A method for production of high purity silica sols comprising the steps: (a) adding a phosphonic acid-based complexing agent to the silicic acid-containing solution forming complexes with metal cations present in said solution; (b) forming in said silicic acid-containing solution a precipitation containing phosphonic acid-based complexing agent and metal cations; (c) removing the precipitation from the solution; and, (d) polymerising the silicic acid in the solution to obtain a silica sol. The invention also relates to silica sols containing at least one phosphonic acid-based complexing agent.

The present invention relates to a method for manufacturing of high purity silica sols. More specifically, the invention relates to a method of manufacturing of high purity silica sols involving use of phosphonic acid-based complexing agents.
Silica sols have been known for decades and are nowadays used in a great variety of applications such as in the paper production, coatings, catalysts, anti-skid products, polishing agents for various industries including the electronic industry, especially for wafer polishing. In many applications, the use of silica sols contaminated with traces of transition metals, alkali and alkaline earth metals, aluminum and the like have often caused problems. The presence of these metals, also in small amounts, interfere which leads to poorly performing silica sols.
Presence of e.g. contaminating metals like alkali metals such as Na, K, alkaline earth metals like Ca and Mg, transition metals such as Fe, Cu, Mn, Ni, Zn and the like are harmful when present in silica sols. Especially, aluminum is known to cause severe problems when present in the silica sol.
It has thus been elaborated various methods to prepare silica sols, having low contents of the mentioned contaminating metals.
Previous methods to produce silica sols have involved treatment of silicic acid solutions, derived from alkali metal silicates by use of various types of complexing agents such as EDTA and oxalic acid to reduce the contents of the above-mentioned disturbing metal cations.
EP-B1-464 289 discloses a method for preparation of a purified silica sol. In this method, an alkali metal silicate solution is first diluted in water, then exposed to a strong cation exchange resin to remove sodium ions from a sodium silicate solution thus forming a silicic acid solution to which oxalic acid is added. The oxalic acid is believed to form anionic complexes with metal ions, especially iron ions in the silicic acid solution. These complexes can be removed from the solution by means of an anion exchange step. Yet another cationic exchange step is required to remove remaining metal cations from the solution. The silicic acid solution is then subjected to polymerisation to form a silica sol.
The method according to EP-B1-464 289 yields some reduction in metal cations, e.g. Al, Fe, in the silicic acid solution. One drawback with the method according to EP-B1-464 289 is that a strong anionic resin must be used to separate the oxalate metal complexes. This will require regeneration of the anion exchange resin before it can be reused. Furthermore, multiple exchange steps increase the risk of contamination.
Manufacturing of high purity silica sols from fused silica or silicon metal is also known in the art. Fused silica and silicon metal are, however, highly priced raw materials which make the production very expensive.
The present invention provides for an inexpensive and effective way to produce high purity silica.
The invention is a method for producing high purity silica sols using a phosphonic acid-based complexing agent, and the high purity silica sols produced therefrom.
According to the present invention, a new method for manufacturing of high purity silica sols has been provided. The new method involves treating a silicic acid-containing solution by adding a phosphonic acid-based complexing agent to the solution, forming a precipitate of complexes of phosphonic acid-based complexing agent and metal cations, removing said complexes whereafter the silicic acid can be subjected to polymerisation. The invention is further defined in the appended claims.
More specifically, the method for the manufacturing of high purity silica sols from a silicic acid-containing solution comprises the following steps:
(a) adding a phosphonic acid-based complexing agent to the silicic acid-containing solution forming complexes with metal cations present in the solution;
(b) forming in said silicic acid-containing solution a precipitation containing phosphonic acid-based complexing agent and metal cations;
(c) removing the precipitation from the solution; and,
(d) polymerising the silicic acid in the solution to obtain a silica sol.
The silicic acid-containing solution of step (a), has a SiO2-concentration of from about 1 to about 20%, preferably containing from about 4 to about 10 weight % SiO2, most preferably from about 5 to about 7 weight % SiO2 and having a pH of from about 1 to about 4.5, preferably from about 1.5 to about 4, most preferably from about 2 to about 3, can be prepared in any known way from any alkali metal silicate including potassium silicate, sodium silicate, and lithium silicate or mixtures thereof. The alkali metal silicates are well known in the art of silica sol manufacturing and are available in various grades. Preferably, the alkali metal silicate used for production of silica sol will be sodium silicate which will be further described herebelow. In case other alkali metal silicates will be used, the same processing steps will be applicable.
Suitably, sodium silicates have a SiO2:Na2O molar ratio of from about 1 to about 5, preferably from about 3 to about 4. The silicic acid-containing solution can be obtained by increasing the SiO2:Na2O molar ratio of the silicate solution. This can be performed by cation exchange, as described in The Chemistry of Silica, Iler, R. 1979 pages 333-334, preferably by contacting a sodium silicate-containing solution with a strong cation exchange resin to yield a silicic acid-containing solution. The silicic acid is presumed to comprise an aqueous solution of one or several units of Si(OH)4 linked together.
Before the cation exchange step is performed, the sodium silicate solution is suitably diluted. Normally, the cation exchange step will dilute the alkali metal silicate solution further as water can be added during the cation exchange treatment thus yielding a lower SiO2-concentration.
Phosphonic acid-based complexing agents added in step (a) refer to phosphonic acids and salts thereof. The phosphonic acid-based complexing agents are capable of forming complexes with harmful metal cations, e.g. Al, Ca, Cr, Fe, Ti, Zr present as impurities in the silicic acid-containing solution.
Any phosphonic acid-based complexing agents soluble in the silicic acid-containing solution can be used as a complexing agent.
The phosphonic acid-based complexing agent may be added to the silicic acid-containing solution in acidic form, as a salt, or a mixture of salts.
Examples of useful phosphonic acid-based complexing agents include ethylene diamine tetra (methylene phosphonic acid), hexamethylene diamine tetra(methylene phosphonic acid), diethylene triamine penta(methylene phosphonic acid), 2-phosphonobutan-1,2,3-tricarboxylic acid, propylene diamine tetra methylene phosphonic acid)(N,N,Nxe2x80x2,Nxe2x80x2-tetra(phosphonomethyl)-1,2-diaminopropane(PDTP), 2-hydroxyethyl iminobis(methylene phosphonic acid), 2-ethylhexyl iminobis(methylene phosphonic acid), n-oktyliminobis(methylene phosphonic acid), cyclohexane-1,2-diaminetetrakis(methylene phosphonic acid), cyclohexane,1,2-diaminetetrakis(methylene phosphonic acid), pentaethylenehexamineoctakis(methylene phosphonic acid), N,N-bis(3-aminopropyl)amine hexakis(methylene phosphonic acid), glycine-N,N-di(methylene phosphonic acid), N-(2-hydroxyethyl)-N,N-di(methylene phosphonic acid), aminotris(methylene phosphonic acid), and acetodiphosphonic acid, and salts thereof.
Preferably, aminotris(methylene phosphonic acid)(ATMP) (also named nitrilotris(methylene phosphonic acid)) and (acetodiphosphonic acid(ADPA) (also named 1-hydroxyethane 1,1-diphosphonic acid) or mixtures of these phosphonic acid-based complexing agents are added to the silicic acid-containing solution.
It has been found that the formation of complexes and precipitation according to step (b) normally is optimal at a pH from about 1.2 to about 2.2, preferably from about 1.6 to about 2, most preferably from about 1.7 to about 1.9. Normally, the suitable pH value can be obtained by addition of an appropriate amount of phosphonic acid-based complexing agents, but if necessary the pH value can also be adjusted by addition of any acid or base not disturbing the process, such as phosphoric acid, diphosphoric acid, triphosphoric acid, phosphonic acid, diphosphonic, phosphonic acid and other phosphorous based acids.
Precipitation of complexes of metal cations and phosphonic acid-based complexing agents can thus be formed. Suitably, the formation of the precipitation in step (b) is carried out by ageing the solution while having the preferred pH value maintained. The formation of complexes starts almost immediately. The silicic acid-containing solution will normally turn turbid directly after the addition of phosphonic acid-based complexing agents. Usually, the initiation of precipitation can be observed after a few minutes. The process can be performed until the precipitation of the phosphonic complexes is complete. The ageing preferably is carried out for at least about 5 minutes, most preferably at least about 2 hours before the formed precipitation is removed from the solution. Usually, only 2-3 hours is enough but more time may be required before the removal of the formed complexes of the phosphonic acid-based complexing agents and the metal cations will take place, e.g. up to about 10 hours or more. When the precipitation is complete, the turbid solution will turn clear. Precipitation of e.g. Al, Fe, Ca and Zr together with the phosphonic acid-based complexing agents will occur during the ageing process resulting in a purified silicic acid-containing solution.
Means of removal of the precipitation in step (c) may include any known separation method such as filtration, decantation, or centrifugation, or combinations thereof, but also other conventional separation methods for removing formed precipitation known in the art may be considered.
Preferably, at least a portion of the cations remaining in the silicic acid-containing solution after step (c) is removed e.g. by means of ion exchange, suitably by means of a strong cation exchange resin.
It may also be desirable to remove at least a portion of the phosphonic acid-based complexing agents. This can be effected e.g. by means of ion exchange, suitably by means of a strong anion exchange resin after step (c) by means of an anion exchange resin, preferably a strong anion exchange resin. This removal step may also be omitted to retain more phosphonic acid-based complexing agents in the silica sol.
The optional cation and anion exchange steps may be carried out in any order. The cation and anion exchange step may even be integrated and carried out simultaneously by use of a prepared column containing both cation and anion exchange resin.
The temperatures in steps (a)-(c) are normally from about 5 to about 40xc2x0 C., preferably from about 15 to about 30xc2x0 C.
Polymerisation of the silicic acid in the solution in step (d) can then be performed according to a conventional polymerisation method, e.g. as described in The Chemistry of Silica, Iler, R. 1979 pages 174-176, comprising addition of the silicic acid solution to an alkaline solution, suitably having a pH of from about 7 to about 11. An example of such a method is disclosed in U.S. Pat. No. 3,440,175, hereby incorporated by reference. The solution is suitably heated, preferably to a temperature from about 80 to about 100xc2x0 C., most preferably from about 95 to about 100xc2x0 C., to start the polymerisation. The polymerisation process may take up to about 10 hours or more, preferably between 4-5 hours.
Through the invention, it is possible to produce highly pure silica sols. In a 10 weight % SiO2 sol, the content of Al is preferably below 65 ppm, most preferably below 30 ppm, Ca preferably below 15 ppm, most preferably below 10 ppm, Na preferably below 700 ppm, most preferably below 100 ppm, Fe preferably below 15 ppm, most preferably below 10 ppm, Ti preferably below 15 ppm, most preferably below 10 ppm, and Zr preferably below 12 ppm, most preferably below 10 ppm. All values refer to ppm by weight and can be determined by inductive coupled plasma (ICP). In more concentrated or diluted silica sols, the level of impurities will increase or decrease proportionally to the SiO2 content.
The invention further concerns a silica sol comprising at least one phosphonic acid-based complexing agent, suitably in an amount from about 10 to about 50000 ppm based on a 10 weight % silica sol, preferably from about 100 to about 10000 ppm, most preferably from about 1000 to about 7000 ppm. The presence of phosphonic acid-based complexing agents is advantageous in certain applications, e.g. wafer polishing. The silica sol containing phosphonic acid-based complexing agents can be prepared by the method as described above, but with phosphonic acid-based complexing agents remaining in the solution after separation of the precipitation. The phosphonic acid-based complexing agents are not removed or are only partly removed from the solution. The content of impurities in the phosphonic acid-based complexing agent-containing silica sol is preferably low as described above. Concerning other suitable and preferred features of the silica sol, such as choice of phosphonic acid-based complexing agents, the above description of the method is referred to.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the gist and scope of the present invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the claims. While the examples here below provide more specific details of the reactions, the following general principles may here be disclosed. The following example will further illustrate how the described invention may be performed without limiting the scope of it.
All parts and percentages refer to part and percent by weight, if not otherwise stated.


Described is an apparatus which comprises: an adjustable power supply source to generate an adjustable power supply; a node to provide the adjustable power supply to a device; and a bus which is operable to: send a first message to the device indicating that the adjustable power supply source is capable of dynamically providing an adjustable power supply; and receive a request from the device, the request indicating a new voltage or current specification.

The Universal Serial Bus (USB) Revision 3.1 Power Delivery (USB-PD) Specification Revision 2.0 V1.1 of May 7, 2015 states that the USB has evolved from a data interface capable of supplying limited power to a primary provider of power with a data interface. Today, many devices charge or get their power from USB ports contained in laptops, cars, aircraft, or even wall sockets. USB has become a ubiquitous power socket for many small devices such as cell phones, MP3 players and other hand-held devices. Users need USB to fulfill their requirements not only in terms of data but also to provide power to, or charge, their devices simply, often without the need to load a driver, in order to carry out "traditional" USB functions.

Adjustable power delivery scheme for universal serial bus


The use of 4-ethyloctanal as a fragrance chemical, suitable for use in creating fragrance, and scents in items such as perfumes, colognes and personal care products is disclosed.

The use of 4-ethyloctanal is disclosed as a fragrance chemical suitable for incorporation in fine fragrances, cosmetics, toiletries and related applications.
There is an ongoing need in the fragrance industry to provide new chemicals to give perfumers and other persons ability to create new fragrances for perfumes, colognes and personal care products.
The preparation of the compound 4-ethyloctanal is disclosed by Weitzel, G. et al; HSZPZAZ; Hoppe-Seyler""s Z. Physiol.Chem.; GE; 353; 1972, pages 641-653. The authors disclose the preparation of the compound by the dehydrogenation of the corresponding alcohol to the aldehyde. This article is silent as to odor of the compound or the suitability of the compound to be employed as a fragrance chemical.
The present invention is directed to the use of 4-ethyloctanal as a fragrance chemical to enhance fragrance in perfumes, toilet waters, colognes, personal products and the like. More specifically, the present invention is a method for enhancing a perfume by incorporating an olfactory acceptable amount of compounds of the formula:
These and other embodiments of the present invention will be apparent by reading the following specification.
The present invention is directed to the use of the compound, 4-ethyloctanal in fragrance formulations. The preparation of the compound, 4-ethyloctanal is described in Weitzel, G. et al; HSZPZAZ; Hoppe-Seyler""s Z. Physiol.Chem.; GE; 353; 1972, pages 641-653.
We have discovered that 4-ethyloctanal has an orange, costus odor or note, that is well suited for use as a fragrance chemical.
The use of this compound is widely applicable in current perfumery products, including the preparation of perfumes and colognes, the perfuming of personal care products such as soaps, shower gels, and hair care products as well as air fresheners, candles and cosmetic products. The compound can also be used to perfume candles and cleaning agents, such as, but not limited to soaps, detergents, dishwashing materials, scrubbing compositions, window cleaners, and the like.
In these preparations, the compound of the present invention can be used alone or in combination with other fragrance compositions, solvents, adjuvants and the like. Those with skill in the art will appreciate the nature and variety of the other ingredients that can be used in combination with the compound of the present invention.
Many types of fragrances can be employed in the present invention, the only limitation being the compatibility with the other components being employed. Suitable fragrances include but are not limited to fruits such as almond, apple, cherry, grape, pear, pineapple, orange, strawberry, raspberry; musk, flower scents such as lavender-like, rose-like, iris-like, and carnation-like. Other pleasant scents include herbal and woodland scents derived from pine, spruce and other forest smells. Fragrances may also be derived from various oils, such as essential oils, or from plant materials such as peppermint, spearmint and the like.
A list of suitable fragrances is provided in U.S. Pat. No. 4,534,891, the contents of which are incorporated by reference as if set forth in its entirety. Another source of suitable fragrances is found in Perfumes, Cosmetics and Soaps, Second Edition, edited by W. A. Poucher, 1959. Among the fragrances provided in this treatise are acacia, cassie, chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle, hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cut hay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose, vanilla, violet, wallflower, and the like.
As used herein olfactory effective amount is understood to mean the amount of compound in perfume compositions the individual component will contribute to its particular olfactory characteristics, but the olfactory effect of the perfume composition will be the sum of the effects of each of the perfume or fragrance ingredients. Thus the compounds of the invention can be used to alter the aroma characteristics of the perfume composition by modifying the olfactory reaction contributed by another ingredient in the composition. The amount will vary depending on many factors including other ingredients, their relative amounts and the effect that is desired.
The level of compound of the invention employed in the perfumed article varies from about 0.005 to about 10 weight percent, preferably from about 0.1 to about 8 and most preferably from about 0.5 to about 5 weight percent. In addition to the compounds, other agents can be used in conjunction with the fragrance. Well known materials such as surfactants, emulsifiers, and polymers to encapsulate the fragrance can also be employed without departing from the scope of the present invention.
Another method of reporting the level of the compound of the invention in the perfumed composition, i.e., the compounds as a weight percentage of the materials added to impart the desired fragrance. The compounds of the invention can range widely from 0.005 to about 10 weight percent of the perfumed composition, and preferably from about 0.1 to about 5 weight percent. Those with skill in the art will be able to employ the desired level of the compound of the invention to provide the desired fragrance and intensity.
The following are provided as specific embodiments of the present invention. Other modifications of this invention will be readily apparent to those skilled in the art, without departing from the scope of this invention. As used herein all percentages are weight percent. IFF as used in the examples is understood to mean International Flavors and Fragrances Inc., DPG is understood to mean dipropylene glycol, DEP is understood to mean diethylphthalate.

Use of 4-ethyloctanal in perfume compositions


Nucleic acid labeling compounds are disclosed. The compounds are synthesized by condensing a heterocyclic derivative with a cyclic group (e.g. a ribofuranose derivative). The labeling compounds are suitable for enzymatic attachment to a nucleic acid, either terminally or internally, to provide a mechanism of nucleic acid detection.

Gene expression in diseased and healthy individuals is oftentimes different and characterizable. The ability to monitor gene expression in such cases provides medical professionals with a powerful diagnostic tool. This form of diagnosis is especially important in the area of oncology, where it is thought that the overexpression of an oncogene, or the underexpression of a tumor suppressor gene, results in tumorogenesis. See Mikkelson et al. J. Cell. Biochem. 1991, 46, 3-8.
One can indirectly monitor gene expression, for example, by measuring a nucleic acid (e.g., mRNA) that is the transcription product of a targeted gene. The nucleic acid is chemically or biochemically labeled with a detectable moiety and allowed to hybridize with a localized nucleic acid probe of known sequence. The detection of a labeled nucleic acid at the probe position indicates that the targeted gene has been expressed. See, e.g., International Application Publication Nos. WO 97/27317, WO 92/10588 and WO 97/10365.
The labeling of a nucleic acid is typically performed by covalently attaching a detectable group (label) to either an internal or terminal position. Scientists have reported a number of detectable nucleotide analogues that have been enzymatically incorporated into an oligo- or polynucleotide. Langer et al., for example, disclosed analogues of dUTP and UTP that contain a covalently bound biotin moiety. Proc. Natl. Acad. Sci. USA 1981, 78, 6633-6637. The analogues, shown below, possess an allylamine linker arm that is attached to the C-5 position of the pyrimidine ring. The dUTP and UTP analogues, wherein R is H or OH, were incorporated into a polynucleotide.

Petrie et al. disclosed a dATP analogue, 3-[5-[(N-biotinyl-6-aminocaproyl)-amino]pentyl]-1-(2-deoxy-β-D-erythro-pentofuranosyl)-1H-pyrazolo[3,4-d]pyrimidin-4-amine-5′-triphosphate. Bioconjugate Chem. 1991, 2, 441-446. The analogue, shown below, is modified at the 3-position with a linker arm that is attached to a biotin moiety. Petrie et al. reported that the compound wherein R is biotin is incorporated into DNA by nick translation.

Prober et al. disclosed a set of four dideoxynucleotides, each containing a succinylfluorescein dye. Science 1987, 238, 336-341. The dideoxynucleotides, one of which is shown below, were enzymatically incorporated into an oligonucleotide through a template directed extension of a primer. The compounds provided for a DNA sequencing method based on gel migration.

Herrlein et al. disclosed modified nucleoside trisphosphates of the four DNA bases. Helv. Chim. Acta 1994, 77, 586-596. The compounds, one of which is shown below, contain a 3′-amino group containing radioactive or fluorescent moieties. Herrlein et al. further described the use of the nucleoside analogues as DNA chain terminators.

Cech et al. disclosed 3′-amino-functionalized nucleoside triphosphates. Collect. Czech. Chem. Commun. 1996, 61, S297-S300. The compounds, one of which is shown below, contain a fluorescein attached to the 3′-position through an amino linker. Cech et al. proposed that the described functioialized nucleosides would be useful as terminators for DNA sequencing.

The development of novel nucleic acid labeling compounds that are effectively incorporated into a nucleic acid to provide a readily detectable composition would benefit genetic analysis technologies. It would aid, for example, in the monitoring of gene expression and the detection and screening of mutations and polymorphisms. Such a compound should be suitable for enzymatic incorporation into a nucleic acid. Furthermore, the nucleic acid to which the labeling compound is attached should maintain its ability to bind to a probe, such as a complementary nucleic acid.
Although nucleic acid labeling compounds for use as coupling agents for probes are available there is a continuing need for additional compounds that are more efficient labeling compounds. There also exists a need for compounds that have increased solubility. This will make the compounds more useful for monitoring gene expression.


An automated retail terminal in which a plurality of goods and/or services are provided in an integrated system. The integrated system generally avoids duplicating hardware or functions in the course of delivering the goods or services offered, so for example in a combination ATM and Internet kiosk the same credit card or smart card reader is used for both the ATM and the Internet kiosk functions, the same control screen activates the ATM functions and the Internet functions, and etc.

For decades, retail sales and services have been automated to greater or lesser degrees. Historically in many European countries, shopkeepers of bakeries and other purveyors have long provided simple vending machines to dispense their products at their street entrances after business hours. More ambitiously automated restaurants are already legendary in the history of the United States. Other and more recent entrants in the automated retail sales and service industries include automated teller machines (ATMs), custom greeting card kiosks, automated lottery machines and other home and commercial business terminals including various Internet services available via personal computer.
Retail terminal technology generally, however, has been pervaded by a fundamental flaw which itself has gone completely unrecognized. This flaw becomes apparent when one considers the piecemeal character of retail terminals of all types in the applicable prior art. Without any known exception, automated retail functions are provided only to address particular and narrow needs. An ATM may dispense postage stamps, but treats the stamp sheets virtually as an alternate currency in a limited menu of deposit and cash access services. Lottery machines dispense lottery tickets; insurance machines dispense insurance policies; and fancy pay telephones and the most advanced home computers function primarily as old-fashioned credit card order lines for the various products and services available online. In short, even in the most recent instances the only advantage in retail automation has been the same as it has been for many years—the elimination of the human attendant.
A need thus remains for an innovation in the area of automated retail goods and services in which an automated transaction machine does more than merely provide existing goods and services in a simple automated way.

This patent is subject to a terminal disclaimer.


A process for the production of colored detergent particles. The process is characterized in that a slurry comprising at least one powdering agent and at least one dye is spray dried so that a colored powdering agent is formed. The thus formed colored powdering agent is then applied to detergent particles.

This invention relates to a process for the production of colored detergent particles.
Heavy-duty detergents sometimes contain dyes in the form of specks. Colors commonly used are green and blue. The function of the dyes is, for example, to compensate for the yellowing of washed fabrics or to color the particles and hence to make the detergents more attractive to the consumer.
European patent application EP 0 138 410 describes a process for the production of colored washing powder in which a particulate dye is intensively mixed with a washing powder, for example in a feed screw, so that a colored washing powder is obtained. The dyes used are ultramarine blue, Duasyn Acid Blau and Polar Brillant Blau.
U.S. Pat. No. 3,519,054 describes a process for the production of multicolored particulate products in which two liquid streams are dried in countercurrent in the form of droplets and a dye is added to one or both liquid streams, the droplets being converted into dried multicolored particles. Ultramarine blue, for example, is used as the dye. Other examples mentioned include phthalocyanine blue, indigo, rhodamine pigment, azo ruby, chrome orange, alizarin, Indanthren(copyright) Gelb, phthalocyanine green, wool violet or anthraquinone violet.
In addition, powder-form detergents containing colored, generally green or blue, specks in the powder are known from the prior art. The colored particles are often colored detergent additives such as, for example, bleach activator particles.
DE-A-195 42 320 describes colored particles for incorporation in detergents containing surfactants, builders and/or bleaching agents and a dye which can be completely or partly destroyed by oxidation in the washing process. These colored particles are produced by a process in which the individual components and the dye are made into a slurry in water and then subjected to spray drying. In this process, however, the detergents are made up in the presence of dye solutions. As a result, the production units are heavily soiled by dyes and have to be cleaned at considerable expense.
Accordingly, the problem addressed by the present invention was to provide a process for the production of colored detergent particles for incorporation in detergents which would not have any of the disadvantages of the prior art.
Accordingly, the present invention relates to a process for the production of colored detergent particles containing surfactants, builders and/or bleaching agents and a dye, characterized in that (A) the powdering agent and the dye are made into a slurry and subjected to spray drying and (B) the colored and spray-dried powdering agent is then applied to detergent particles, process steps (A) and (B) being carried out in separate steps.
The process according to the invention is preferably carried out as a spray drying process in step (A). To this end, the powdering agent and dye are first made into a slurry. The slurry thus formed is then spray dried in a spray drying tower by introducing hot air from below. Depending on the consistency of the slurry, nuclei may also be added to accelerate particle formation. The most suitable procedure is familiar to the expert. Particularly uniformly colored homogeneous powdering agent particles can be obtained by this process step and may then be used for coloring detergents.
However, instead of the spray drying process, the powdering agent particles may also be colored by spraying the dye solution onto the powdering agent particles in known manner. In this case, however, the colored powdering agent particles have to be dried in a separate step to prevent them from agglomerating.
Parallel to the production of the colored powdering agent, uncolored detergent particles are produced. Finally, the colored powdering agents are transferred from the spray drying tower to a separate unit after step (B) of the process. In this separate unit, the uncolored detergent particles are powdered with the separately produced colored particles of powdering agent. Accordingly, powdering with the colored particles of powdering agent is carried out separately from their production.
Colored particles suitable for incorporation in a detergent in accordance with the present invention are those which, besides the dye, contain at least one other component which contributes towards the washing or cleaning performance of the detergent. The particles produced by the process according to the invention may be used as constituents of heavy-duty detergents or as heavy-duty detergents themselves, the dyes either being very quickly destroyed by oxidation in the wash liquor so that they do not give off any dye to the laundry, even at high washing temperatures, or being used to color laundry through the release of dye during the washing process, depending entirely on the choice of the dye. It is also possible to use dye mixtures which, besides dyes capable of oxidative destruction, contain blue dyes suitable for detergents which, as blueing agents, compensate for the yellowing of washed laundry.
Any dyes capable of oxidative destruction in the washing and mixtures thereof with suitable blue dyes, so-called blueing agents, are preferred. It has proved to be of advantage to use dyes which are soluble in water or in liquid organic substances at room temperature. Suitable dyes are, for example, anionic dyes, for example anionic nitroso dyes. One possible dye is, for example, naphthol green (Colour Index (CI) Part 1: Acid Green 1, Part 2: 10020), which is commercially obtainable, for example, as Basacid(copyright) Grxc3xcn 970 from BASF, Ludwigshafen, and mixtures thereof with suitable blue dyes. Other suitable dyes are Pigmosol(copyright) Blau 6900 (CI 74160), Pigmosol(copyright) Grxc3xcn 8730 (CI 74260), Basonyl(copyright) Rot 545 FL (CI 45170), Sandolan(copyright) Rhodamin EB400 (CI 45100), Basacid(copyright) Gelb 094 (CI 47005), Sicovit(copyright) Patentblau 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol(copyright) Blau GLW (CAS 12219-32-8, CI Acidblue 221)), Nylosan(copyright) Gelb N-7GL SGR (CAS 61914-57-1, CI Acidyellow 218) and/or Sandolan(copyright) Blau (CI Acid Blue 182, CAS 12219-26-0).
In choosing the dye, it is important to ensure that it does not have an excessive affinity for the textile surfaces and, more particularly, for synthetic fibers. Another factor to be taken into account in the choice of suitable dyes is that dyes differ in their stability to oxidation. In general, water-insoluble dyes are more stable to oxidation than water-soluble dyes. The concentration of the dye in the detergents varies according to its solubility and, hence, its sensitivity to oxidation. In the case of readily water-soluble dyes, for example the Basacid(copyright) Grxc3xcn mentioned above or the Sandolan(copyright) Blau also mentioned above, dye concentrations of 10xe2x88x922 to 10xe2x88x923% by weight are typically selected. By contrast, in the case of the pigment dyes particularly preferred for their brilliance, but less readily soluble in water, for example the above-mentioned Pigmosol(copyright) dyes (Pigmosol(copyright) TAED), suitable dye concentrations in detergents are typically 10xe2x88x923 to 10xe2x88x924% by weight.
To prevent destruction of the dye in storage, it is of advantage if the dye is stable at temperatures of up to 40xc2x0 C. The stability of the detergents containing the particles produced by the process according to the invention can be increased by a low water content. In the presence of water, the dyesxe2x80x94in a particularly preferred embodimentxe2x80x94react to a certain extent with atmospheric oxygen or with oxygen present in the water. In this case, there is no need for bleaching agents to be present, which is particularly advantageous for light-duty detergents.
The dyes used for producing the colored particles should be sufficiently resistant to heat and alkalis and should not color the laundry or parts of the washing machine, even after repeated washing, and at the same time should not show any substantivity towards textile fibers so as not to color the laundry.
However, if the dyes are absorbed onto the textile fibers, the color absorbed onto the textiles should be destroyed by reaction with the oxidizing agents so that coloring of the textiles, particularly over several washing cycles, is avoided. In one preferred embodiment of the present invention, therefore, the dye is completely or partly destroyed by oxidation in the washing process.
The oxidative reaction of the dye with an oxidizing agent should be a fast reaction so that the dye decomposes on contact with the oxidizing agent. If the particles produced by the process according to the invention come into contact with water, a colored wash liquor is generally formed to begin with, but is soon decolored by the bleaching agent which also dissolves on contact with water. The colored wash liquor is at least 50%, preferably at least 80% and more preferably at least 90% decolored at 60xc2x0 C., preferably 5 to 10 minutes after dissolution in water. The degree of oxidative destruction of the dye may be determined, for example, from extinction measurements, i.e. by measuring the extinction E0 of the wash liquor with a known concentration C0 of dye and the extinction E1 of the wash liquor after a certain time. The quantity C0 of dye still present may be calculated from the extinction values thus determined using the Lambert-Beer law. The rate at which the dye oxidizes should be greater, the higher its substantivity towards the laundry.
The colored particles produced by the process according to the invention or detergents containing these particles preferably have such a low substantivity towards textiles that, after 25 washing cycles, the Ganz/Grieser color deviation value of cotton fabrics with a Ganz whiteness of more than 200 is between xe2x88x921.5 and xe2x89xa62.5.
Suitable oxidizing agents are, for example, the substances typically present as bleaching agents in the detergents. These include in particular compounds which yield H2O2 in water. Of these compounds, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-yielding peracidic salts or peracids, such as perbenzoates, peroxyphthalates, diperazelaic acid or diperdodecanedioic acid. In order to decolor the dye completely in the time mentioned above, the oxidizing agent should be present in a sufficient quantity. If it is intended to incorporate the particles produced in accordance with the invention in a light-duty detergent intended in particular for colored fabrics which are not intended to be bleached, the dye may be used without a separately added oxidizing agent. The dye and the oxidizing agent may be present in a ratio by weight of up to about 1:104 and preferably 1:100 to 8xc3x97103, the quantities of oxidizing agent being kept as small as possible to preserve the fibers of the fabrics. Accordingly, the dye and the bleaching agent for decoloring the dye are preferably present in a ratio by weight of up to 1:500.
The detergent produced by the process according to the invention may be a heavy-duty detergent, a color detergent or a light-duty detergent. If the detergent is a light-duty detergent, it should not contain any bleaching agent other than the bleaching agent required to oxidize the dye unless the dye is oxidized by oxygen in the presence of water.
The detergents produced by a process according to the invention in which the bleaching agents are also intended to contribute towards the washing performance, for example to the removal of bleachable soils, have a total content of bleaching agents of preferably 5 to 30% by weight and more preferably 10 to 25% by weight.
In one preferred embodiment, the process is carried out using colored particles containing bleach activator. This is because the effectiveness of the oxidizing or bleaching agent can be significantly increased by the addition of so-called bleach activators. Accordingly, detergent particles containing bleach activators are colored in the practical application of the production process according to the invention and, finally, are incorporated in bleach-containing detergents in order to obtain an improved bleaching effect where washing is carried out at temperatures of 60xc2x0 C. or lower. Examples of bleach activators are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N,Nxe2x80x2-tetraacylated diamines, alkanoyloxybenzenesulfonates, such as iso- and n-nonanoyloxybenzene-sulfonates, carboxylic anhydrides and esters of polyols, such as glucose pentaacetate. Other known bleach activators are the acetylated mixtures of sorbitol and mannitol which are described, for example, in European patent application EP-A-0 525 239. The content of bleach activators in the bleach-containing detergents is in the usual range, preferably between 1 and 10% by weight and more preferably between 2 and 8% by weight. Particularly preferred bleach activators are N,N,Nxe2x80x2,Nxe2x80x2-tetraacetyl ethylenediamine (TAED), 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol/mannitol mixtures (SORMAN(copyright)).
In one preferred embodiment, the colored spray-dried powdering agents and the detergent particles are thoroughly mixed. Mixing units suitable for this purpose are known to the expert. In this way, the powdering agents adhere to the surface of the detergent particles and provide the detergent with the required color characteristics.
The detergent particles to which the colored powdering agents are added may be granulated detergent particles, spray-dried detergent particles or solid detergent particles. Before the colored powdering agent is applied, the detergent particles may be produced in known manner, for example by spray drying, by granulation or by extrusion. The particles may be produced in particular by granulation and simultaneous drying, advantageously by the fluidized-bed process described in International patent application WO 93/04162.
However, the uncolored surfactant-containing detergent particles may also be produced by extrusion as described, for example, in European patent applications EP-A-0 339 996, EP-A-0 420 317 or International patent application WO-A-93/23523 or European patent EP-B-0 486 592.
Suitable powdering agents which are colored with dye by the process according to the invention are inorganic builders. Besides the traditional phosphates, alumosilicates of the zeolite type are particularly suitable for this purpose. In one particularly preferred embodiment, the finely crystalline, synthetic zeolite containing bound water used is zeolite NaA, above all Wessalith(copyright) P, in detergent quality. However, zeolite X and zeolite P and mixtures of A and X or A and X and/or P are also suitable.
A commercially obtainable inorganic builder which may be used with advantage for the purposes of the present invention is the co-crystallizate of zeolite X and zeolite A (ca. 80% by weight zeolite X) marketed by CONDEA Augusta S.p.A. under the name of VEGOBOND AX(copyright) which may be described by the following formula:
nNa2O.(1-n)K2O.Al2O3.(2-2.5)SiO2.(3.5-5.5)H2O
Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline layer-form sodium silicates with the general formula NaMSixO2x+1.y H2O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4. Crystalline layer silicates such as these are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layer silicates are those in which M is sodium and x assumes the value 2 or 3. Both xcex2- and xcex4-sodium disilicates Na2Si2O5.y H2O are particularly preferred powdering agents.
In one preferred embodiment of the process according to the invention, a ratio by weight of detergent particles to colored powdering agent of 95:5 to 99.5:0.5 and, more particularly, a ratio by weight of 97:3 to 99:1 is adjusted during application of the colored and spray-dried powdering agent to the detergent particles. With ratios by weight such as these, the resulting detergent creates a satisfactory color impression.
The detergent particles used in the process according to the invention may advantageously contain the components typically used in detergents such as, for example, anionic, nonionic and/or amphoteric surfactants and/or builders.
The anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C9-13 alkyl benzenesulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C12-18 monoolefins with an internal or terminal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Other suitable surfactants of the sulfonate type are the alkane sulfonates obtained from C12-18 alkanes, for example by sulfochlorination and subsequent hydrolysis or neutralization. The esters of xcex1-sulfofatty acids (ester sulfonates), for example the xcex1-sulfonated methyl esters of hydrogenated coconut oil, palm kernel oil or tallow fatty acids, are also suitable.
Suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols of natural and synthetic origin. Preferred alk(en)yl sulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric acid semiesters of C12-18 fatty alcohols, for example cocofatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C10-20 oxoalcohols and the corresponding semiesters of secondary alcohols with the same chain length. Other preferred alk(en)yl sulfates are those with the chain length mentioned which contain a synthetic, linear alkyl chain based on a petrochemical and which are similar in their degradation behavior to the corresponding compounds based on oleochemical raw materials.
C12-16 alkyl sulfates and C12-15 alkyl sulfates and also C14-15 alkyl sulfates are particularly preferred from the washing performance point of view.
The sulfuric acid monoesters of linear or branched C7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9-11 alcohols containing on average 3.5 moles of ethylene oxide (EO) or C12-18 fatty alcohols containing 1 to 4 EO, are also suitable. In view of their high foaming capacity, they are only used in relatively small quantities, for example in quantities of 1 to 5% by weight, in detergents.
Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, i.e. the monoesters, diesters and triesters and mixtures thereof which are obtained where production is carried out by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
Other suitable anionic surfactants are the salts of alkyl sulfosuccinic acid which are also known as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and, more particularly, ethoxylated fatty alcohols. Preferred sulfosuccinates contain C8-18 fatty alcohol molecules or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol molecule derived from ethoxylated fatty alcohols which, considered in isolation, represent nonionic surfactants (for a description, see below). Of these sulfosuccinates, those of which the fatty alcohol molecules are derived from narrow-range ethoxylated fatty alcohols are particularly preferred. Alk(en)yl succinic acid preferably containing 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof may also be used.
Other suitable anionic surfactants are, in particular, soaps. Suitable soaps are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and soap mixtures derived in particular from natural fatty acids, for example coconut oil, palm kernel oil or tallow fatty acids.
The synthetic anionic surfactants and soaps may be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts and, more preferably, in the form of their sodium salts.
Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated, more particularly primary alcohols preferably containing 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or, preferably, 2-methyl-branched or may contain linear and methyl-branched radicals in the form of the mixtures typically present in oxoalcohol radicals. However, alcohol ethoxylates containing linear radicals of alcohols of native origin with 12 to 18 carbon atoms, for example coconut oil fatty alcohol, palm oil fatty alcohol, tallow fatty alcohol or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C12-14 alcohols containing 3 EO or 4 EO, C9-11 alcohols containing 7 EO, C13-15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C12-18 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C12-14 alcohol containing 3 EO and C12-18 alcohol containing 5 EO. The degrees of ethoxylation mentioned are statistical mean values which, for a special product, may be either a whole number or a broken number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols containing more than 12 EO may also be used. Examples of such fatty alcohols are tallow fatty alcohol containing 14 EO, 25 EO, 30 EO or 40 EO.
Other suitable nonionic surfactants include alkyl glycosides with the general formula RO(G)x where R is a primary, linear or methyl-branched, more particularly 2-methyl-branched, aliphatic radical containing 8 to 22 and preferably 12 to 18 carbon atoms, G is a glycose unit containing 5 or 6 carbon atoms, preferably glucose, and the degree of oligomerization xxe2x80x94which indicates the distribution of monoglycosides and oligoglycosidesxe2x80x94is a number of 1 to 10 and preferably a number of 1.2 to 1.4.
Other nonionic surfactants which are used either as sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters preferably containing 1 to 4 carbon atoms in the alkyl chain, more particularly the fatty acid methyl esters which are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in International patent application WO-A-90/13533.
Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethyl amine oxide, and the fatty acid alkanolamide type are also suitable. The quantity in which these nonionic surfactants are used is preferably no more, in particular no more than half, the quantity of ethoxylated fatty alcohols used. Other suitable surfactants are polyhydroxyfatty acid amides corresponding to formula (I):
in which R2xe2x80x94CO is an aliphatic acyl radical containing 6 to 22 carbon atoms, R3 is hydrogen, an alkyl or hydroxyalkyl radical containing 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical containing 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid amides are known substances which may normally be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
Besides the surfactants already described in detail, the other ingredients include in partiular inorganic and organic builders, components which prevent the resoiling of fabrics (soil repellents) and redeposition inhibitors, alkaline salts, bleaching agents and bleach activators, foam inhibitors, fabric softeners, neutral salts and dyes and perfumes.
Apart from the conventional phosphates, suitable inorganic builders are in particular alumosilicates of the zeolite type. The finely crystalline synthetic zeolite containing bound water used is preferably detergent-quality zeolite NaA. However, zeolite X and zeolite P and mixtures of A and X and/or P are also suitable.
Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline layer-form sodium silicates corresponding to the general formula NaMSixO2x+1.yH2O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4. Crystalline layer silicates such as these are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layer silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. Both xcex2- and xcex4-sodium disilicates xe2x80x94Na2Si2O5.yH2O are particularly preferred.
Useful organic builders are, for example, polycarboxylic acids usable in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), providing their use is not ecologically unsafe, and mixtures thereof. Preferred salts are the salts of the polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Acrylic acid/maleic acid copolymers containing 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proved to be particularly suitable. Their relative molecular weight, based on free acids, is generally in the range from 5,000 to 200,000, preferably in the range from 10,000 to 120,000 and more preferably in the range from 50,000 to 100,000. Also particularly preferred are biodegradable terpolymers, for example those which contain salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives as monomers (DE-A-43 00 772) or salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives as monomers (DE-C-42 21 381).
Other preferred builders are the known polyaspartic acids and salts and derivatives thereof.
Other suitable builders are polyacetals which may be obtained by reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least three hydroxyl groups, for example as described in European patent application EP-A0 280 223. Preferred polyacetals are obtained from dialdehydes, such as glyoxal, glutaraldehyde, terephthal-aldehyde and mixtures thereof and from polyol carboxylic acids, such as gluconic acid and/or glucoheptonic acid.
The inorganic and/or organic builders are used in the detergents produced in accordance with the invention in quantities of preferably about 10 to 60% by weight and more preferably 15 to 50% by weight. The detergents according to the invention may additionally contain components which have a positive effect on the removability of oil and fats from textiles by washing. This effect becomes particularly clear when a textile which has already been repeatedly washed with a detergent according to the invention containing this oil- and fat-dissolving component is soiled. Preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers, such as methyl cellulose and more particularly methyl hydroxypropyl cellulose containing 15 to 30% by weight of methoxyl groups and 1 to 15% by weight of hydroxypropoxyl groups, based on the nonionic cellulose ether, and the polymers of phthalic acid and/or terephthalic acid known from the prior art or derivatives thereof, more particularly polymers of ethylene terephthalates and/or polyethylene glycol terephthalates or anionically and/or nonionically modified derivatives thereof. They can be effective in only small quantites. Accordingly, their content is preferably 0.2 to 10% by weight and more particularly up to 5% by weight.
In addition, redeposition inhibitors are also preferably present in the detergent particles to be produced in accordance with the invention. The function of redeposition inhibitors is to keep the soil detached from the fibers suspended in the wash liquor and thus to prevent the soil from being re-absorbed by the washing. Suitable redeposition inhibitors are water-soluble, generally organic colloids, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatine, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and other starch products than those mentioned above, for example degraded starch, aldehyde starches, etc., may also be used. Polyvinyl pyrrolidone is also suitable. However, cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose, and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone are also preferably used, for example in quantities of 0.1 to 5% by weight, based on the formulation as a whole.
Other suitable ingredients of the detergents are water-soluble inorganic salts, such as bicarbonates, carbonates, amorphous silicates or mixtures thereof; alkali metal carbonate and amorphous alkali metal silicate, above all sodium silicate with a molar Na2O:SiO2 ratio of 1:1 to 1:4.5 and preferably 1:2 to 1:3.5, are particularly suitable. The sodium carbonate content of the detergents is preferably up to 20% by weight and advantageously between 5 and 15% by weight. The sodium silicate content of the detergents is generally up to 10% by weight and preferably between 2 and 8% by weight.
The amorphous silicates, like some commercially obtainable compounds of carbonates and amorphous silicates, are suitable for partly or completely replacing the traditional builders, such as phosphate, zeolite and crystalline layer silicates. If such substances are used, their content may even exceed the quantities mentioned above for carbonates and amorphous silicates. Contents of up to 40% by weight or even 60% by weight are entirely within the scope of the invention.
In addition, foam inhibitors are preferably present in the detergent particles to be produced in accordance with the invention. More particularly, it is of advantage to use foam inhibitors for formulations which are used in machine washing processes. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin which have a high percentage content of C18-24 fatty acids. Suitable non-surface-active foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized, silica or bis-stearyl ethylenediamide. Mixtures of different foam inhibitors, for example mixtures of silicones, paraffins and waxes, may also be used with advantage. The foam inhibitors, more particularly silicone- and/or paraffin-containing foam inhibitors, are preferably fixed to a granular water-soluble or water-dispersible support. Mixtures of paraffins and bis-stearyl ethylenediamides are particularly preferred.
The neutrally reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriamine pentamethylene phosphonate or ethylenediamine tetramethylene phosphonate in quantities of 0.1 to 1.5% by weight are preferably used as the salts of polyphosphonic acids.
In addition, enzymes may optionally be used in the detergent particles produced in accordance with the invention. Particularly suitable enzymes are, in particular, enzymes from the class of proteases, lipases, amylases, cellulases and mixtures thereof. Enzymes obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type are preferably used, proteases obtained from Bacillus lentus being particularly preferred. Of particular interest in this regard are enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but especially cellulase-containing mixtures. Peroxidases or oxidases have also proved to be suitable in some cases. The enzymes may be adsorbed to supports and/or encapsulated in membrane materials to protect them against premature decomposition. The percentage content of enzymes, enzyme mixtures or enzyme granules is, for example, about 0.1 to 5% by weight and preferably 0.1 to 2% by weight.
Components which prevent the resoiling of fabrics (soil repellents) are, in particular, compounds which prevent the soil particles detached during the washing process from settling and thus avoid the formation of a so-called grey bloom without affecting enzyme activity or washing performance. Such components are generally polymeric and copolymeric compounds, such as polyesters of aliphatic and/or aromatic dicarboxylic acids and glycols and/or polyglycols.
The particles produced in accordance with the invention may contain derivatives of diaminostilbene disulfonic acid or alkali metal salts thereof as optical brighteners. Suitable optical brighteners are, for example, salts of 4,4xe2x80x2-bis-(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)-stilbene-2,2xe2x80x2-di-sulfonic acid or compounds of similar structure which contain a diethanolamino group, a methylamino group and anilino group or a 2-methoxyethylamino group instead of the morpholino group. Brighteners of the substituted diphenyl styryl type, for example alkali metal salts of 4,4xe2x80x2-bis-(2-sulfostyryl)-diphenyl, 4,4xe2x80x2-bis-(4-chloro-3-sulfostyryl)-diphenyl or 4-(4-chlorostyryl)4xe2x80x2-(2-sulfostyryl)-diphenyl, may also be present. Mixtures of the brighteners mentioned may also be used.
The invention is illustrated by the following Examples.

Method for producing colored detergents and cleaning agents


In a cosmetic unit comprising two different cosmetic products and two different applicators, provision is made, with a view to cost-saving manufacture based on a minimum of components and simplicity of assembly, for a central sleeve; a threaded plug which is fixable in the central sleeve; a threaded spindle which reaches through a hole, with a female thread, of the threaded plug and on the outer end of which is provided a cup that houses a cartridge, the cup being mounted, via axial projections, non-rotatably, but axially displaceably in a protective guide section; an insert which is plugged into the central sleeve in the vicinity of the threaded spindle and which includes the protective guide section that is formed outside the central sleeve; an applicator handle which adjoins the inside end of the threaded spindle; and a helical spring which extends between the threaded plug and the inner front end of the applicator handle, forcing the applicator outwards against a cosmetic compound contained in the screw cap which is screwed on the central sleeve.

1. Field of the Invention
The invention relates to a cosmetic unit comprising two different cosmetic products and two different applicators.
2. Background Art
A cosmetic unit or cosmetic pencil of the generic type is known from DEU-94 18 823 specifying a cosmetic pencil of a design such that an applicator is spring-loaded and dips into a cosmetic compound when a cap-type housing member that is filled with the cosmetic compound is screwed on or off.
DE 101 11 570 teaches a cosmetic pen which includes a rotary type pusher mechanism, offering a wide range of use.
Furthermore, there are numerous familiar prior art solutions, combining two different types of applicators in a single utensil; these familiar products either are very complicated to manufacture or unsatisfactory in use.
It is an object of the invention to embody a cosmetic unit of the type mentioned at the outset in such a way that cost-saving manufacture is ensured by a minimum of components and simplicity of assembly, it being desirable for the combined appliances to be purchased, selected, handled and refilled separately.
According to the invention, this object is attained in a cosmetic unit comprising a central sleeve; a threaded plug which is fixable in the central sleeve; a threaded spindle which reaches through a hole, with a female thread, of the threaded plug and on the outer end of which provision is made for a cup that houses a cartridge, the cup being mounted, via axial projections, non-rotatably, but axially displaceably in a protective guide section; an insert which is plugged into the central sleeve in the vicinity of the threaded spindle and which includes the protective guide section that is formed outside the central sleeve; an applicator handle which adjoins the inside end of the threaded spindle; and a helical spring which extends between the threaded plug and the inner front end of the applicator handle, forcing the applicator outwards against a cosmetic compound contained in the screw cap which is screwed on the central sleeve.
The above-specified design according to the invention requires comparatively few components and ensures simplicity of assembly.
In particular, it offers a multiplicity of combinations of varying cosmetic utensils with varying applicators and/or varying cosmetic compounds, it being conceivable, proceeding from identical basic components, to have units of double function as well as separate single-function units.
If for instance the insert for cartridge advance that is plugged into the central sleeve is removed from where it is locked into place, a simple cover sleeve can be placed on instead of the central sleeve, offering a high-quality lipstick and cartridge advance in working order.
The released end of the rest of the central sleeve with screw cap and the cosmetics contained therein, for instance an eye cosmetic compound, can easily be equipped with a cap instead of the lipstick so that the device for eye-cosmetic application may as well be used independently.
From a viewpoint of manufacture, it is conceivable to have two entirely different cosmetic appliances produced, including different applicators and varying cosmetics, possibly by different manufacturers, and to offer them separately to customers in a store so that customers may select the parts corresponding to their specific requirements and combine them in the form of a twin unit for use in practice. As compared to familiar prior art solutions, this offers surprising and extraordinarily advantageous combinations to the manufacturer as well as to the consumer.
In keeping with another embodiment of the invention, provision can be made for the helical spring to support itself, by its inner end, on an insert that is axially fixed by arresting beads. This feature too helps obtain a cosmetic device, including a helical spring, which can be manufactured, offered and used independently.
The same applies to the feature according to which the threaded plug is axially fixed by arresting beads and corresponding annular grooves. If, for dismantling, traction is exercised on the insert that is insertable into the central sleeve, the threaded plug is extracted axially by interaction through the threaded spindle and can be inserted in a separate sleeve with corresponding annular locking recesses instead of being placed in the central sleeve of the combined appliance.
The insert is rotatably mounted in the central sleeve for advance and retraction of a cartridge that is arranged in the mentioned cup, i.e., it is axially locked into place, but its movability in the peripheral direction is maintained.
Details of the invention will become apparent from ensuing description of a preferred exemplary embodiment, taken in conjunction with the drawing.


A new and distinct Hosta plant named ‘Little Jay’ characterized by lance-leafed, dwarfsized, leaves with blue green margins, light yellow to creamy leaf centers, vertical flower scapes with light purple flowers, suitable for landscape, potted culture, or cut flower arrangements.

The present invention relates to the new and distinct hosta plant, Hosta 'Little Jay' discovered by Hendrik Jan van den Top at a nursery in The Netherlands. The Plant is an uninduced whole plant sport of the Hosta cultivar 'Beauty Little Blue' (not patented). 'Beauty Little Blue' is a cross of Hosta 'Blue Cadet' (not patented) with Hosta clausa var. normalis (not patented). The plant has been successfully asexually propagated by division and tissue culture methods at a plant nursery in Barneveld, The Netherlands and found to produce identical plants that maintain the unique characteristics of the original plant. The plant is stable and reproduces true to type in successive generations of asexual reproduction.
Hosta 'Little Jay' differs from its parents, as well as all other hostas known to the applicant, in that the plant has a very narrow variegated leaf that emerges with the center pale yellow in the spring and with sunlight and warmer temperatures lightens to a white. The leaf margin is green with a slight glaucous bloom producing a slightly bluish cast.
The most similar known hosta cultivar is Hosta 'Fireworks' U.S. Plant Pat. Ser. No. 16,062. 'Fireworks' has a larger and wider leaf, does not start up as yellow in the center, and the flower is lighter lavender.


A power lawn roller has a left roller drum and a right roller drum, both journalled side by side on the same axle and rotatable independently of one another. Left and right hydraulic drives provide motive power to the left and right roller drums, and each is capable of rotating the associated drum forward, reverse, or at intermediate speeds. Removable external weights are rack mounted on the frame of the unit. The operator can easily control the direction and speed, and the unit is capable of a zero-radius turn.

This invention relates to lawn and landscaping equipment, and is more particularly directed to self-powered equipment for rolling or compacting soil. The invention is specifically directed to a walk-behind lawn roller that permits an operator to control the direction and speed of travel with great precision, and without risk of damage to existing lawn, pavement or soil.
There now exists a need for a convenient method for rolling down topsoil in preparation for laying down of a new lawn. A need exists for rolling flat existing lawns, as well. At the present time what exists for this purpose is a lawn roller that has to be pulled or dragged by hand, or a roller that has to be towed behind a tractor. Both of these techniques are slow and awkward, and are somewhat unworkable if the terrain is anything but flat. What is needed is a lawn roller that is easy to turn and move about on a yard or lawn, without having to be pushed, pulled, or towed. In order to work the soil in areas near trees, buildings, or other structures, the lawn roller should be turnable in a small a radius as possible, but without noticeable damage to the lawn. In addition, to increase the mobility of the unit between work sites, and to adjust the weight of the unit to a given application, a means of removable weighting or ballasting should be used, and the use of water filled drums should be avoided.
Some lawn and construction equipment now exists for rolling earth or topsoil, but these are not entirely suited for the purposes served by this invention. An example of an existing self-propelled lawn roller is described in Cross U.S. Pat. No. 4,208,151. In that example, there is only a single drum roller. There is no means for turning the roller or changing direction, except brute force applied to the handle bar. This construction limits the total width of the roller. Another walk-behind soil compactor is described in Artzberger U.S. Pat. No. 4,732,507, which employs a pair of drums journalled side by side on a drum frame. These drums are driven by a common gear drive, and thus both drums turns together.
Hydraulic drive mechanisms have recently been employed in walk-behind self-propelled lawn mowers, one example of which is described in Zvolanek U.S. Pat. No. 5,518,079. In these lawn mowers, there is a separate hydraulic drive motor associated with the drive wheel on each side of the mower, and the operator can control the speed and direction of travel by squeezing control levers on the handle. However, despite the longstanding need for an improved lawn roller, no one has yet been motivated to incorporate the drive mechanism of this type of lawn mower into a split drum lawn roller.
Accordingly, it is an object of the invention to provide an effective and efficient technique for rolling and flattening soil in preparation for laying a lawn, or for rolling and flattening an existing lawn.
It is another object to provide a an improved self-propelled lawn roller for lawn installation and maintenance, which may be employed at golf courses, athletic fields, or parks, and which may be used in lawn care for commercial and residential applications.
It is a further object to provide a lawn roller that may be of increased width, and which may be used without difficulty and without a need to pull, push or tow it.
It is a still further object to provide a lawn roller that can be turned in a zero radius turn without damage to the lawn.
It is still another object to provide a lawn roller in which weight can be added or removed, and which avoids having to carry water within the roller drums.
According to an aspect of this invention, a power lawn roller has two roller drums that share a common axis and are individually movable. There is a frame that carries a transverse axle, and a left roller drum and a right roller drum are both journalled, side by side, on the axle. An engine is mounted on the frame and powers separate left and right independent hydraulic drive mechanisms providing motive power to the left and right roller drums, respectively. The hydraulic drive mechanism are each capable of rotating the associated drum at a forward speed and at a reverse speed, and at any desired speed in between, including idle. The control handle assembly for the unit has left and right control handles or squeeze handles, each operatively coupled to the associated drive mechanism, and this permits the operator to control the rotation speed of each of the drums. Directional control is entirely at the discretion of the operator. This arrangement allows the operator to move the lawn roller in a forward, reverse, left, or right direction, with the lawn roller responding immediately to the operator""s hand actions on the squeeze levers. The drums can be rotated in different directions at the same time, allowing the operator to spin the lawn roller at its own center. There is a rear balance wheel or caster that also serves to press down the narrow strip of earth that is left by the gap between the two drums.
In a preferred mode, the hydraulic drive includes left and right hydraulic motors, and a continuous web drive between each hydraulic motor and the respective drum roller. The web drive may be a chain and sprocket drive, or may be a timing belt drive, for example.
Instead of using water to add weight to the drums, there are external weights, e.g., xe2x80x9csuitcasexe2x80x9d weights, mounted removably on racks to the left and right of the engine above the drums and somewhat forward of the drum axis. These weights can be removed when not needed, for example, when using the lawn roller on very loose soil, or when loading the unit onto a truck.
The principle of this invention can be employed in an extra-wide roller, for example, more than 48 inches across.
The propulsion system may be a gasoline engine, or may be any other available power source.
The above and many other objects, features, and advantages of this invention will become apparent to persons skilled in the art from the ensuing description of a preferred embodiment, which should be considered in connection with the accompanying Drawing.


Data read from a database may be transferred to an external system utilizing a dynamic interface, through a remote procedure call (RPC) communication mechanism. In particular embodiments within the SAP environment, data is transferred utilizing an executable program in a high level language such as Advanced Business Application Programming (ABAP). Data may be streamed from the ABAP executable program directly to a Data Services Job engine via a NetWeaver remote function call (NWRFC) C/C++ connector.

The present invention relates to storage of data in databases, and in particular, to a dynamic interface for accessing information from a database.
Unless otherwise indicated herein, the approaches described in this section are not prior art to the claims in this application and are not admitted to be prior art by inclusion in this section.
Databases comprising rows and columns are highly useful tools allowing users to manage complex relationships between different types of data. In general, a database is created in a lower level code such as structured query language (SQL), and stored on a server. A user (typically at a remote client) accesses this data through a data services engine running a higher level language that provides a high level of abstraction from the basic database level. One example of such a higher level language is the Advanced Business Application Programming (ABAP) language of SAP AG.
FIG. 1 is a block diagram illustrating a highly simplified process flow 100 of a user posing a request for information from a database. In a first step, a human user 102 designs an extraction dataflow 104 using the data services designer 106 of a data services client 107. Herein, the extraction dataflow designed by a user in the context of a SAP system, is referred to herein as the ABAP Dataflow. However, the present invention is not limited to a SAP system, and could relate to other higher level languages used to interact with databases created in lower level languages.
Design of the extraction dataflow comprises specifying: i) the Source object(s) 104a, ii) the extraction transformations 104b, and iii) the structure of the output data table 104c. The specific structure of the output table is also referred to herein as the schema.
In a second step, the particular extraction dataflow designed by the user, is saved in a computer readable storage medium 108 that is in communication with the data services engine. While in this particular drawing, the computer readable storage medium is shown as part of the data services client, this is not required and the computer readable storage medium could be accessed remotely by the data services client through a computer network.
In a third step, a higher level language report 110 is generated by the data services designer based upon the extraction dataflow specified by the user. In a fourth step, the higher level language report 110 is communicated from the data services client through a remote function call connection 112 to the database application server 114, where it is processed by processor 115 and stored in repository 116 for processing to return the database information desired by the user.
Specifically, the processor of the application server interrogates the database in the low level language, and returns information relevant to the higher level language report 110 and the extraction dataflow present therein. In the particular context of a SAP system, an ABAP executable program writes a result to SAP Application Server file system.
Conventionally, this information returned from the database may be communicated back to the user at the client as shown in FIG. 2. This figure shows a simplified block diagram of a method 200 of data extraction from a SAP system.
In a first step 201, the data services engine 204 accesses the ABAP dataflow specification from the computer-readable storage medium in which it was previously saved. The data services engine retrieves ABAP report name from ABAP dataflow specification, and submits an ABAP job to execute the ABAP report.
The ABAP dataflow establishes a remote function call connection 205 to the SAP application server 206 using the NetWeaver Remote Function Call (RFC) Library 208 of the Data Services Engine 204. A submit batch job for the ABAP report communicated from the data services engine to the SAP application server includes the following pieces of information:                Dataflow parameters        SAP Application Server Local Directory        Data file name.
In a second step 202, the dialog work process 208 of the SAP Application server 206 receives the batch job request through the gateway 210. This batch job includes the ABAP report including the above information.
In a third step 203, the batch work process 212 causes the ABAP report to execute a query to extract data from the source object pursuant to the dataflow. An ABAP internal table is created to load data from the extractor source object.
For each iteration of a data packet, the ABAP report writes 205 to the local file of the directory of the SAP application server host file system 213 specified as parameter. The data is converted to character format in order to write to the local file. The ABAP report then exits after writing the data to the local file.
In a fourth step 207, the data services engine monitors the dispatcher of the application server to detect when the batch job has finished. According to this conventional approach, the Data Services engine remains idle for the period of time that the ABAP report writes data to the local file. The idleness of the Data Services engine is attributable to at least two possible reasons.
First, data will be in inconsistent state when ABAP report is writing data in batches to a specified local file. During this period, if the Data Services engine (in step 207) reads the data from the specified file and process, then the result will be inconsistent. Hence the Data Services engine waits for step 203 to be completed.
A second reason is that when step 207 writes data to an operating system (OS) file, it may have held write lock. For some operating systems, it may not be possible to read data.
In a fifth step 209, when Data Services engine detects that the ABAP report has finished its execution, it connects to SAP Application Server host 206 through an operating system call 214. In a sixth step 211, the Data Services engine transfers the data to its local directory using its host file system 216. Conventionally, this transfer of data may be accomplished using either a shared directory copy, a file transfer protocol (FTP), or a third-party file transfer software.
In a seventh step 217, the data services engine reads the data from its local file, and processes the data. The retrieved data may then be displayed to the user from the data services engine.
While effective, the conventional approach for reading data from the application server may raise certain issues. For example, the conventional approach to transferring information may create large files that occupy space in the file system of the host application server. Moreover, accessing this information stored locally at the application server may consume processing resources by incurring input/output from the disk, delaying processing performance.
Another issue is that a user must specify in advance, the local file of the application server to which data of the report is to be written. This requires the user have knowledge and familiarity of the file system of a host application server, which he or she may not possess.
Still another issue is that in conventional approaches, the ABAP report reads the data from the internal table and converts the data to character format before writing as a delimited record. In doing so, the designer identifies a particular character for the local file which is not part of the data, and which can be used as delimiter (column and row). Thus under conventional read approaches, in designing ABAP dataflow the designer needs to recognize possible characters that can be extracted as part of dataset. The designer comes up with special characters (as delimiters) which are not part of dataset in order to separate data into columns and records. This can be a difficult task where a user is unfamiliar with the file system (and characters used) of a remote host application server.
Security is another possible issue raised by this conventional approach for transferring data. In particular, owing to security reasons it may be impractical to open a FTP port or a shared directory between the client and server. The system host and the data services engine host may also be located in separate network areas.
The present disclosure addresses these and other issues with systems and methods for implementing a dynamic interface allowing an external system to read data from a database through a unique remote function call (RFC) session.

Dynamic interface to read database through remote procedure call


Alloying and/or reducing powder is pumped directly into the steel melt at a pressure of at least 20 bar, preferably at least 40 bar, with at most 20% of a fluidizing agent and the powder is discharged from the delivery line by a plunger extending across the cross section thereof.

This is a national stage of PCT/DE99/00932 filed Mar. 27, 1999 and is based upon the German national application 198 14 748.1 filed Apr. 2, 1998 under the International Convention.
The invention relates to a method for alloying steel by introducing metallic additives and/or reducing agents in powder form into a fluid metallic melt. The invention relates further to a device for implementing the method.
The present invention pertains to the field of secondary metallurgy, i.e. the further processing of, for instance, a steel produced by means of a refining process in a converter or in an electric-arc oven. A particular part of this further processing is establishing the composition of the steel alloys, during which the desired metallic additives are introduced. Optionally in this phase also an additional deoxidation, decarburization or desulfurization of trace elements can be performed.
From DE 42 37 177 A1 a mechanically adjustable dosage and delivery device for goods in powder form is known, which introduces one or more kinds of various powders in metered amounts into a pig iron melt, through a delivery device ending in an immersion lance. This dosage and delivery device is used for blowing and particularly for co-injection of calcium carbide and magnesium powders into pig iron melts.
The DE 44 00 029 A1 attempts in a similar fashion to achieve an adjustably metered introduction of additives into electric-arc furnaces, crucibles or pouring ladles. In all these cases the respective solid material in powder form is introduced by means of a carrier gas which according to the state of the art amounts to approximately 80% and more of the total gas-solids mixture. However, a difference in flow rates or flow velocity of the used carrier gases and the solid materials makes impossible a precise dosage or adjustment of the alloying elements to be introduced, or of the alloying elements in relation to the deoxidation elements, which negatively influences the production of the alloyed steel.
For this reason in establishing the composition of the steel alloy, one works with hollow wire in whose inner space the metals and/or deoxidizing agents are arranged in compressed powder form. This wire is unwound by means of a spooler directly into the bath, where the wire melts and releases the alloying elements. For instance wires with a diameter of up to 23 mm and a wall thickness of 0.5 mm are used and the filling material is disposed therein. The production of such wires filled with alloying elements in powder form is expensive. Furthermore the wire spooling method has the disadvantage that the melting wire end does not always lie in the desired location under the bath surface, so that different concentrations of alloying elements arise in the melt.
The more cost-efficient and technically simpler technology, which allows the alloy powders to trickle from above onto the bath surface has again the disadvantage that, because of the existing bath movements, which are directed radially outward on the surface of the metal bath, the alloying agents are pushed against the ladle or converter walls, where they adhere to the slag deposits or to the inner surface of the melt container. Since this happens in an uncontrollable manner depending on different bath movements, this method also can lead to undesirable alloy compositions, which do not correspond with the metal alloying requirements.
It is therefore the object of the present invention to so improve the method described at the outset that alloying additives alone or alloying additives in connection with reducing agents can be introduced in a precise dosage into the melt, with better dosage accuracy.
This object is achieved, according to the invention, in that the alloying additives and/or the alloying additives and reducing agents are introduced in the melt as powders (dry) from a supply container via a conveying device directly to one or more lances and/or below-bath nozzles into the melt, or are introduced into the melt in a mixture with a fluidizing agent, whose proportion in the injected amount is xe2x89xa620%, whereby the pressure used for the powder conveyance is at least 20 bar, preferably 40 bar, or whereby the powders in the delivery line are discharged by means of a plunger covering the cross section of the delivery line.
The injection technology of solids via lances or below-bath nozzles is used in a modified manner, in that the respective additives are injected into the melt dry (i.e. without gas or other fluidizing agent) at a conveying pressure of 40 bar and more or that the amount of the fluidizing agent is limited to a maximum of ⅕ in the gas-solid powder mixture and the mixture is injected at a pressure of more than 20 bar. The conveying pressure decreases correspondingly to the friction losses towards the lance or below-bath nozzle, whereby the pressure at which the powders are discharged decreases to values which are only slightly above the ferrostatic pressure. Surprisingly it has been found that an optimal dosage can be achieved, in spite of the considerable friction losses, which exist and which according to earlier assumptions were considered to endanger a uniform introduction of additives. It is also surprising that, when one is working with a lower proportion of fluidizing agents or without fluidizing agents, pressures between 20 bar and 40 bar are sufficient in order to overcome the frictional resistance.
As an alternative it is possible to push out the powder in the delivery line and/or the lance by means of a plunger covering the entire cross section of the delivery line. This method limits the amount of powder which can be introduced by means of the plunger, as well as the cross section of the delivery line through which the plunger is moved. The delivery line or lance segment has to be filled again after each powder discharge. Suitably the powder exit point at the lance is closed by a cover during refilling, which melts away when the lance is introduced into the melt.
As already mentioned, fluidizing agents can also be used, such as small amounts of inert gas, particularly argon or nitrogen, or of liquid hydrocarbons, such as heating or diesel oil, heavy oil, waste oil, rape seed oil or paraffin. The use of liquid hydrocarbons, such as waste oil, which burns in the melt, create disposal possibilities, which make it possible to avoid the treatment of waste oil as a special disposal waste.
So for instance preferably powders with a maximum grain size of 1 mm, preferably of maximum 0.1 mm, are used, particularly in the xe2x80x9cdryxe2x80x9d injection without gas or liquids.
A fluidization of the powders can also be performed so that compressed alloying additives form a core surrounded by a shell containing lubricants, e.g. paraffin, wax, oil or the like. The respective particles consisting of core and shell can be used without the addition of further fluidizing agents, or with a further small proportion of gaseous or liquid fluidizing agents.
According to a further embodiment of the invention, the alloying additives are injected in powder form through a swingable lance.
By this one has to understand such oscillating motions which make possible to move the lance exit opening out of the bath, as well as such oscillating motions which allow the setting of different positions of the lance exit opening below the bath surface.
Advantageously the lance is designed as a ring nozzle, and in a further embodiment as a double-wall ring nozzle, whereby through one of the exit openings defined by the double wall inert gases can be injected into the melt, by means of which the lance can be cooled and/or a stirring motion can be produced in the melt. An optimization of this stirring motion can be achieved when the lance exit opening is designed so that the inert gases are delivered tangentially. Through the second exit opening, the dry or fluidized powder, consisting of additives, is then pressed in. In this way it is possible to generate different bath motions with the pure inert gas injected through the lance, depending on the dosage of the additives, which are supposed to be the more intensive the greater the amount of metal or deoxidizing agents introduced per unit time. Different from the methods known to the state of the art, it is possible to adjust independently the dosage amount per time unit and the bath motion.
According to a further development of the invention, a pressure between 50 bar and 100 bar is used for the compression of the additives in powder form.
The aforedescribed process of the invention, which can be applied in steel plants as well as in foundries, offers several possibilities for introducing alloy components, such as aluminum, silicon, magnesia, calcium, and various carbides into the melt. In addition to the volumetric dry transport over a dosage and compression transport, there is the volumetric conveyance of the gas-powder mixture or of the gas-liquid mixture, whereby the proportion of gas or liquid amounts to a maximum of 20% of the mixture. The fourth possibility consists in the aforedescribed volumetric transport of the mixture with a xe2x80x9cdry corexe2x80x9d of the additives to be introduced and a wet shell or a pasteous powder mix, consisting preferably of hydrocarbons, which have lubricant capability.
Thereby the following advantages result:
The proportion of fluidizing agent (inert gas, liquid) is reduced to a minimum. The dosage takes place via a volume measurement, which is more accurate than the conventional gravimetrical method, or of a throughflow measurement. The conveying pressure can be varied depending on the flowability of the powdery solid materials. Finally it is possible to establish the composition of the alloys according to specification during treatment. The dosages can be performed dust-free and with reduced emissions. Since there are no large amounts of transport gas (as is normally the case according to the state of the art), or only a small fluidization in the supplied product, the additives, the residence time of the additives in the reaction zone of the lance opening in the melt also increases.
For implementing the aforedescribed method a device is used wherein, a delivery line having a high-pressure pump leads directly from a supply container to a lance or a below-bath nozzle. These measures reduce considerably the energy consumption with respect to the conventional techniques. Also reduced are the service and maintenance.
According to a further development of the invention, the delivery line has an air or liquid inlet, preferably with an dosage adjusting device depending on the amounts supplied from the supply container, by means of which the desired mixing ratio powder: (fluidizing agents, respectively lubricants) can be set.
The lance has a double shell with two discharge openings, through one of which flows the metal in powder form or the reducing agent, optionally fluidized, and through the other flows the inert gas. In the ideal case, the discharge opening, respectively openings of the lance are arranged so that they abut tangentially. The lance itself is preferably swingable. The bath (the melt) can be arranged in a converter, a ladle or a torpedo carriage.

Method for alloying steels and device for carrying out the method