The distributed architecture switch of the invention provides a scalable, flexible switching device to route telephone calls and other data (e.g., frame relay, ISDN) over an asynchronous transfer mode (ATM) network. The switch includes multiple service modules that can be geographically disparate and function as a single switching device. The multiple service modules are coupled to a system controller that controls the service modules and passes messages between the service modules.

The invention relates to internetworking of multiple services using an asynchronous transfer mode (ATM) network. More particularly, the invention relates to use of dynamic ATM bearer trunking to support multiple services.
Common Channel Signaling System No. 7 (SS7 or C7) is a global standard for telecommunications defined by the International Telecommunications Union (ITU) to define procedures and protocols by which network elements of public switched telephone networks (PSTNs) exchange information to provide call setup, routing and control. The ITU definition of SS7 allows for regional variations such as, for example, the American National Standards Institute (ANSI) and Bell Communications Research (Bellcore) standards in North America and the European Telecommunications Standards Institute (ETSI) standard used in Europe.
SS7 provides a framework in which telephone networks provide basic call setup, management, and tear down, wireless services, local number portability, enhanced call features (e.g., call forwarding, calling party name/number information, three-way calling), etc. SS7 messages are exchanged between network elements over bi-directional channels called signaling links. These messages are communicated out-of-band on dedicated channels rather than in-band on voice channels. Out-of-band signaling provides faster call setup times, more efficient use of voice circuits, improved control over fraudulent network usage, and other advantages, compared to in-band signaling.
FIG. 1 is a block diagram of a Common Channel Signaling System No. 7 (SS7) network. In general, each signaling point in an SS7 network is uniquely identified by a numeric point code. Point codes are carried in signaling message between signaling points to identify the source and destination points for the message. Signaling points use routing tables to select an appropriate signal path for a message.
Service switching points (SSPs), such as SSPs 130 and 132, are switches that originate, terminate, or relay calls. SSPs are typically located in end offices that are coupled to multiple telephones or other devices that use telephone service. Telephones, such as telephones 110, 112, 120 and 122, are coupled to SSPs via local connections. Facsimile machines, modems and other devices can also be coupled to SSPs 130 and 132. An SSP sends signaling messages to other SSPs to setup, manage, and release voice circuits required for a call. An SSP can also send a query message to a service control point (SCP), such as SCPs 170 and 172, which acts as a database for certain types of calls, for example, 1-800/888 calls. The SCP sends a response to the originating SSP with routing information for the dialed number.
Traffic between SSPs can be routed by signal transfer points (STPs), such as STPs 140, 142, 150, 152, 160 and 162. STPs operate to route incoming messages to an outgoing signal link based on routing information contained in an SS7 message. In other words, STs operate as network hubs and eliminate the need for direct links between signaling points. An STP can perform global title translation to determine a destination signaling point based on digits present in the signaling message.
Signaling links between signaling points are logically organized by link type according to the purpose of the link. Access (xe2x80x9cAxe2x80x9d) links 180 connect a signaling end point (e.g., an SCP or SSP) to an STP. Only messages originating from or destined to the signaling end point are transmitted by an access link. Bridge (xe2x80x9cBxe2x80x9d) links 182 connect an STP to another STP. Typically, a group of four bridge links interconnect peer (or primary) STPs (e.g., the STPs from one network to STPs of another network).
Cross (xe2x80x9cCxe2x80x9d) links 184 connect STPs performing identical functions into a mated pair. A cross link is used only when an STP has no other route available to a destination signaling point due to, for example, a link failure. Diagonal (xe2x80x9cDxe2x80x9d) links 186 connect secondary (e.g., local or regional) STP pairs in a quad-link configuration.
Extended (xe2x80x9cExe2x80x9d) links 188 connect an SSP to an alternate STP. Extended links provide an alternate signaling path if an SSP""s primary STP cannot be reached via an access link. Fully associated (xe2x80x9cFxe2x80x9d) links 190 can be used to connect two signaling end points (e.g., SSPs and SCPs). Fully associated links are generally not used in networks with STPs.
When a party initiates a call, the call is held at SSP servicing the caller. For example, if the party initiates the call from telephone 110, the call is held at SSP 130. SSP 130 then transmits the information necessary to locate the called location and determines if the called location is busy or available to accept the call. If the called party is telephone 112, SSP 130 can directly determine whether telephone 112 is busy.
If the call destination is a telephone that is not coupled to SSP 130, call information is routed through network 100 to the appropriate SSP. If, for example, the call destination is telephone 120 or telephone 122, SSP 130 routes call information to SSP 132. The call information can be routed directly between SSP 130 and SSP 132 by a fully associated link, if present. Otherwise, the call information can be routed, for example, to STP 142 via an access link to STP 152 via a diagonal link to STP 162 via a bridge link to SSP 132 via an access link. SSP 132 determines whether the destination telephone is available to receive the call and returns the appropriate information to SSP 130.
If the destination telephone is available to receive the call, a trunk is established through network 100 from the call source to the call destination to establish a talk path and the call is established. When the call is completed, the trunk is torn down (call tear down) and the call is terminated. Connections through network 100 are established for each call in a similar manner.
Current PSTNs are based on designs and hardware from the 1970s. As the usage of these PSTNs changes because of, for example, Internet access and related activities, traditional PSTNs have become less optimal and other networking protocols have been used for specific purposes. For example, many telephone companies maintain both PSTNs and asynchronous transfer mode (ATM) networks for supporting various services. However, maintaining multiple networks with multiple protocols and hardware components is more time consuming and more expensive than maintaining a single network type. What is needed is a single network that can efficiently support multiple types of network services.
A switching device having a distributed architecture is described. The switching device includes a system controller coupled to multiple service modules. Each of the service modules has a first interface to receive and transmit telephone calls, a second interface to receive and transmit data according to a first protocol, and a third interface to transmit and receive data according to a second protocol. Telephone calls received via the first interface and data received via the second interface are converted to the second protocol and routed to an external device. Data received from the third interface is converted to one of the first protocol and a telephone protocol and routed to the second interface, if converted to the first protocol, and routed to the first interface if converted to the telephone protocol.

Public switched telephone network call routing using dyamic asynchronous mode transfer bearer voice trunking


The invention is directed to an improvement or enhancement of a keyboard. Particularly, the keys of a keyboard are enhanced or modified, to improve or instill a tactile sensation to a person doing the typing. In this respect, certain of the keys are modified by adding tactile edges to the keys, typing school and instructors and instructions for the beginners instruct the learners to place their fingers in the middle row of the lettered keyboard. Instructions further advise to divide this middle row into two groups, one for the left hand and one for the right hand. Both groups involve the four fingers of each group excluding the thumb. The four fingers of the left hand will be placed over the letters A through F and the fingers of the right hand are placed over the letters J, K, L including the semi colon. The outside edges of the key letter A of the left hand and on the semicolon key of the right hand have outside raised edges placed thereon. This way the four fingers of the left hand and the four fingers of the right are sort of cradled between the raised edges and gives the typist a tactile sensation indicating where exactly the fingers are placed on the keyboard which enhances the speed and the accuracy of the person doing the typing.

The invention is directed to a modification of a keyboard, particularly to the keys of a keyboard. The keyboard can be that of a simple type writer, the keyboard of a word processor or a computer. The purpose of the modifications is for enhancing the speed and accuracy of the person doing the typing.
More particularly, there are certain keys only that will be modified. The keyboard being modified is the internationally well known keyboard under the name or designation of xe2x80x9cQWERTYxe2x80x9d by taking the first six letters of the upper first row of letters. It is very common for a typist to misplace their fingers while typing, causing typing errors. The inventive concept is directed toward certain keys by improving the tactile contact with the certain keys. Many devices have been developed which will enhance the tactility of a user to be able to quicker find certain keys. For example, such enhancements are found on Braille type writers. Another way of enhancing keys on a keyboard has been developed by the DATACAL ENTERPRISES by color coding certain keys. Other products are known through the catalogs by HOOLEON claiming increased productivity and cut training costs by putting required keystrokes right on the keys there is no need to jump between required cryptic manuals and the requisite keyboard. What is being used here are large print touchdown key top label sets which will enhance any vision problems.
Another enhancement of keys by HOOLEAN is a set of blank keys that may be placed on a keyboard and by pulling the original keys off the keyboard and replacing the same with blank keys. A special key puller is provided to accomplish the above noted task. This set-up may improve the memory of a person typing but does not contribute to a tactical feel when typing.
Another system is known under the name of xe2x80x9cKeyguardxe2x80x9d which is distributed by xe2x80x9cDon Johnston Development Equipmentxe2x80x9d. These keyguards are metal shields with holes over the key position which help prevent the unintentional activation of more than one key at a time. The round holes above each key provide a guide for a finger or pointer and provide the inadvertent pressing of keys.
xe2x80x9cQuickeysxe2x80x9d by CE Software Inc. present Home-row Indicators that are small adhesive-backed labels that can be attached to home row or any appropriate keys. A raised bump in the center of the indicators serves as a tactile guide for placing the fingers. This teaching is the closest tactile guide known to the applicant.
xe2x80x9cLoc-Dots distributed by xe2x80x9cARTS computer products Inc. provides the same principle as xe2x80x98Quickeysxe2x80x99 above in that xe2x80x9cLoc-Dotsxe2x80x9d are adhesive-backed raised dots that can be applied to any keys on any keyboard. They may be used as tactile cues to identify home row keys or other keys as determined by the user.
Then there are xe2x80x9cTouchdown Key Expandersxe2x80x9d distributed by the xe2x80x9cHOOLEANxe2x80x9d Corp. which are caps which fit over the top of keys. These caps present a larger surface for the user to strike. These caps are designed to fit those keys which are large but have a smaller and raised area for the user to strike.
The keys that are modified according to the invention are eight keys located in the middle row of the alphabetical letters. These eight letters are subdivided into two groups of four letters each. These two groups have been chosen because they are used as basic tools or indicators in typing schools or typing instructions. The two letter groups involve the left first group of letters A S D F.
On the right side the second group of letters J K L including the semi colon is being used or designated. The typing instructions always place the left hand four fingers on the first group and the right hand four fingers on the second group of keys. Even professional and proficient typists make typing mistakes because the outside left and right fingers of each hand overreach the positions on the keys where they should be which will cause double strikes, wrong keys or missed lineage. This invention solves the above noted problems by adding tactile means to each of the four outside keys


Laminates are prepared from resin-impregnated flexible graphite sheets. Impregnated sheets are calendered and layers of the calendered sheets, which may also be coated with a resin adhesive, are stacked into structures which optionally contains layers of metals or plastics. After curing at elevated temperature and pressure, 2500 psi and 150xc2x0 C., the laminates form dense machinable structures suitable for uses such as electronic thermal management (ETM) devices.

This invention relates to laminates prepared from resin impregnated flexible graphite sheets. The laminates, which may also include layers of other materials such as metals and plastics, are cured under heat and pressure and are machinable structures useful in applications such as heat transporters used in electronic thermal management (ETM).
Laminates in which one or more of the layers consist of flexible graphite sheets are known in the art. These structures find utility, for example, in gasket manufacture. See U.S. Pat. No. 4,961,991 to Howard. Howard discloses various laminate structures which contain metal or plastic sheets, bonded between sheets of flexible graphite. Howard discloses that such structures can be prepared by cold-working a flexible graphite sheet on both sides of a metal net and then press-adhering the graphite to the metal net. Howard also discloses placing a polymer resin coated cloth between two sheets of flexible graphite while heating to a temperature sufficient to soften the polymer resin, thereby bonding the polymer resin coated cloth between the two sheets of flexible graphite to produce a flexible graphite laminate. Similarly, Hirschvogel, U.S. Pat. No. 5,509,993, discloses flexible graphite/metal laminates prepared by a process which involves as a first step applying a surface active agent to one of the surfaces to be bonded. Mercuri, U.S. Pat. No. 5,192,605, also forms laminates from flexible graphite sheets bonded to a core material which may be metal, fiberglass or carbon. Mercuri deposits and then cures a coating of an epoxy resin and particles of a thermoplastic agent on the core material before feeding core material and flexible graphite through calender rolls to form the laminate.
In addition to their utility in gasket materials, graphite laminates also find utility as heat transfer or cooling apparatus. The use of various solid structures as heat transporters is known in the art. For example, Banks, U.S. Pat. Nos. 5,316,080 and 5,224,030 discloses the utility of diamonds and gas-derived graphite fibers, joined with a suitable binder, as heat transfer devices. Such devices are employed to passively conduct heat from a source, such as a semiconductor, to a heat sink.
Graphite layered thermal management components offer several advantages in electronic applications and can help eliminate the potential negative impacts of heat generating components in computers, communications equipment, and other electronic devices. Graphite based thermal management components include heat sinks, heat pipes and heat spreaders. All offer thermal conductivity equivalent to or better than copper or aluminum, but are a fraction of the weight of those materials, and provide significantly greater design flexibility. Graphite based thermal management products take advantage of the highly directional properties of graphite to move heat away from sensitive components. Compared to typical aluminum alloys used for heat management, graphite components can exhibit up to 300% higher thermal conductivity, with values comparable to copper (xcx9c400 watts per meter degree Kelvin, i.e., W/mC) or greater attainable. Further, aluminum and copper are isotropic, making it impossible to channel the heat in a preferred direction.
The flexible graphite preferred for use in the laminate of this invention is flexible graphite sheet material.
The following is a brief description of graphite and the manner in which it is typically processed to form flexible sheet materials. Graphite, on a microscopic scale, is made up of layer planes of hexagonal arrays or networks of carbon atoms. These layer planes of hexagonally arranged carbon atoms are substantially flat and are oriented or ordered so as to be substantially parallel and equidistant to one another. The substantially-flat, parallel, equidistant sheets or layers of carbon atoms, usually referred to as graphene layers or basal planes, are linked or bonded together and groups thereof are arranged in crystallites. Highly-ordered graphite materials consist of crystallites of considerable size, the crystallites being highly aligned or oriented with respect to each other and having well ordered carbon layers. In other words, highly ordered graphites have a high degree of preferred crystallite orientation. It should be noted that graphites, by definition, possess anisotropic structures and thus exhibit or possess many characteristics that are highly directional, e.g., thermal and electrical conductivity and fluid diffusion.
Briefly, graphites may be characterized as laminated structures of carbon, that is, structures consisting of superposed layers or laminae of carbon atoms joined together by weak van der Waals forces. In considering the graphite structure, two axes or directions are usually noted, to wit, the xe2x80x9ccxe2x80x9d axis or direction and the xe2x80x9caxe2x80x9d axes or directions. For simplicity, the xe2x80x9ccxe2x80x9d axis or direction may be considered as the direction perpendicular to the carbon layers. The xe2x80x9caxe2x80x9d axes or directions may be considered as the directions parallel to the carbon layers or the directions perpendicular to the xe2x80x9ccxe2x80x9d direction. The graphites suitable for manufacturing flexible graphite sheets possess a very high degree of orientation.
As noted above, the bonding forces holding the parallel layers of carbon atoms together are only weak van der Waals forces. Natural graphites can be chemically treated so that the spacing between the superposed carbon layers or laminae can be appreciably opened up so as to provide a marked expansion in the direction perpendicular to the layers, that is, in the xe2x80x9ccxe2x80x9d direction, and thus form an expanded or intumesced graphite structure in which the laminar character of the carbon layers is substantially retained.
Graphite flake which has been chemically or thermally expanded and more particularly expanded so as to have a final thickness or xe2x80x9ccxe2x80x9d direction dimension which is as much as about 80 or more times the original xe2x80x9ccxe2x80x9d direction dimension, can be formed without the use of a binder into cohesive or integrated sheets of expanded graphite, e.g. webs, papers, strips, tapes, or the like (typically referred to as xe2x80x9cflexible graphitexe2x80x9d). The formation of graphite particles which have been expanded to have a final thickness or xe2x80x9ccxe2x80x9d dimension which is as much as about 80 times or more the original xe2x80x9ccxe2x80x9d direction dimension into integrated flexible sheets by compression, without the use of any binding material, is believed to be possible due to the mechanical interlocking, or cohesion, which is achieved between the voluminously expanded graphite particles.
In addition to flexibility, the sheet material, as noted above, has also been found to possess a high degree of anisotropy to thermal and electrical conductivity and fluid diffusion, somewhat less, but comparable to the natural graphite starting material due to orientation of the expanded graphite particles substantially parallel to the opposed faces of the sheet resulting from very high compression, e.g. roll processing. Sheet material thus produced has excellent flexibility, good strength and a very high degree or orientation. There is a need for processing that more fully takes advantage of these properties.
Briefly, the process of producing flexible, binderless anisotropic graphite sheet material, e.g. web, paper, strip, tape, foil, mat, or the like, comprises compressing or compacting under a predetermined load and in the absence of a binder, expanded graphite particles which have a xe2x80x9ccxe2x80x9d direction dimension which is as much as about 80 or more times that of the original particles so as to form a substantially flat, flexible, integrated graphite sheet. The expanded graphite particles that generally are worm-like or vermiform in appearance will, once compressed, maintain the compression set and alignment with the opposed major surfaces of the sheet. Properties of the sheets may be altered by coatings and/or the addition of binders or additives prior to the compression step. See U.S. Pat. No. 3,404,061 to Shane, et al. The density and thickness of the sheet material can be varied by controlling the degree of compression.
Lower densities are advantageous where surface detail requires embossing or molding, and lower densities aid in achieving good detail. However, higher in-plane strength, thermal conductivity and electrical conductivity are generally favored by more dense sheets. Typically, the density of the sheet material will be within the range of from about 0.04 cm3 to about 1.4 cm3.
Flexible graphite sheet material made as described above typically exhibits an appreciable degree of anisotropy due to the alignment of graphite particles parallel to the major opposed, parallel surfaces of the sheet, with the degree of anisotropy increasing upon roll pressing of the sheet material to increased density. In roll-pressed anisotropic sheet material, the thickness, i.e. the direction perpendicular to the opposed, parallel sheet surfaces comprises the xe2x80x9ccxe2x80x9d direction and the directions ranging along the length and width, i.e. along or parallel to the opposed, major surfaces comprises the xe2x80x9caxe2x80x9d directions and the thermal, electrical and fluid diffusion properties of the sheet are very different, by orders of magnitude typically, for the xe2x80x9ccxe2x80x9d and xe2x80x9caxe2x80x9d directions.
It is an object of the invention to provide a machinable laminate of resin impregnated graphite sheets suitable for use in electronic thermal management (ETM).
It is a further object of the invention to provide a high density graphite laminate utilizing relatively modest curing pressures.
It is a further object of this invention to provide laminated graphite structures having enhanced in-plane properties.
It is a further object of the invention to provide a machinable graphite laminate structure having relatively high thermal conductivity in the xe2x80x9caxe2x80x9d directions and relatively low conductivity in the xe2x80x9ccxe2x80x9d direction.
These and other objects are accomplished by the present invention, which provides a machinable structure comprising layers of epoxy impregnated flexible graphite together with optional layers of metals or non-metallic materials including plastics.
This invention is based upon the finding that when flexible sheets of epoxy impregnated graphite are calendered, stacked and cured at elevated temperatures and pressures, the resultant laminate is of unexpectedly good mechanical and thermal properties and also possesses good machinability.
Before describing the manner in which the invention improves current materials, a brief description of graphite and its formation into flexible sheets, which will become the primary substrate for forming the products of the invention, is in order.
Graphite is a crystalline form of carbon comprising atoms covalently bonded in flat layered planes with weaker bonds between the planes. By treating particles of graphite, such as natural graphite flake, with an intercalant of, e.g. a solution of sulfuric and nitric acid, the crystal structure of the graphite reacts to form a compound of graphite and the intercalant. The treated particles of graphite are hereafter referred to as xe2x80x9cparticles of intercalated graphite.xe2x80x9d Upon exposure to high temperature, the intercalant within the graphite decomposes and volatilizes, causing the particles of intercalated graphite to expand in dimension as much as about 80 or more times its original volume in an accordion-like fashion in the xe2x80x9ccxe2x80x9d direction, i.e. in the direction perpendicular to the crystalline planes of the graphite. The exfoliated graphite particles are vermiform in appearance, and are therefore commonly referred to as worms, and are sometimes referred to herein as xe2x80x9cparticles of expanded graphite.xe2x80x9d The worms may be compressed together into flexible sheets that, unlike the original graphite flakes, can be formed and cut into various shapes and provided with small transverse openings by deforming mechanical impact.
Graphite starting materials suitable for use in the present invention include highly graphitic carbonaceous materials capable of intercalating organic and inorganic acids as well as halogens and then expanding when exposed to heat. These highly graphitic carbonaceous materials most preferably have a degree of graphitization of about 1.0. As used in this disclosure, the term xe2x80x9cdegree of graphitizationxe2x80x9d refers to the value g according to the formula:   g  =            3.45      -              d                          (          002          )                      0.095
where d(002) is the spacing between the graphitic layers of the carbons in the crystal structure measured in Angstrom units. The spacing d between graphite layers is measured by standard X-ray diffraction techniques. The positions of diffraction peaks corresponding to the (002), (004) and (006) Miller Indices are measured, and standard least-squares techniques are employed to derive spacing which minimizes the total error for all of these peaks. Examples of highly graphitic carbonaceous materials include natural graphites from various sources, as well as other carbonaceous materials such as carbons prepared by chemical vapor deposition and the like. Natural graphite is most preferred.
The graphite starting materials used in the present invention may contain non-carbon components so long as the crystal structure of the starting materials maintains the required degree of graphitization and they are capable of exfoliation. Generally, any carbon-containing material, the crystal structure of which possesses the required degree of graphitization and which can be intercalated and exfoliated, is suitable for use with the present invention. Such graphite preferably has an ash content of less than twenty weight percent. More preferably, the graphite employed for the present invention will have a purity of at least about 94%. In the most preferred embodiment, the graphite employed will have a purity of at least about 98%.
A common method for manufacturing graphite sheet is described by Shane et al. in U.S. Pat. No. 3,404,061, the disclosure of which is incorporated herein by reference. In the typical practice of the Shane et al. method, natural graphite flakes are intercalated by dispersing the flakes in a solution containing e.g., a mixture of nitric and sulfuric acid, advantageously at a level of about 20 to about 300 parts by weight of intercalant solution per 100 parts by weight of graphite flakes (pph). The intercalation solution contains oxidizing and other intercalating agents known in the art. Examples include those containing oxidizing agents and oxidizing mixtures, such as solutions containing nitric acid, potassium chlorate, chromic acid, potassium permanganate, potassium chromate, potassium dichromate, perchloric acid, and the like, or mixtures, such as for example, concentrated nitric acid and chlorate, chromic acid and phosphoric acid, sulfuric acid and nitric acid, or mixtures of a strong organic acid, e.g. trifluoroacetic acid, and a strong oxidizing agent soluble in the organic acid. Alternatively, an electric potential can be used to bring about oxidation of the graphite. Chemical species that can be introduced into the graphite crystal using electrolytic oxidation include sulfuric acid as well as other acids.
In a preferred embodiment, the intercalating agent is a solution of a mixture of sulfuric acid, or sulfuric acid and phosphoric acid, and an oxidizing agent, i.e. nitric acid, perchloric acid, chromic acid, potassium permanganate, hydrogen peroxide, iodic or periodic acids, or the like. The intercalation solution may also contain metal halides such as ferric chloride, and ferric chloride mixed with sulfuric acid, or a halide, such as bromine, as a solution of bromine and sulfuric acid or bromine, in an organic solvent.
The quantity of intercalation solution may range from about 20 to about 150 pph and more typically about 50 to about 120 pph. After the flakes are intercalated, any excess solution is drained from the flakes and the flakes are water-washed. Alternatively, the quantity of the intercalation solution may be limited to between about 10 and about 50 pph, which permits the washing step to be eliminated as taught and described in U.S. Pat. No. 4,895,713, the disclosure of which is also herein incorporated by reference.
The particles of graphite flake treated with intercalation solution can optionally be contacted, e.g. by blending, with a reducing organic agent selected from alcohols, sugars, aldehydes and esters which are reactive with the surface film of oxidizing intercalating solution at temperatures in the range of 25xc2x0 C. and 125xc2x0 C. Suitable specific organic agents include hexadecanol, octadecanol, 1-octanol, 2-octanol, decylalcohol, 1,10 decanediol, decylaldehyde, 1-propanol, 1,3 propanediol, ethyleneglycol, polypropylene glycol, dextrose, fructose, lactose, sucrose, potato starch, ethylene glycol monostearate, diethylene glycol dibenzoate, propylene glycol monostearate, glycerol monostearate, dimethyl oxylate, diethyl oxylate, methyl formate, ethyl formate, ascorbic acid and lignin-derived compounds, such as sodium lignosulfate. The amount of organic reducing agent is suitably from about 0.5 to 4% by weight of the particles of graphite flake.
The use of an expansion aid applied prior to, during or immediately after intercalation can also provide improvements. Among these improvements can be reduced exfoliation temperature and increased expanded volume (also referred to as xe2x80x9cworm volumexe2x80x9d). An expansion aid in this context will advantageously be an organic material sufficiently soluble in the intercalation solution to achieve an improvement in expansion. More narrowly, organic materials of this type that contain carbon, hydrogen and oxygen, preferably exclusively, may be employed. Carboxylic acids have been found especially effective. A suitable carboxylic acid useful as the expansion aid can be selected from aromatic, aliphatic or cycloaliphatic, straight chain or branched chain, saturated and unsaturated monocarboxylic acids, dicarboxylic acids and polycarboxylic acids which have at least 1 carbon atom, and preferably up to about 15 carbon atoms, which is soluble in the intercalation solution in amounts effective to provide a measurable improvement of one or more aspects of exfoliation. Suitable organic solvents can be employed to improve solubility of an organic expansion aid in the intercalation solution.
Representative examples of saturated aliphatic carboxylic acids are acids such as those of the formula H(CH2)nCOOH wherein n is a number of from 0 to about 5, including formic, acetic, propionic, butyric, pentanoic, hexanoic, and the like. In place of the carboxylic acids, the anhydrides or reactive carboxylic acid derivatives such as alkyl esters can also be employed. Representative of alkyl esters are methyl formate and ethyl formate. Sulfuric acid, nitric acid and other known aqueous intercalants have the ability to decompose formic acid, ultimately to water and carbon dioxide. Because of this, formic acid and other sensitive expansion aids are advantageously contacted with the graphite flake prior to immersion of the flake in aqueous intercalant. Representative of dicarboxylic acids are aliphatic dicarboxylic acids having 2-12 carbon atoms, in particular oxalic acid, fumaric acid, malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, 1,5-pentanedicarboxylic acid, 1,6-hexanedicarboxylic acid, 1,10-decanedicarboxylic acid, cyclohexane-1,4-dicarboxylic acid and aromatic dicarboxylic acids such as phthalic acid or terephthalic acid. Representative of alkyl esters are dimethyl oxylate and diethyl oxylate. Representative of cycloaliphatic acids is cyclohexane carboxylic acid and of aromatic carboxylic acids are benzoic acid, naphthoic acid, anthranilic acid, p-aminobenzoic acid, salicylic acid, o-, m- and p-tolyl acids, methoxy and ethoxybenzoic acids, acetoacetamidobenzoic acids and, acetamidobenzoic acids, phenylacetic acid and naphthoic acids. Representative of hydroxy aromatic acids are hydroxybenzoic acid, 3-hydroxy-1-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4-hydroxy-2-naphthoic acid, 5-hydroxy-1-naphthoic acid, 5-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid and 7-hydroxy-2-naphthoic acid. Prominent among the polycarboxylic acids is citric acid.
The intercalation solution will be aqueous and will preferably contain an amount of expansion aid of from about 1 to 10%, the amount being effective to enhance exfoliation. In the embodiment wherein the expansion aid is contacted with the graphite flake prior to or after immersing in the aqueous intercalation solution, the expansion aid can be admixed with the graphite by suitable means, such as a V-blender, typically in an amount of from about 0.2% to about 10% by weight of the graphite flake.
After intercalating the graphite flake, and following the blending of the intercalant coated intercalated graphite flake with the organic reducing agent, the blend is exposed to temperatures in the range of 25xc2x0 to 125xc2x0 C. to promote reaction of the reducing agent and intercalant coating. The heating period is up to about 20 hours, with shorter heating periods, e.g., at least about 10 minutes, for higher temperatures in the above-noted range. Times of one half hour or less, e.g., on the order of 10 to 25 minutes, can be employed at the higher temperatures.
The thus treated particles of graphite are sometimes referred to as xe2x80x9cparticles of intercalated graphite.xe2x80x9d Upon exposure to high temperature, e.g. temperatures of at least about 160xc2x0 C. and especially about 700xc2x0 C. to 1000xc2x0 C. and higher, the particles of intercalated graphite expand as much as about 80 to 1000 or more times their original volume in an accordion-like fashion in the c-direction, i.e. in the direction perpendicular to the crystalline planes of the constituent graphite particles. The expanded, i.e. exfoliated, graphite particles are vermiform in appearance, and are therefore commonly referred to as worms, and are sometimes referred herein as xe2x80x9cparticles of expanded graphite.xe2x80x9d The worms may be compressed together into flexible sheets that, unlike the original graphite flakes, can be formed and cut into various shapes and provided with small transverse openings by deforming mechanical impact as hereinafter described.
Flexible graphite sheet and foil are coherent, with good handling strength, and are suitably compressed, e.g. by roll-pressing, to a thickness of about 0.075 mm to 3.75 mm and a typical density of about 0.1 to 1.4 grams per cubic centimeter (g/cm3).
The individual layers of graphite within the flexible graphite sheet are not stacked close enough and with the proper crystal stacking sequence to have the same degree of orientation as single crystals of graphite. Therefore, this material has only limited thermal conductivity in the plane of the sheet. Single crystals of graphite will exhibit a thermal conductivity of about 2000 W/mC in plane and 10 out of plane. Flexible graphite sheets of the sort above described have a thermal conductivity of about 100-250 W/mC in plane and about 6-9 W/mC out of plane.
According to the invention, flexible graphite sheets prepared as described above and having a thickness of about 4 mm to 7 mm are impregnated with a thermosetting resin such as an epoxy, acrylic or phenolic resin system. Suitable epoxy resins include diglycidyl ether of bisphenol A (DGEBA) resin systems; other multifunctional epoxy resins systems are also suitable for use in the present invention. Suitable phenolic resin systems include those containing resole and novolak resins. The sheets are then calendered to a thickness of about 0.35 mm to 0.5 mm, at which time the calendered, epoxy impregnated flexible mats have a density of about 1.4 g/cm3 to about 1.9 g/cm3.
The amount of resin within the epoxy impregnated graphite sheets should be an amount sufficient to ensure that the final assembled and cured layered structure is dense and cohesive, yet the anisotropic thermal conductivity associated with a densified graphite structure has not been adversely impacted. Suitable resin content is preferably at least about 3% by weight, more preferably from about 5% to about 35% by weight depending on the characteristics desired in the final product.
In a typical resin impregnation step, the flexible graphite sheet is passed through a vessel and impregnated with the resin system from, e.g. spray nozzles, the resin system advantageously being xe2x80x9cpulled through the matxe2x80x9d by means of a vacuum chamber. Typically, but not necessarily, the resin system is solvated to facilitate application into the flexible graphite sheet. The resin is thereafter preferably dried, reducing the tack of the resin and the resin-impregnated sheet.
One form of apparatus for continuously forming resin-impregnated and calendered flexible graphite sheet is shown in International Publication No. WO 00/64808, the disclosure of which is incorporated herein by reference.
Following the calendering step, the impregnated sheets are cut to suitable-sized pieces which are stacked together and placed in a press, where they are cured at an elevated temperature. The temperature should be sufficient to ensure that the lamellar structure is densified at the curing pressure, while the thermal properties of the structure are not adversely impacted. Generally, this will require a temperature of from about 150xc2x0 C. to 200xc2x0 C. The pressure employed for curing will be somewhat a function of the temperature utilized, but will be sufficient to ensure that the lamellar structure is densified without adversely impacting the thermal properties of the structure. Generally, for convenience of manufacture, the minimum required pressure to densify the structure to the required degree will be utilized. Such a pressure will generally be from 1000 to 3000 pounds per square inch (psi). The curing time may vary depending on the resin system and the temperature and pressure employed, but generally will range from 0.5 hours to 2 hours. After curing is complete, the composites are seen to have a density of from about 1.8 g/cm3 to 2.0 g/cm3.
Advantageously, the resin present in the impregnated sheets can act as the adhesive for the composite material. According to another embodiment of the invention, however, the calendered, impregnated, flexible graphite sheets are coated with an adhesive before the flexible sheets are stacked and cured. Suitable adhesives include epoxy-, acrlylic- and phenolic-based resins. Phenolic resins found especially useful in the practice of the present invention include phenolic-based resin systems including resole and novolak phenolics.
According to another embodiment of the invention, non-graphite layers may be included in the pre-pressed stack. Such non-graphite layers may include metals, plastics or other non-metallics such as fiberglass or ceramics. The epoxy polymer in the impregnated graphite sheets is sufficient to, upon curing, adhesively bond the non-graphite as well as the impregnated graphite layers of the structure into place.
The following examples are presented to further illustrate and explain the invention and are not intended to be limiting in any regard. Unless otherwise indicated, all parts and percentages are by weight.

Laminates prepared from impregnated flexible graphite sheets


A portable olfactometer for sensing and measuring odors by sniffing has a barrel which carries selectively different D/T ratios of odorous air to a nose mask and has a selective set of inserts for providing different D/T ratios at the input to the barrel.

This invention relates to sensing or detecting and measuring odors and in particular is aimed at detecting and measuring odors in the field, i.e., not under laboratory conditions.
U.S. Pat. No. 6,018,984 and an earlier U.S. Pat. No. 3,902,851, referenced in the ""984 patent, discuss and describe in considerable detail olfactometers for detecting and measuring air polluting odors. These devices are quite sophisticated and are used as laboratory instruments in which the sample odors are fed from a container into the olfactometer in various dilution ratios commonly known as D/T, (xe2x80x9cDilution to Thresholdxe2x80x9d). In the device described in the ""984 patent odorous air is fed to a venturi mixing nozzle through various branches containing solenoid operated valves and different sized orifices for mixing with odor-free air to provide various D/T levels. The prior art also includes a device for field use for detecting and measuring air pollution in the form of a Scentometer manufactured and sold by Barnebey and Sutcliffe Corporation (now Barnebey-Cheney Company). The Scentometer essentially is a rectangular clear plastic box containing two chambers of activated carbon, two nasal outlet ports for sniffing separately into each nostril, two air inlets (one for each activated carbon bed) and six odorous air inlets of different sizes, to provide the various D/T ratios, which are directly connected with a mixing chamber and the nasal outlets. Odorless or odor-free air is obtained by air being drawn through beds of carbon and filtered air is mixed with the odorous air. The Scentometer user follows the generally accepted or standard practice of detecting and measuring the odor by first sniffing with the smallest odorous air inlet opening (lowest D/T ratio) and then successively opening the next largest odorous air inlet until the user or tester finds that an odor is discernible. The size of the opening or orifice for the odor inlet at which the odor is discernible then indicates to the tester the approximate concentration of the odor or the odor level. In the past, conventionally D/T was calculated by dividing the volume of odor free air by the volume of odorous air but more recently, the more sophisticated laboratory instruments calculate D/T by dividing the total air flow volume by the volume of odorous air.
The present invention utilizes a fairly small lightweight housing suitable to be hand carried so it is convenient to use in the field. The housing contains a hollow tube or barrel open at both ends. One end is the air input end, the other is the air output end. Odorous air, i.e., the ambient polluted air, enters the inlet end and travels down the tube to the outlet end to which is attached a nose mask for directing the air to the sensor or tester""s nostrils when the user inhales. The nose mask also has an outlet opening and there are check valves for the nose mask inlet openings and outlet openings so that the former is open and the latter closed when the user inhales and vice versa. Odorless or odor-free air is obtained from ambient air passing through a multi-media filter and is fed into the housing where it is mixed with the polluted or odorous air at the inlet end of the barrel. In the preferred form a disk having a series of apertures is rotatably attached to the housing at the air inlet end of the barrel with the apertures containing inserts having respectively different sized orifices and thicknesses. The disk is rotated by the user to bring each aperture successively to a position opposite the inlet opening of the barrel and sniffs as necessary to draw the air mixture into the nose mask. The setting at which the odor is discernible gives the D/T ratio. Filtering the ambient air through a multi-media filter instead of through a carbon filter as in the Scentometer provides a more universal and more complete filtering of odors out of the ambient air that is used to mix with the odorous air. Preferably these filters are commercially available devices which can be releasably secured to the housing in some convenient fashion such as snapping or press-fitting or threading them into place. They are suitably sealed to prevent any leakage of any of the polluted air into the odor-free air passageway yet they are attached in some fashion so they can be easily and quickly removed and replaced as necessary.

Portable odor detecting and measuring device


In order to design a blast furnace in a space and cost-saving manner, the invention provides for an especially compact blast furnace (10) having no hearth, wherein the burden is transported to the charging platform by vertical conveyers (20) and a compactly designed burdening (30) and pouring bay (50) are placed in the immediate proximity of said installation.

The invention relates to a blast furnace installation comprising a blast furnace of a shaft furnace construction and of a free-standing configuration without frame as well as correlated installation parts such as hot blast generating device, burdening, and pouring bay for continuous smelting of at least partially treated iron ore to hot metal.
Such blast furnaces without frame are known. For example, such blast furnaces without frame (American configuration) are described in xe2x80x9cHtttexe2x80x9d, Taschenbuch fxc3xcr Eisenhxc3xcttenleute, publishing house Wilhelm Ernst and Sohn, Berlin, 1961, on page 528, wherein the shaft is armored with a steel sheet mantle and is supported by means of a support ring on supports which are positioned closely adjacent to the blast furnace.
Modern blast furnace installation technology is based on the design and an installation arrangement which is based on the available technology and the logistic necessities for charging of the blast furnace with raw materials as well as for transporting the liquid products hot metal and slag.
The generally available technology results in a blast furnace which is provided with a blast furnace frame in order to free the furnace construction itself as much as possible from all loads. On this blast furnace frame, the entire upper furnace construction, including top closing device, gas removal pipes, and safety valves inclusive of pressure compensation, is supported as well as the charging belt by which the raw materials are transported to the upper end of the blast furnacexe2x80x94the charging platform.
The blast furnace installation of known installations includes, in addition to the blast furnace, a burdening apparatus containing a burdening or mixture of ores (hereinafter referred to simply as xe2x80x9ca burdeningxe2x80x9d or xe2x80x9cthe burdeningxe2x80x9d), which is connected with the blast furnace by a charging belt and, corresponding to the incline angle of the charging belt and the height of the blast furnace, approximately 55 to 65 m, is arranged approximately 300 m away from the blast furnace. Moreover, adjacent to the blast furnace a hot blast generating device is provided in which, by means of currently usually three hot blast apparatus, the required reaction gas (combustion air) is pre-heated as well as, furthermore, a dust removal and cleaning device for the blast furnace gas in the vicinity of the blast furnace. The frame armor of the blast furnace is cooled generally by means of a conventional frame open-surface cooler also known as a trickling apparatus.
In an unpublished German patent application (application No. 198 24 367.7) it has been suggested to replace the inclined elevator or the charging belt for the transport of the raw materials to the charging platform by a vertical elevator, and in a further unpublished application (application No. 198 16 867.5) it has been recommended to manufacture the water-cooled cooling elements, arranged between the frame armor and the refractory blast furnace wall, of a material having high thermal conductivity in order to minimize the danger of break-out within the frame area during operation of the blast furnace.
Based on this known prior art, it is the object of the invention to develop for a blast furnace a new space-saving and cost-saving concept of a blast furnace installation by which the crude steel production is economical even for small throughput.
This object is solved for a blast furnace installation wherein the blast furnace with a frame diameter of between 5 and 10 m is of a compact configuration with the features:
(a) a self-supporting blast furnace armor construction wherein the entire upper blast furnace construction of the blast furnacexe2x80x94with a top closing device configured as a revolving chute with a fixedly installed slant angle without tilting mechanism, gas removal pipe, and safety valves including pressure compensationxe2x80x94is supported on the blast furnace armor;
b) in the frame area, in the zones of belly of the blast furnace, waist of the blast furnace, and lower shaft, water-cooled cooling elements of a material having high thermal conductivity are arranged between the refractory furnace wall and the blast furnace armor; and
c) for tapping of the hot metal only one tap hole is installed on the furnace with only one set of tap hole plugging and drilling machines.
With the measures of the invention, to configure the blast furnace in a compact configuration as well as to configure or arrange the arrangement of the most important installation parts belonging to the blast furnace in a compact way in direct vicinity of the blast furnace, a completely new design of a compact blast furnace installation is obtained. There is the possibility of installing a conventional frame open-surface cooler or trickling apparatus.
By employing cooling elements in the thermally highly loaded frame area of the blast furnace, which elements are manufactured of a material having high thermal conductivity, the blast furnace armor is optimally cooled in this area which is at risk for break-out. The danger of cooling failure with local overheating, in connection with failure of the material strength, is therefore no longer present. This results directly in that the blast furnace armor is particularly loaded and the complex blast furnace frame that was required in the past can be eliminated in any case. Required working platforms can be fastened directly on the armor of the furnace. Also, the entire upper furnace construction with a top closing device, gas removal pipes, and the safety valves including pressure compensation are now supported on the blast furnace armor.
According to an advantageous configuration of the invention, in this connections the otherwise conventional complex top closing device is formed by a revolving chute of a simplified configuration wherein a tilting mechanism is eliminated and the slant angle of the revolving chute is fixedly adjusted once according to the furnace size. This has the advantage, in particular, in the case of smaller blast furnaces, that the top closing device drive (the revolving chute carrier) can be constructed in a much simpler way and the material distribution can be controlled with the radially movable throat armor that is present.
Moreover, the support of a charging belt on the blast furnace or on the blast furnace frame is no longer required with the configuration of the compact blast furnace according to the invention because the charging belt is replaced by a vertical conveyor which does not require any supporting action and which is arranged directly adjacent to the blast furnace. The spacing of the vertical conveyor is approximately 25 to 35 m away from the center axis of the blast furnace. This makes it possible to arrange the burdening directly adjacent theretoxe2x80x94it is conventional in known blast furnace installations to have a spacing of the burdening housing from the blast furnace of approximately 300 mxe2x80x94so that a considerable savings in regard to the space requirement for the blast furnace arrangement according to the invention is obtained.
Also, the burdening itself is advantageously of a more compact design in that the working and material storage volume of 10 to 12 hours, conventional according to the prior art, is preferably reduced to 3 to 4 hours. This is sufficient for a safe consumption supply of the installation because the operation, as a result of the installed automation and control, is optimally monitored.
Since on the blast furnace only one tap hole aperture is installed (with only one set of tap hole plugging and drilling machines), it is now advantageously possible to design the pouring bay configuration much smaller (more compact) and thus in a more cost-beneficial way. The pouring bay, according to the invention, is arranged directly adjacent to the blast furnace and is configured such that the rail system for transporting the hot metal and liquid slag is no longer needed. By means of a gutter system the hot metal is transported into correspondingly large ladles and transported in a wheel-bound container, while the liquid slag is transported into a slag blanket and/or into a slag granulation apparatus.
With the hot blast generating device installed according to the invention with preferably only two hot blast apparatus, there is the possibility to configure the blast furnace installation in an even more space-saving and more compact way. In this connection, the installed automation and control device than ensures that, for example, the blast furnace installation can be operated with an annual production of approximately one million tons of hot metal in an optimal and extremely cost-beneficial way.
The construction of a compact blast furnace in connection with a compact burdening, a compact pouring bay (and its compact arrangement in direct vicinity of the blast furnace made possible by the use of the vertical conveyor) provides in this combination a technically totally new blast furnace installation which contributes considerably to the cost reduction of a modern steel making installation to be operated safely.
In particular, the compact blast furnace installation configured accordingly can be used for so-called mini mills. These are mini steel works with an annual capacity of approximately 0.5 to 2 million tons of crude steel. In such mini mills which are operated currently on the basis of direct reduction and/or melting of scrap metal by electric arc furnaces (EAF) and, as a result of their increased flexibility and economic benefits, have gained importance, a compact blast furnace device, as suggested by the invention, could be used advantageously.
Further details, features, and advantages of the invention will be explained in more detail in the following by means of the embodiments schematically illustrated in the drawings.


Machine logic that traces increases (or decreases) in query drift by performing the following steps: retrieving a first response list responding to a first query; retrieving a second response list responding to a second query, wherein the second query is based, at least in part, on a topic related to the first query; determining a set of scores for each of the first response list and the second response list, calculating a normalized query commitment (“NQC”) for each of the first response list and the second response list; and responsive to determining that a ratio representing a relative difference between the NQC for the first response list and the NQC for the second response list is above a predetermined threshold, determining to use the second response list to respond to the first query.

The present invention relates generally to the field of information retrieval, and more particularly to query performance prediction.
Information retrieval (IR) is the activity of obtaining information resources relevant to an information need from a collection of information resources. Searches can be based on metadata or on full-text (or other content-based) indexing. Automated information retrieval systems are used to reduce what has been called "information overload". Many universities and public libraries use IR systems to provide access to books, journals, and other documents. Web search engines are the most visible IR applications.
An information retrieval process begins when a user enters a query into the system. Queries are formal statements of information needs, for example search strings in web search engines. In information retrieval a query does not uniquely identify a single object in the collection. Instead, several objects may match the query, perhaps with different degrees of relevancy. An object is an entity that is represented by information in a database. User queries are matched against the database information. Depending on the application the data objects may be, for example, text documents, images, audio, mind maps, or videos. Often the documents themselves are not kept or stored directly in the IR system, but are instead represented in the system by document surrogates or metadata. Most IR systems compute a numeric score on how well each object in the database matches the query, and rank the objects according to this value. The top ranking objects are then shown to the user. The process may then be iterated if the user wishes to refine the query.

International Business Machines Corporation


The self-retaining vaginal retractor comprises an inverted-U-shaped slotted base plate. A top and pair of cooperating side vagina retracting blades are selectively, removably and adjustably secured to the base plate. Each blade comprises a curved tongue portion and an integral slotted handle portion. The blades are secured by adjustably tensionable fasteners extending through the slots. The blades are adjustable both horizontally and vertically. An optional bag is selectively removably secured to snap fasteners mounted on the base. The bag comprises a top portion and a pair of side portions coinciding with the base. A lower portion extends downward from the side portions defining a pouch to hold the blades and fasteners, and catch debris and fluid. Preferably, the fastener comprises a carriage bolt indexed to a slot in the base, extending through a slot in a blade handle and a wing nut.

1. Field of the Invention
The present invention broadly relates to medical devices and gynecological instruments. Specifically, the present invention is a Self-Retaining Vaginal Retractor used to dilate the vaginal cavity for surgical and examination procedures. Art pertinent to the subject matter of the present invention can be found in various Subclasses of United States Patent Class 600, including Subclasses 220 through 224.
2. Description of the Prior Art
Numerous patents have been issued on surgical and examination instruments. Devices for retracting the vaginal cavity for gynecological procedures include medical or surgical instruments known variously as retractors or speculums.
Perez, U.S. Pat. No. 4,597,382; Beck, U.S. Pat. No. 5,499,964; Dickie, U.S. Pat. No. 5,231,973; Patton, U.S. Pat. No. 5,505,690; and, Lundberg, U.S. Pat. No. 5,318,010 disclose speculums having a xe2x80x9cpistol gripxe2x80x9d configuration. These speculums have xe2x80x9cbillxe2x80x9d shaped blades and once deployed define openings between the blades.
A single bar frame mounting a fixed retractor and a sliding retractor is disclosed in Forder, U.S. Pat. No. 4,344,420. An adjustable, frame mounting a pair of retractors is disclosed in Smith, U.S. Pat. No. 1,706,500. Both of these are specifically intended for use in abdominal surgery. A ring mounted, four blade, Speculum is disclosed in Van Meter, U.S. Pat. No. 497,064. The handles for the speculums extend through slots defined in the ring and the speculums are held in an extended position by a pawl-and-rack arrangement anchored to the ring. Pisarik, U.S. Pat. No. 6,024,697, discloses a three blade speculum having a hinged frame and ratchet mechanism for holding it open. A base mounting a rather complicated retractor opening mechanism is presented in Villalta, U.S. Pat. No. 5,183,032. This device uses a cam and set of arms to deploy four retractor blades. The vaginal dilator disclosed in Holland, U.S. Pat. No. 605,547 employs a base mounted, U-shaped frame to mount three spring-loaded speculum blades. An open-ended frame for a speculum is disclosed in Burgin, U.S. Pat. No. 4,156,424. The width of the frame is adjustable and the height of the speculum blades is adjustable as well.
Grieshaber and Gauthier U.S. Pat. Nos. 2,693,795 and 3,384,077, are retractors, primarily intended for abdominal surgery. Each discloses a blade mounted on a slotted handle. The blades are slidably mounted to the frames through the slots. The vaginal speculum disclosed in Rose, U.S. Pat. No. 3,985,125, is a xe2x80x9cbillxe2x80x9d type, pistol grip speculum which has a pair of slots defined in the sides of one member to allow the blades to be slid apart as well as hinged apart. Similarly, a bill/pistol-grip speculum using slots is disclosed in Jamieson, U.S. Pat. No. 4,323,057. Here the slots are in the back of the speculum handles, once again allowing the blades to be slid apart as well as hinged apart. A pistol grip speculum with sidewall support blades is disclosed in Hoftman, U.S. Pat. No. 6,024,696. A slot in the handle allows the hinged top and fixed bottom blade to be slid apart. Another four-blade speculum is shown in Weiss, U.S. Pat. No. 5,868,668. This is another pistol grip speculum with side blades and a thumb-operated lever.
An adjustable rectangular framed retractor for vaginal surgery is illustrated in Mahmoodian, U.S. Pat. No. 4,924,857. Palmer, U.S. Pat. No. 1,030,530 discloses a two bladed speculum mounted to a slotted frame, which also employs a plate mounted on a threaded rod. The plate is intended to bear on the symphisis pubis to hold the speculum in place. A pair of single blade, slotted frame, bearing plate retractors for vaginal surgery are presented by Richmond, U.S. Pat. No. 3,709,215 and Rizvi, U.S. Pat. No. 6,120,438. The bearing plate in Richmond bears against the suprapubic area of the abdomen, while the plate in Rizvi is positioned under the patient. A three bladed speculum employing a lower blade extending from a slotted frame and two upper/side blades is disclosed in Guttman, U.S. Pat. No. 2,374,863.
Use of retractors having upper and side blades in a single instrument for a hysterectomy is problematic due to the mechanism obstructing the Surgeon""s operating space. Additionally, such devices are cumbersome.
Conventionally, separate upper, side and lower manual retractors are employed for vaginal procedures. A conventional lower retractor is a weighted vaginal speculum, which maintains stretching action through gravity. The conventional upper retractor protects and supports the urethra and urinary bladder and also gives the Surgeon more exposure and operating space.
Heretofore, the upper and side retractors have been L-shaped right angle instruments with a long upwardly extending handle which is held in place manually, although their position is virtually static. Constant force of only a pound or two in an upward, or outward direction is required to maintain retraction. The task of holding the upper retractor is very difficult and tiring because it must be held in place from thirty minutes to over an hour in some cases. Furthermore, when the patient is positioned for vaginal procedures, her thighs and legs are in the way of an Assistant standing on either side of the operating table. On the other hand, if the Assistant holding the upper retractor sits beside the Surgeon it is still difficult because of the crowded conditions resulting from three people sitting and working between the patient""s legs. Assistants must, at intervals, use both hands in aiding the Surgeon. As a result, the task of holding a retractor then temporarily occupies one of the instrument Assistantsxe2x80x2 busy hands.
The prior art fails to disclose a multi-bladed self-retaining vaginal retractor in which each of the blades are independently adjustable both vertically and horizontally. Hence, it is desirous to provide a Self-Retaining Vaginal Retractor which has adjustably mounted blades which can be multi-directionally manipulated to provide a Surgeon relatively free access to the uterus of a patient.
My invention is an improved and simple to use self retaining anterior and side retractor for vaginal procedures and surgery. The present retractor comprises four major parts, which are adjustable in relation to each other to fit the anatomy of the patient. An inverted U-shaped frame, with three slotted openings, which mounts an upper and two side vagina retracting blades using adjustable fasteners.
To use my self-retaining vaginal retractor a patient""s legs are flexed in the lithotomy position for the performance of vaginal surgery/procedures. The slotted, inverted-U-Shaped base plate, fits between the thighs of the patient bearing against the pubic bone area. The blades are angled and are equipped with a slotted opening in the handles, allowing the blades to be placed onto screws extending from the base plate. The blades can then be adjusted and tightened into place with a wing nut or similar fastener.
The retracting blades are generally L-shape with an upturned distal portion. The device operates in the manner of a clamp wherein the downward pressure of the base plate against the exterior surface of the pubic area applies an upward and outward pressure to the respective retracting blades. This clamping action holds the retractor securely in place, leaving Surgical Assistants available at all times for their primary duties of aiding the Surgeon. This will also reduce the number of Assistants required for these procedures.
Therefore, a primary object of the present invention is to provide a self-retaining vaginal retractor which does not obstruct a Surgeon""s operating space.
Another primary object of the present invention is to provide a self-retaining vaginal retractor which simplifies successful dilation of the vaginal cavity for surgical and nonsurgical procedures,
A related object of the present invention is to provide an upper and side blade self-retaining vaginal retractor which is small and easy to use for gynecological procedures.
An object of the present invention is to provide a self-retaining vaginal retractor which will maintain itself in position without being held manually.
An object of the present invention is to provide a self-retaining vaginal retractor which is adjustable to the anatomy of the patient.
An object of the present invention is to provide a self-retaining vaginal retractor which will eliminate the need for assistants whose sole task is to hold retractors.
A related object of the present invention is to provide a self-retaining vaginal retractor which will reduce costs associated with vaginal procedures.
Specifically, an object of the present invention is to provide a self-retaining vaginal retractor which will reduce cost by reducing the number of assistants required for vaginal procedures.
An object of the present invention is to provide a self-retaining vaginal retractor which can be adjusted during a procedure.
An object of the present invention is to provide an upper and side blade self-retaining vaginal retractor which allows independent vertical and horizontal adjustment of each retracting blade.
These and other objects and advantages of the present invention, along with features of novelty appurtenant thereto, will appear or become apparent in the course of the following descriptive sections.


Particulate bleach activators comprising 15 to 60% by weight of an acetonitrile, 20 to 70% by weight of a silicon-containing carrier material and 20 to 30% by weight of water, which are obtained by applying an aqueous solution, saturated at 10 to 40xc2x0 C., of an acetonitrile onto the carrier material without subsequent drying, where the amount of saturated aqueous solution is measured such that the given limits for acetonitrile, carrier material and water are observed.

The present invention relates to particulate bleach activators based on acetonitriles, to a process for their preparation which consists in applying acetonitriles to silicon-containing carrier materials, and to the use of these products as bleach activators in solid laundry detergents and cleaning compositions.
Bleach activators are important constituents in compact detergents, stain-removal salts and machine dishwashing detergents. At temperatures as low as 40 to 60xc2x0 C., they permit a bleaching result comparable with that of a boil wash by reacting with hydrogen peroxide-donors (in most cases perborates, percarbonates, persilicates and perphosphates) to release peroxy acids.
Many substances are known as bleach activators in the prior art. They are usually reactive organic compounds with an O-acyl or N-acyl group which, in alkaline solution together with a source of hydrogen peroxide, form the corresponding peroxy acids.
Representative examples of bleach activators are N,N,Nxe2x80x2,Nxe2x80x2-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), sodium trimethylhexanoyloxybenzenesulfonate (STHOBS), tetraacetylglucoluril (TAGU), tetraacetylcyanic acid (TACA), di-N-acetyidimethylglyoxine (ADMG) and 1-phenyl-3-acetylhydantoin (PAH).
Ammonium nitrites form a particular class of cationic bleach activators. Compounds of this type and the use thereof as bleach activators in bleaches are described in EP-A-0 303 520, EP-A-0 464 880, EP-A-0 458 396, EP-A-0 897 974 and EP-A-0 790 244.
For the use of the ammonium nitrites as bleach activator in laundry detergents and cleaning compositions, the hygroscopicity of the ammonium nitrites and the sensitivity to hydrolysis in the presence of alkaline laundry detergent constituents and a correspondingly low storage stability associated therewith are highly disadvantageous.
WO 98/23531 and WO 00/36061 describe that acetonitrile derivatives, in particular cyclic acetonitrile compounds, are converted into a solid form for incorporation into solid laundry detergents and cleaning compositions by stirring a carrier material having the largest possible surface area, for example silica, into an aqueous acetonitrile solution, or by spraying the aqueous solution onto the carrier, and subjecting the resulting mixture to drying under reduced pressure at elevated temperatures. The granules or particles described in these specifications have water contents of up to 20% by weight, preferably less than 1 percent by weight. An unsatisfactory aspect is the hygroscopicity and, consequently, the storage stability of the products, in particular of the linear acetonitrile derivatives at fluctuating atmospheric humidity, and the partial decomposition of the hydrolysis-sensitive acetonitrile compounds during the thermal drying process.
Surprisingly, it has been found that formulating in the form of granules or particles of the acetonitrile derivatives can be carried out in a manner which is very gentle to the active ingredient, but is also very advantageous with regard to costs and environment, by spraying aqueous solutions, saturated at room temperature, of acetonitrile derivatives onto a silicon-containing carrier material, in particular silica, without subsequent drying. This gives solid products with a water content of from 20 to 30% by weight. A drying process, which is energy-intensive and unfavorable for the active ingredient, can be dispensed with. The active ingredient concentration of the products prepared by the process according to the invention is greater than that of conventional products, and the hygroscopicity of the acetonitrile derivatives formulated in accordance with the invention is significantly lower.
The invention provides particulate bleach activators comprising 15 to 60% by weight, preferably 20 to 50% by weight, in particular 35 to 45% by weight, of an acetonitrile, 20 to 70% by weight, preferably 30 to 50% by weight, in particular 35 to 45% by weight, of a silicon-containing carrier matieral, and 20 to 30% by weight, preferably 22 to 25% by weight, of water.
Such acetonitriles are compounds of the formula
in which R1, R2, R3 are identical or different and are linear or branched C1-C24-alkyl groups, C2-C24-alkenyl groups or are C1-C4-alkoxy-C1-C4-alkyl groups, substituted or unsubstituted benzyl, or in which R1 and R2, together with the nitrogen atom to which they are bonded, form a ring having 4 to 6 carbon atoms which may be substituted by C1-C5-alkyl, C1-C5-alkoxy, C1- to C5-alkanoyl, phenyl, amino, ammonium, cyano, cyanamino, chlorine or bromine, and, in addition to the nitrogen atom, may contain one or two oxygen or nitrogen atoms, a group Nxe2x80x94R6 or a group R3xe2x80x94Nxe2x80x94R6 instead of carbon atoms, in which R6 is hydrogen, C1- to C5-alkyl, C2- to C5-alkenyl, C2- to C5-alkynyl, phenyl, C7- to C9-aralkyl, C5- to C7-cycloalkyl, C1- to C6-alkanoyl, cyanomethyl or cyano, R4 and R5 are hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl or C1-C3-alkylphenyl, preferably hydrogen, methyl or phenyl, where, in particular, R4 is hydrogen if R5 is not hydrogen, and A is any desired anion, for example chloride, bromide, iodide, fluoride, sulfate, hydrogensulfate, carbonate, hydrogencarbonate, phosphate, mono- and di-hydrogenphosphate, pyrophosphate, metaphosphate, nitrate, methylsulfate, phosphonate, methylphosphonate, methanedisulfonate, methylsulfonate, ethanesulfonate or is an anion of the formulae RSO3xe2x8ax96, R1SO4xe2x8ax96 or R2COOxe2x8ax96, where R, R1 and R2 are C8-C20-alkyl, preferably C10-C18-alkyl, and R1 is additionally also substituted aryl, preferably C1-C18-alkylphenyl. Particular preference is given to cumenesulfonate and C12/18-alcohol sulfate as anion.
Particular preference is given to compounds of the above formula in which R1, R2 and R3 are C1-C4-alkyl, and R4 and R5 are hydrogen, and A is any desired cation, preferably chloride, methosulfate, cumenesulfonate, lauryl sulfate or fatty acid alkyl carboxylates or mixtures of these cations.
The synthesis of these acetonitriles can be carried out by known processes, as published, for example, by Abraham in Progr. Phys. Org. Chem. 11 (1974), p. 1 ff, or by Arnett in J. Am Chem. Soc. 102 (1980), p. 5892 ff.
These acetonitriles are used to prepare a saturated aqueous solution which is applied to the silicon-containing carrier material, preferably by spraying, for example via a two-material nozzle. The temperature of this saturated aqueous solution is preferably 10 to 40xc2x0 C., particularly preferably 20 to 25xc2x0 C. The material can then be after-mixed. The amount of saturated aqueous solution is measured such that the limits given above for acetonitrile, carrier material and water are observed.
Preferred silicon-containing carrier materials are preferably those whose internal surface area is in the range from 10 m2/g to 500 m2/g, in particular 100 m2/g to 450 m2/g. Examples of suitable materials are silicates, silicas, silica gels and clays, and mixtures thereof. The carrier material is preferably free from strongly alkaline constituents.
Silicas which have been prepared by the thermal process (flame hydrolysis of SiCl4) (so-called pyrogenic silicas) can be used as well as silicas prepared by wet processes. Silica gels are colloidal silicas with elastic to solid consistency and a largely loose pore structure, resulting in a high liquid absorption capacity. They can be prepared by reacting mineral acids on water glass. Clays are naturally occurring crystalline or amorphous silicates of aluminum, iron, magnesium, calcium, potassium and sodium, for example kaolin, talc, pyrophyllite, aftapulgite, sepiolite, montmorillonite and bauxite. The use of aluminum silicate as carrier material or as component of a carrier material mixture is also possible. The carrier material preferably has particle sizes in the range from 10 xcexcm to 1.5 mm.
In order to ensure sufficient storage stability and to liberate the bleach-activating action only during the wash operation, it is advantageous to then granulate the carrier material loaded with the acetonitrile. The carrier material loaded with the acetonitrile can, with or without the addition of a binder, likewise be compressed, compacted and be gently comminuted to granule sizes of from 200 to 2000 xcexcm.
Also suitable is a build-up granulation in a mixer, for example in a plowshare mixer, annular bed mixer or intensive mixer with or without the addition of a binder, for example a water-based binder, such as Tylose(trademark) (carboxymethylcellulose) or an anhydrous binder system, such as fatty alcohol polyglycol ether.
In a further embodiment, the particulate product obtained by spraying a saturated solution of the acetonitrile onto a carrier material can, with or without the addition of a binder, be subjected to a shaping granulation through dies in an extruder, or else in annular edge-runner presses, edge runners, optionally with downstream rounding equipment.
The particulate bleach activators obtained according to the invention are suitable for direct use in laundry detergents and cleaning compositions. In order to avoid fabric and color damage, it is advantageous, however, to provide the particulate bleach activators with a coating in accordance with processes known in the art. For this purpose, the granules are coated in an additional step with a film-forming substance by methods known in the art, as a result of which the product properties can be considerably influenced. Suitable coating materials are all film-forming substances, such as waxes, silicones, fatty acids, soaps, anionic surfactants, nonionic surfactants, cationic surfactants, and anionic and cationic polymers, e.g. polyacrylic acids. By using these coating materials, it is possible, inter alia, to delay the dissolution behavior in order, in this way, to also suppress interaction between the bleach activator and the enzyme system at the start of the washing process. If the granules are to be used in machine dishwashing detergents, waxes with melting points of from 40 to 50xc2x0 C. are particularly suitable for this purpose.
Preference is given to using coating substances with a melting point of from 30 to 100xc2x0 C. Examples thereof and an application process are described in EP-A-0 835 926. The coating materials are usually applied by spraying the molten coating materials or coating materials dissolved in a solvent. The coating material can be applied in amounts of from 0 to 30% by weight, preferably 5 to 20% by weight, based on the total weight, onto the granule core according to the invention.
Moreover, the particulate bleach activators according to the invention can also comprise further suitable additives, such as anionic and nonionic surfactants, which contribute to more rapid dissolution of the granules according to the invention. Preferred anionic surfactants are alkali metal salts, ammonium salts, amine salts and salts of aminoalcohols from the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamide sulfates and alkylamide ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, xcex1-olefinsulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, alkylpolyglycerol carboxylates, alkyl phosphates, alkyl ether phosphates, alkyl sarcosinates, alkyl polypeptidates, alkylamidopolypeptidates, alkyl isethionates, alkyl taurates, alkylpolyglycol ether carboxylic acids or fatty acids, such as oleic acid, ricinoleic acid, palmitic acid, stearic acid, copra oil acid salts or hydrogenated copra oil acid salts. The alkyl radical of all of these compounds normally contains 8 to 32, preferably 8 to 22, carbon atoms.
Preferred nonionic surfactants are polyethoxylated, polypropoxylated or polyglycerolated ethers of fatty alcohols, polyethoxylated, polypropoxylated and polyglycerolated fatty acid esters, polyethoxylated esters of fatty acids and of sorbitol, polyethoxylated or polyglycerolated fatty amides.
Suitable additives are also substances which influence the pH during storage and use. These include organic carboxylic acids or salts thereof, such as citric acid in anhydrous or hydrated form, glycolic acid, succinic acid, maleic acid or lactic acid. In addition, additives are possible which influence the bleaching ability, such as complexing agents and transition metal complexes, e.g. iron-, cobalt- or manganese-containing metal complexes, as described in EP-A-0 458 397 and EP-A-0 458 398.
Further possible additives are substances which, in the wash liquor, react with the peroxycarboxylic acid liberated by the activator to form reactive intermediates, such as dioxiranes or oxaziridines, and in this way can increase the reactivity. Corresponding compounds are ketones and sulfonimines corresponding to U.S. Pat. No. 3,822,114 and EP-A-0 446 982.
The amount of the additive depends, in particular, on its nature. For example, acidifying additives and organic catalysts for increasing the performance of the peracid are added in amounts of from 0 to 20% by weight, in particular in amounts of from 1 to 10% by weight, based on the total weight, whereas metal complexes are added in concentrations in the ppm range.
In a further preferred embodiment, the particulate bleach activators according to the invention can be incorporated into tableted laundry detergent and cleaning composition formulations in accordance with customary methods. To prepare cleaning compositions in tablet form, the procedure preferably involves mixing all of the constituents in a mixer and compressing the mixture by means of customary tableting presses, for example eccentric presses or rotary presses, using pressing forces in the range from 200xc3x97105 Pa to 1500xc3x97105 Pa. This gives, without problems, tablets which are resistant to breakage but which nevertheless dissolve sufficiently rapidly under application conditions and which have flexural strengths of more than 150 N. A tablet prepared in this way preferably has a weight of from 15 g to 40 g, in particular from 20 g to 30 g, for a diameter of from 35 mm to 40 mm.
The acetonitrile derivatives formulated according to the invention can be used in heavy-duty detergents, stain-removal salts, machine dishwashing detergents, pulverulent all-purpose cleaners and denture cleansers.
The laundry detergents and cleaning compositions comprising the above-described acetonitrile derivatives formulated in the form of particles are used in combination with a source of hydrogen peroxide, for example perborate monohydrate, perborate tetrahydrate, percarbonate, and hydrogen peroxide adducts with urea or amine oxides, and can comprise all ingredients customary in these compositions such as builder substances, surfactants, enzymes, sequestering agents, electrolytes, pH regulators, foam regulators, abrasives, brighteners, silver corrosion inhibitors, preservatives, perfumes and fragrances.
Suitable builders are phosphate-free builder systems and also phosphate-containing systems, for example alkali metal phosphates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts, such as trisodium phosphate, tetrasodium diphosphate, disodium dihydrogenphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with oligomerization amounts in the range from 5 to 1000, in particular 5 to 50, and mixtures of sodium and potassium salts. Finely crystalline synthetic water-containing zeolites of the NaA type which have a calcium-binding capacity in the range from 100 to 200 mg of CaO/g are preferably used. These zeolites can be present in an amount up to 20% by weight in the composition. Builders which can be used are also the percarboxylic acids used preferably in the form of their sodium salts, such as citric acid and nitriloacetate (NTA), ethylenediaminetetraacetic acid. Analogously thereto, it is also possible to use polymeric carboxylates and salts thereof. These include, for example, the salts of homopolymeric or copolymeric polyacrylates, polymethacrylates and, in particular, copolymers of acrylic acid with maleic acid, and also polyvinylpyrrolidone and urethanes. The relative molecular mass of the homopolymers is generally between 1000 and 100000, that of the copolymers is between 2000 and 200000, preferably 50000 to 120000, based on the free acid. In particular, water-soluble polyacrylates are also suitable which have been crosslinked, for example, with approximately 1% of a polyallyl ether of sucrose and which have a relative molecular mass above one million. Examples thereof are the polymers obtainable under the name Carbopol(copyright) 940 and 941. The crosslinked polyacrylates are used in amounts not exceeding 1% by weight, preferably in amounts of from 0.2 to 0.7% by weight. These backbone substances can be used in amounts up to 5% by weight. Preferred anionic surfactants are C8-C20-fatty acid xcex1-methyl ester sulfonates, alkyl sulfates, alkyl ether sulfates and sec-alkanesulfonates.
The alkyl ether sulfates used in the compositions according to the invention are water-soluble salts or acids of the formula RO(A)mSO3M, in which R is an unsubstituted C10-C24-alkyl or C10-C24-hydroxyalkyl radical, preferably a C12-C20-alkyl or C12-C20-hydroxyalkyl radical, particularly preferably C12-C18-alkyl or C12-C18-hydroxyalkyl radical. xe2x80x9cAxe2x80x9d is an ethoxy or propoxy unit, m is a number greater than 0, preferably between 0.5 and about 6, particularly preferably between about 0.5 and about 3 and M is a hydrogen atom or a cation, such as, for example, a metal cation (e.g. sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a substituted ammonium cation. Specific examples of substituted ammonium cations are methylammonium, dimethylammonium, trimethylammonium and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations, and those which are derived from alkylamines, such as ethylamine, diethylamine, triethylamine. Examples of these alkyl ether sulfates which may be mentioned are C12-C18-alkyl polyethoxylate(1.0) sulfate, (C12-C18E(1.0)M), C12-C18-alkyl polyethoxylate(2.25) sulfate (C12-C18E(2,25)M), C12-C18-alkyl polyethoxylate(3.0) sulfate (C12-C18E(3,0)M), C12-C18-alkyl polyethoxylate(4.0) sulfate (C12-C18E(4.0)M).
In the case of the secondary alkanesulfonates, the alkyl group can either be saturated or unsaturated, branched or linear and optionally substituted by a hydroxyl group. The sulfo group is randomly distributed over the entire carbon chain, where the primary methyl groups on the start of the chain and on the end of the chain do not have sulfonate groups. Preferred secondary alkanesulfonates contain linear alkyl chains having 9 to 25 carbon atoms, preferably from 10 to 20 carbon atoms and particularly preferably 13 to 17 carbon atoms. The cation is sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. For the sake of simplicity, sodium is preferred as cation.
In addition to or instead of these preferred anionic surfactants, the laundry detergents and cleaning compositions can also comprise other types of anionic surfactants, such as, for example, alkyl sulfates, alkylsulfonates, alkyl carboxylates, alkyl phosphates and mixtures of said compounds. Suitable cations are, for example, sodium, potassium, calcium or magnesium, and ammonium, substituted ammonium compounds, including mono-, di- or triethanolammonium cations, and mixtures of these cations.
Here, alkyl sulfates are water-soluble salts or acids of the formula ROSO3M, in which R is preferably a C10-C24-hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical having C10-C20-alkyl components, particularly preferably a C12-C18-alkyl or hydroxyalkyl radical. M is hydrogen or a cation, e.g. sodium, potassium, lithium or ammonium or substituted ammonium, e.g. methyl-, dimethyl- and trimethylammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines, such as ethylamine, diethylamine, triethylamine and mixtures thereof.
A further suitable anionic surfactant is alkylbenzenesulfonate. The alkyl group can either be saturated or unsaturated, branched or linear and optionally substituted by a hydroxyl group.
The preferred alkylbenzenesulfonates contain linear alkyl chains having 9 to 25 carbon atoms, preferably 10 to 13 carbon atoms, and the cation is sodium, potassium, ammonium, mono-, di- or triethylammonium, calcium or magnesium and mixtures thereof.
Further suitable anionic surfactants are carboxylates, e.g. fatty acid soaps and comparable surfactants. The soaps can be saturated or unsaturated and can contain various substituents, such as hydroxyl groups or alpha-sulfonate groups. Preference is given to linear saturated or unsaturated hydrocarbon radicals as hydrophobic component in the soaps. The hydrophobic components usually contain 6 to 30 carbon atoms, preferably 10 to 18 carbon atoms. Further anionic surfactants are salts of acylaminocarboxylic acids, which are formed by reacting fatty acid chlorides with sodium sarcosinate in alkaline medium (acyl sarcosinates), and also fatty acid protein condensation products which are obtained by reacting fatty acid chlorides with oligopeptides. The salts of alkylsulfamidocarboxylic acids and the salts of alkyl and alkylaryl ether carboxylic acids also have surfactant character.
Other anionic surfactants which are useful for use in laundry detergents and cleaning compositions are C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonating the pyrolysis products of alkaline earth metal citrates, as described, for example, in GB 1 082 179, alkylglycerol sulfates, fatty acyl glycerol sulfates, oleylglycerol sulfates, alkylphenol ether sulfates, primary paraffinsulfonates, alkyl phosphates, alkyl ether phosphates, isethionates, such as acyl isethionates, N-acyltaurides, alkyl succinamates, sulfosuccinates, monoesters of sulfosuccinates (particularly saturated and unsaturated C12-C18-monoesters) and diesters of sulfosuccinates (particularly saturated and unsaturated C12-C18-diesters), acylsarcosinates, sulfates of alkyl polysaccharides, such as sulfates of alkyl glycosides, branched primary alkylsulfates and alkyl polyethoxycarboxylates, such as those of the formula RO(CH2CH2)kCH2COOM, in which R is C8-C22-alkyl, k is a number from 0 to 10 and M is a cation which forms a soluble salt. Resin acids or hydrogenated resin acids, such as rosin or hydrogenated rosin or tall oil resins and tall oil resin acids can likewise be used. Further examples are described in xe2x80x9cSurface Active Agents and Detergentsxe2x80x9d (Vol. I and II, Schwartz, Perry and Berch). A large number of such surfactants are also described in U.S. Pat. No. 3,929,678.
Typical examples of anionic surfactants are also alkyl ether sulfonates, glycerol ether sulfonates, sulfo fatty acids, glycerol ether sulfates, hydroxy mixed ether sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, alkyl oligoglucoside sulfates, alkylamino sugar sulfates and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional or a narrowed homolog distribution.
In the laundry detergent and cleaning compositions it is likewise possible to use nonionic surfactants, such as fatty acid alkyl ester alkoxylates, alkyl and/or alkenyl oligoglycosides, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, fatty acid glucamides, polyoil fatty acid esters, sugar esters, sorbitan esters and polysorbates and/or alkoxylated fatty alcohols.
Furthermore, cosurfactants from the group of alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazoliniumbetaines and sulfobetaines, amine oxides and fatty acid alkanolamides or polyhydroxyamides, can be used.
In addition to the bleach-activating acetonitrile derivatives, it is possible to use known conventional bleach activators, i.e. compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids and/or optionally substituted perbenzoic acids.
Suitable substances are organic compounds with a O-acyl or N-acyl group, in particular from the group of activated carboxylates, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxybenzenesulfonate, sodium 4-benzoyloxy-benzenesulfonate, sodium trimethylhexanoyloxybenzenesulfonate, carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, lactones, acylates, carboxamides, acyllactams, acylated ureas and oxamides, N-acylated hydantoins, for example 1-phenyl-3-acetylhydantoin, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazides, sulfurylamides, polyacylated alkylenediamines, for example N,N,Nxe2x80x2,Nxe2x80x2-tetraacetylethylenediamine, acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylimides, in particular N-nonanoylsuccinimide, and acylated sugar derivatives, in particular pentaacetylglucose, pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and acylated, optionally N-alkylated glucamine and gluconolactone and/or N-acylated lactams, for example N-benzoylcaprolactam.
In addition to the abovementioned conventional bleach activators, or instead of them, it is also possible for sulfonimines and/or bleach-boosting transition metal salts or transition metal complexes to be present as so-called bleach catalysts, as described in DE 196 49 375.
Suitable enzymes are those from the class of proteases, such as BLAP, Optimase, Opticlean, Maxacal, Maxapem, Esperase, Savinase, Purifect OxP and/or Durazym, lipases, such as Lipolase, Lipomax, Lumafast and/or Lipozym, amylases, such as Termamyl, Ainylase-LT, Maxamyl, Duramyl and/or Purafect OxAm, and cutinases, pullulanases and mixtures thereof. Their proportion can be from 0.2 to 1% by weight. The enzymes can be adsorbed to carrier substances and/or embedded in coating substances.
Possible silver corrosion inhibitors are the compounds given in DE 196 49 375.
As foam regulators, it is possible to add, preferably, up to 6% by weight, in particular about 0.5 to 4% by weight, of foam-suppressing compounds, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffins, paraffin/alcohol combinations, hydrophobicized silica, bis-fatty acid amides and other known commercially available antifoams.
To set a desired pH, the compositions according to the invention can comprise system- and environmentally-compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipic acid, or else mineral acids, in particular sulfuric acid or alkali metal hydrogensulfates or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are present in the compositions according to the invention in amounts which, preferably, do not exceed 10% by weight, in particular in amounts of from 0.5 to 6% by weight.
Examples of suitable preservatives are phenoxyethanol, formaldehyde solution, pentanediol or sorbic acid. Abrasive substances which can be used are quartz flours, wood flours, plastics flours, chalk and microglass spheres.
Typical individual examples of further additives are sodium borate, starch, sucrose, polydextrose, stilbene compounds, methylcellulose, toluenesulfonate, cumenesulfonate, soaps and silicones.
The preparation of the compositions according to the invention in the form of non-dusting, storage-stable flowable powders and/or granules with high bulk densities in the range from 800 to 1000 g/l can be carried out by, in a first process stage, mixing the builder components with at least a fraction of liquid mixture components, with an increase in the bulk density of this premix, and subsequentlyxe2x80x94if desired after an intermediate dryingxe2x80x94combining the further constituents of the composition, including the bleach activator, with the premix obtained in this way.

Particulate bleach activators based on acetonitriles