Moreover, existing satellite dispensers lack subsystem commonality, propellant compatibility, and/or the ability to adapt to the emerging reusable launch vehicles. Existing satellite dispensers fail to adequately take advantage of the reusable vehicles"" reusable shrouds and orbital satellite release techniques.
Previous dispensers stack multiple satellites vertically, and therefore typically employ discardable shrouds that can clutter the orbital environment with spent hardware, which can endanger other space operations. Shortly, international agreements are expected to limit the placement of satellites to those systems that minimize the debris impact on others.
U.S. Pat. No. 5,568,901 to Stiennon, entitled xe2x80x9cTwo Stage Launch Vehicle and Launch Trajectory Method,xe2x80x9d is purported to be a fully reusable launch vehicle, but fails to mention anything of a satellite dispenser.
The space shuttle is a partly-reusable vehicle and has several expendable satellite assist modules, or third stages, but at significant cost and requiring extensive hardware dispensers specific to the shuttle payload bay and, in some cases, requiring the changing of the axial orientation of the satellite by a significant amount or to exit the payload bay via a Frisbee(copyright)-throwing method.
U.S. Pat. No. 5,242,135 to Scott et al., entitled xe2x80x9cspace Transfer Vehicle and Integrated Guidance System,xe2x80x9d is a space transfer system capable of continuing the propulsive cycle of earlier stages, but lacks the full service structure system to handle the new generation of communications satellites. No provision for both forward and sideways satellite ejection appears to be available from this patent. No shroud reuse or any reuse of any hardware, except the space transfer vehicle, is implied. No provision in the hardware is evident for disposal at end of life.
U.S. Pat. No. 5,884,866 to Steinmeyer et al., entitled xe2x80x9cSatellite Dispenser,xe2x80x9d is a dispenser for the 1990s, but has no propulsion or other active subsystems. The post can accommodate the newer network communication satellites, but it appears the entire upper stage of the poorly defined launch vehicle must be taken to each individual orbit for satellite dispensing.
U.S. Pat. No. 5,337,980 to Homer et al., entitled xe2x80x9cSpacecraft-to-Launch-Vehicle Transition,xe2x80x9d is more a structural connection between a vehicle and a satellite, rather than a dispenser. The drawings seem to depict a rocket engine, but it appears to be a part of the satellite. The adapter and/or structural hardware appears to have no active dispensing function except a release capability.
U.S. Pat. No. 5,199,672 to King et al., entitled xe2x80x9cMethod and Apparatus for Deploying a Satellite,xe2x80x9d is a solid rocket version of a dispenser designed to place many small satellites into a specific orbital plane and focuses on the specific design to accommodate the Pegasus. The four separate pallets are fired into different orbital planes by waiting to fire the solid rocket motors at different times as the earth turns below.
U.S. Pat. No. 5,816,539 to Stotelmeyer et al., entitled xe2x80x9cIntegrated Storage and Transfer System and Method for Spacecraft Propulsion Systems,xe2x80x9d is an orbital assist module (OAM) built into the stack of an expendable launch vehicle (ELV). The orbital assist module propellant comprises hydrazine and is difficult to handle.
In contrast, the present invention uses propellants, preferably liquid propellants, used in a single, pressure-feed engine that preferably utilizes components having commonality with the reusable launch vehicle. This hardware commonality in engine, main propellants, pressurants, radiation-hardened avionics, and attitude control systems (ACS), including the propellant used in the ACS tanks, reduces the testing, procurement, ground handling, support systems, andxe2x80x94most importantlyxe2x80x94the cost. The propellants used also lend themselves to increased ground safety and cost-effective operations within the present invention.
Although the present invention will be described with reference to a preferred embodiment that is designed to be used with the K-1 reusable launch vehicle system, which includes a launch assist platform and an orbital vehicle (hereinafter, the K-1 orbital vehicle, or the like) currently under development by Kistler Aerospace Corporation, it will be appreciated by one of ordinary skill in the art that the invention can be readily adapted for use with other launch systems without departing from the spirit and scope of the disclosed invention.
A primary object of the active dispenser is to transfer the satellite to a higher orbit and position it in the proper orbital location in a cost-effective manner.
An advantage of the present invention is the cost-effective combination of a reusable launch vehicle subsystem, including efficient propulsion subsystems, pre-engineered common computer avionics, propellant, pressurant, and attitude control thruster hardware subsystems, and a dispenser for multiple satellites.
An advantage of the active dispenser on a reusable launch vehicle is the ability to integrate commonality with subsystems used on the launch vehicle and/or satellite hardware providing cost-effective common subsystems through commonality in design, procurement, testing, and propellant loading.
Another advantage of the invention is the ability to integrate common ground handling techniques, technical maintenance, financing, and ownership of the active dispenser, launch vehicle, and satellites.
Another advantage of the invention is an integrated commercial, satellite delivery operation that all works together in a cohesive manner to accomplish the ground processing, launch, transfer to the proper orbit, release of the satellite, and potential follow-on support.
Another advantage of the active dispenser is an integrated design, flexible enough to be capable of accommodating on a general active dispenser, a number of different satellites from numerous organizations with varying requirements, different weights, various final orbits, different ground processing requirements, and varying financial needs.
Another advantage of the invention is the increased energy efficiency in the use of liquid propellants, including the liquid storable propellants, the decreased cost in simplifying the ground handling by using the storable propellants, increased flexibility from the restartable orbital propulsion, and the increased reliability and simplified handling from the common, pre-tested hardware and propellant systems.
Another advantage of the invention is a single, pressure-fed, restartable, liquid bipropellant main engine located at the base of the active dispenser, which fires to propel the active dispenser into its proper orbit.
Another advantage of the active dispenser is a reusable, conical payload adapter at the base of the dispenser and a clampband that attaches the K-1 vehicle or other vehicles to the active dispenser.
Another advantage of the invention is the K-1 orbiter or other launch vehicle, which opens its payload module dome in orbit and deploys either vertically or horizontally everything above the clampband into space.
Another advantage of the invention includes the various satellites with different shapes that are able to be attached to the support mast using adaptable structural interfaces.
Another advantage of the invention is the small thrusters mounted to the active dispenser used for attitude control, a pallet for avionics hardware, and gas storage bottles for pressurization and attitude control.
Another advantage of the invention includes two similar tanks (one or more for fuel and one or more for oxidizer) mounted on either side of the support mast, which connects the engine to the propellant via feed lines.
Another advantage of the invention is the propulsion system design using hardware common to the K-1.
Another advantage of the invention is that the propellant tanks are pressurized by gas storage bottles filled with pressurant gas.
Another advantage of the invention is an active dispenser avionics system, which uses the radiation-hardened hardware for control as the K-1 orbital vehicle.
Another advantage of the invention is the avionics system, which uses a triplex computing architecture with three cross-strapped 1553 avionics databases and a hardware voter.
Another advantage of the invention is the electronics power, which is triply redundant, and the utility power, which is dual redundant.
Another advantage of the invention is the flight software, which is a modified version of the software used on the K-1 orbital vehicle.
Another advantage of the active dispenser, in a nominal mission mated with one or more customer satellites, is its being processed, handled, fueled, and mated to the K-1 payload module in the K-1 payload processing facility, using the same hardware, consumables, and staff already on hand for other similar hardware on the existing reusable launch vehicles.
Another advantage of the invention is that the orbital vehicle deploys the active dispenser and satellites after it reaches a nominal 200 km circular orbit at the desired inclination, depending on the mission.
Another advantage of the invention is achieved after adequate clearance between the active dispenser and orbital vehicle is achieved and the active dispenser performs a series of burns used to place the satellites into their desired final orbits, without further assistance form the launch vehicle.
The active dispenser places satellites into higher orbits than the host launch vehicle. This third stage is cost-effective because it combines the advantages of a reusable launch vehicle with the flexibility and common subsystems.
In a nominal mission, the active dispenser is mated with the customer""s satellite in an off-line vehicle processing operation, including propellant loading, and mated to the K-1 payload module in the K-1 payload processing facility. The launch vehicle deploys the active dispenser and satellites after it reaches a higher circular orbit at the desired orbital inclination. The active dispenser initiates a series of burns to place the satellites into their desired final orbits.
Other objects, advantages, and novel features, and further scope of applicability will be set forth in part in the detailed description to follow, taken in conjunction with the accompanying drawings, FIGS. 1-5, and, in part, will become apparent to those skilled in the art upon examination of the following, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the inventions particularly pointed out in the appended claims.

Active satellite dispenser for reusable launch vehicle