A hydraulically operated setting tool for use in setting a plug or other component in a wellbore, and which is responsive to a supply of input actuating pressure to actuate the tool. An elongate tool housing has an inlet to receive the supply of actuating pressure, and an actuator element is axially displaceable relative to housing and also engageable with the plug or other component to set and release the component with respect to the wellbore. A pressure multiplier arrangement includes a hydraulically operated low pressure and high volume output piston which performs initial loading of the tool, and a high pressure, low volume output piston which provides a multiplied hydraulic force applied to the actuator element to set the plug or other component in a required position in the wellbore.

In the petrochemical industries, there are many occasions when repair to a well is required or when flow should be closed off. This is accomplished by use of a device called a plug. This device seals pressure from above and below and normally features a rubber or similar packing element arranged around the outside of the plug, a "slip" mechanism to engage and lock the plug with the metal tubulars of the wellbore and a body to join the elements together. This plug becomes a pressure barrier and allows work to be safely carried out above with no possibility of well fluids escaping. Pressure retaining capability may be as much as 10,000 psi and it may operate in temperatures of 300 deg F. or higher.
Many types of plug exist available in a complete range of sizes and from a multitude of manufacturers. The plugs may be conveyed to the required setting depth in the wellbore on pipe but more commonly on a wireline. When positioned at the required depth, the plug must be set, normally requiring locating pins to be sheared with a moderate force, the slips to be energised, again with a moderate force and the rubber element to be expanded again with moderate force. During this stage of setting, the forces required are only a few thousand pounds but the stroke may be quite long (7 inches or more). Finally, large forces of 20 thousand pounds or more are required (over a short stroke of 1.0″ or less) to fully energise the rubber packing element, to force the slips into a biting engagement with the tubing wall and to disconnect the hydraulic power device from the plug.
The generic name for the running tool which provides the large setting forces required is a "setting tool". There are two industry standard setting tools, namely the Baker E4 setting tool and the Halliburton (or GRC as formally known) "Shorty". Both these tools operate using the same method. The method is to create and contain a high pressure gas by igniting a pyrotechnic charge in a closed chamber. The pyrotechnic or "black powder" charge is initiated by application of an electrical current typically of around 20 volts. This is most usually supplied from surface down an electric wireline cable but may also be supplied from batteries used in conjunction with a pre-programmed clock or other memory device which switches the power to the charge. The chamber which contains the high pressure gas features a floating hydraulic piston with an oil filled chamber below splitting the chamber into two sections. The hydraulic oil is pressured by the gas and provides hydraulic power which when diverted to a secondary piston, performs the setting task as described previously. The power generated by the setting tool is available over the entire stroke of the setting tool, the device automatically adjusting to different stroke requirements.
The setting tool is connected to the plug by a "shear stud", normally a threaded rod with a waisted middle to provide a weak point. The shear stud may be rated to as much as 50,000 lbs. Use of the shear stud guarantees the required amount of force has been imparted to the plug below. Following setting, one half of the shear stud will be returned with the setting tool, and the other will remain with the plug.
Following setting, the setting tool will retain the gas pressure until this is relieved. This normally entails opening a valve following recovery on surface. The high pressure gas is vented to atmosphere under controlled conditions. Not only is the handling of a highly pressurised gas containing vessel dangerous, but the venting of the gas is a hazardous operation and must be conducted under strictly controlled conditions.
Many rules and regulations exist regarding the shipping and handling of pyrotechnics as they are part of the family of explosives. Trained personnel are required at every stage and there are many limitations on the use of pyrotechnics, especially regarding air freight. Safety provisions must be made such as storage in licensed premises and many third parties must be involved including notification of the Harbour Master when shipping by sea, regular inspections both by the Fire Brigade, local authority (for licensing requirements) and the Police for security issues. The gas chambers of setting tools must undergo regular N.D.T. inspections for cracks and other damage due to their onerous use.
Obviously, as can be seen from the above, the use of pyrotechnics is to be avoided if at all possible, but there are only limited alternatives at present. One method is to use a "Hydrostatic Setting Tool". This type of tool converts the ambient hydrostatic pressure in a wellbore into an hydraulic force to set the plug. The tool is equipped with a series of pistons which each have atmospheric pressure on both sides of the piston. They are modified pyrotechnic setting tools and retain the hydraulic lower section replacing the gas section with the pistons. When a valve is opened (either by a signal from surface or by a timer device) well pressure is allowed to act upon one side of the pistons causing an imbalance similar to the hydrostatic ambient pressure. As bottom hole well pressures are commonly in the range of 2,000 to 8,000 psi, a straight 1 to 1 ratio will not produce sufficient hydraulic power to set a plug. The pistons must therefore incorporate a pressure multiplier to generate the high pressures needed. Typically a 1 to 5 multiplier may be required. This means therefore that for the volume of hydraulic oil required for the stroke to set the tool, at least 5 times that volume (or stroke) in the well pressure chamber must be present. A contingency of around 50% of the stroke is also required in order that the setting pistons do not bottom out without releasing the shear stud and disconnecting from the plug. This tool is very cumbersome and unwieldy due to its extreme length and its performance is only marginal in certain circumstances. Limited space is available to introduce tools into a wellbore and extreme lengths preclude some tools from operational use. Without increasing the pressure multiplier ratio to perhaps 10 to 1 and increasing the length accordingly, this device has very limited application and is seldom used.
It is an object of the invention, to provide a pressure activated setting tool which can offer all the benefits of a non pyrotechnic setting tool but with the performance, output and short length of the explosive type.
According to the invention there is provided a hydraulically operated setting tool as defined in claim 1.
Preferred aspects of the invention are set out in dependent claims 2 to 11.
As has been stated earlier, the output from a pyrotechnic setting tool is a high pressure gas charge with the high pressure available over the entire stroke. This is due to the compressibility of gas, but is inefficient as around ⅘ of the stroke is used to "take up the slack" in the setting tool and the bridge plug. This includes shearing light retaining pins, expanding elastomers and stroking mandrels to close up gaps. Only a few thousand pounds force is required for this.
Once all the slack has gone and the major movement has finished, high forces are required to energise the slips with the tubing wall, energise the packing element the final portion and to shear the release shear stud. The setting process requires two distinct hydraulic operations, each with different properties. Firstly a long stroke low pressure operation followed by a short stroke high pressure operation.
In response to well pressure entering the top of the tool, (shown in FIG. 1b) the LP piston combined with the HP piston both displace hydraulic oil into an outer sleeve type piston forcing it downwards and causing an attached plug to compress. The centre portion of the plug (not shown) is retained at this time by a shear stud 16 which is shown at the bottom of the illustration with the outer setting tool hydraulic sleeve pressing downwards. The L.P. section of the tool has a ratio of 1 to 2, doubling the available well pressure until such time as all movement has been accomplished with this pressure. The shear connection linking the LP and HP pistons will now shear allowing the HP piston to exert increased loads on the plug. The ratchet arrangement prevents the hydraulic pressure from returning the LP piston back to its starting point and isolates the LP piston from the system. The HP piston has a ratio of 1 to 10 increasing well pressure 10 times. This will now produce the last part of the stroke required to fully set the plug and release the shear stud.
A plug adapter 15, shown in FIG. 1c carries the shear stud 16 (which attaches the plug to the tool), and is secured to the lower end of the tool 14.
By use of this method, hydraulic forces well in excess of 50,000 lbs are available to set a variety of plugs without use of pyrotechnics. The device will self compensate for different plug types and will automatically change over from LP to HP operation once the required "slack" has been removed from the system.
The construction of the tool will now be described in detail, with reference to FIGS. 1a, b and c of the drawing.
The hydraulically operated setting tool is designated generally by reference 14, and is intended to be used in setting a plug or other component in a wellbore, and being responsive to a supply of input actuating pressure to actuate the tool. Any suitable one of the connector modules 10, 11 and 12, shown in FIG. 1a, may be used in order to complete the assembly of the tool, ready to be raised and lowered to a required position along the length of the wellbore, via suitable flexible connection to the surface. The module 10 may be used to connect the tool to an electric wireline, whereas the module 11 can be used to connect the tool to a slickline. The module 12 may be used to provide an hydraulic connection to surface, in shallow drilling depths, when a remote input actuating pressure is used in order to actuate the tool. However, in the case of the modules 10 and 11, it will be wellbore ambient pressure which will be used in order to actuate the tool.
The plug adapter 15 is detachably connected to a lower end of the tool 14, and carries shear stud 16 which is the means employed in order to attach a plug (not shown), or other component which is to be set in position in the wellbore.
The tool 14 has an external elongate housing designated generally by reference 17, and which is movable lengthwise during lowering and raising of the tool 14 in the wellbore. Housing 17 has an inlet 18 to receive the supply of actuating pressure which, as mentioned above, may be wellbore pressure, or an external supply of actuating pressure from the surface.
An actuator element is axially displaceably mounted on the housing 17, and the illustrated arrangement comprises an outer hydraulic setting sleeve 19. Sleeve 19 is engageable with the plug or other component, to set and release the component with respect to the wellbore, upon axial displacement of the sleeve 19.
A pressure multiplier arrangement is provided in the housing 17, and comprises a detachable connection together of a low pressure piston 20 and a high pressure piston 21. In the illustrated example, a detachable connection between pistons 20 and 21 takes the form of shear pins 22. However, it should be understood that other means may be utilised in order to provide a detachable connection between pistons 20 and 21, upon application of a predetermined load therebetween.
The void outside the low pressure and high pressure pistons is oil filled via oil fill port 23 (forming a closed chamber).
The pressure multiplier arrangement disclosed is therefore operative, upon supply of actuating pressure to the housing 17 via inlet 18, to provide a low pressure and high volume output to perform the initial loading of the tool 14, and a high pressure, low volume output to provide a multiplied hydraulic force applied to the actuator element (outer hydraulic setting sleeve 19) to set the plug or other component in a required position in the wellbore.
The low pressure piston 20 and the high pressure piston 21 are connected together by a detachable connection, as mentioned above, and which yields under a predetermined load in order to allow the high pressure piston 21 to apply the multiplied hydraulic force to the actuator element.
A ratchet arrangement 26 is mounted in the housing 17, and it has the function of preventing return movement of the low pressure piston 20 after yielding of the connection.
As shown in FIG. 1b, the low pressure piston 20 is an annular piston, and the high pressure piston 21 is a rod like piston.
The disclosed embodiment of hydraulically operated setting tool according to the invention can therefore be used to set a plug or other component in a wellbore, and has the advantage of providing the benefits of using a non-pyrotechnic setting tool i.e. avoiding the dangers and inconveniences of using an explosive tool, but having the performance, output and short length associated with use of explosive type setting tools. The hydraulic operation of the tool, upon actuation by supply of input actuating pressure, utilizes two hydraulic chambers, in which one chamber will always be at atmospheric pressure, whereas the other one will be at atmospheric pressure until the tool is operated, and will then be exposed to high pressure from both the low pressure piston 20 and the high pressure piston 21. The plug (not shown) is attached by the shear stud 16, and the two assemblies, housing 17 and adapter 15, are threaded together. The outer "setting sleeve" (19) butts on the outside of the plug, and effectively pushes the plug down, while the shear stud 16 remains anchored to the internal components of the plug, during "setting" of the plug.
Once the plug is fully set, the shear stud 16 will separate (under load of 30,000 lbs or more), and this detaches the plug from the setting tool.
The design of the plug adaptor 15 is not critical, but will be designed according to the particular proprietary type of plug which is utilised.
To conclude, the hydrostatically operated setting tool disclosed herein addresses an industry requirement for a non-pyrotechnic setting device for downhole use. The setting tool converts the hydrostatic pressure at the tool into an axial force. The short overall length of the tool can be achieved by incorporating a high volume low-pressure piston and a low volume high-pressure piston into the setting tool. This hydraulically operated pressure multiplier arrangement, combined with a unique regulating device within the tool, allows the hydrostatic well pressure to be boosted within the tool, providing a force of about 29,000 lbs for each 1,000 psi well pressure. The setting tool has been designed to run on slickline, and also electric line, but can also be adapted for coil tubing and pipe applications. The setting tool can be quickly converted from slickline to electric line deployment on a rig site, by replacing two components at the top of the tool.
When run on slickline, a timer is used, which features an external switch allowing the timer to be started just before the tool string is picked up. A timer disconnect feature is also provided, in the event that the tool string hangs up R.I.H. This feature can be enabled or disabled as required.
In the event of insufficient hydrostatic pressure being available e.g. during low level drilling, a pressure module may be run on top of the setting tool to provide sufficient input pressure. This would only be required if it were not possible to apply pressure from surface.
The hydrostatic setting tool is ideally suited to tree change out operations, where pressure may be applied against a deep-set plug.
The setting tool provides a highly cost effective alternative to existing use of pyrotechnic setting tools. In the case of slickline operation, the slickline timer is powered by two AA cell lithium batteries, which do not require dangerous goods certification for transportation. This feature, combined with the short overall length of the tool, makes it ideal for transportation by helicopter.
The illustrated embodiment provides a detachable connection between the low pressure piston and the high pressure piston, and taking the form of a shear pin. However, it is within the scope of the invention to provide a hydraulic connection between the low pressure piston and the high pressure piston, and which couples these pistons together, and is adjustable from piston to piston to provide required output.
If there is insufficient pressure available in the wellbore, a reservoir may be provided to increase the activating pressure supplied to the tool. The reservoir may take the form of a nitrogen gas pressure bottle or accumulator, screwed onto the top of the tool.

Hydraulic setting tool with pressure multiplier


A resistive composition for screen printing onto a substrate. The resistive composition, based on total composition has a) 5-30 wt. % of polymer resin, b) greater than 0 up to and including 10 wt. % of thermosetting resin, c) 10-30 wt. % conductive particles selected from the group consisting of carbon black, graphite and mixtures thereof and d) 0.025-20 wt. % carbon nanoparticles, wherein all of (a), (b), (c) and (d) are dispersed in a 60-80 wt. % organic solvent.

1. Field of the Invention
This invention generally relates to polymer thick film conductive compositions containing nanomaterials. In particular, the invention is directed to such compositions, which are suitable for making variable resistive elements such as those used in position sensing elements.
2. Description of the Related Art
Electrically resistive polymer thick film compositions have numerous applications. Polymer thick film (PTF) resistive compositions are screenable pastes which are used to form resistive elements in electronic applications. Such compositions contain conductive filler material dispersed in polymeric resins which remain an integral part of the final composition after processing.
Resistive compositions are used as resistive elements in variable resistors, potentiometers, and position sensor applications. A resistive element is, in most cases, printed over a conductive element which acts as a collector element. In position sensing applications, a metallic wiper slides over the resistive element. The wiper can slide back and forth for several million cycles over the collector and resistive elements during the lifetime of the electronic component. For accurate position sensing, the wiper should give continuous electrical output throughout the life of the sensor.
The durability of these position sensing elements depends on the mechanical properties of both the resistor and the conductive film. The polymer thick films tend to wear out after several million cycles of sliding with a metallic contactor over the elements at extreme temperature conditions typically seen in an environment such as an automotive engine compartment. Therefore, polymer resistive and conductive compositions having excellent mechanical properties and wear resistance are required for performance and signal output in these applications.
In addition to good mechanical properties, these materials should also have good thermal properties. Polymer thick films show a decrease in storage modulus as temperature is increased. A sharp decrease in mechanical properties is observed near the glass transition temperature. In addition to loss in modulus, these materials also tend to show an increase in coefficient of thermal expansion, which increases significantly above the glass transition temperature (Tg). When used in, for example, motor vehicles, a position sensor is exposed to high temperatures in under the hood applications. At these temperatures resistive elements show a high rate of wear due to a decrease in modulus properties. In addition to the surrounding temperature, a still higher temperature is observed at the interface between the metallic wiper and the resistive element surface due to frictional heating. In some cases, these temperatures can approach the glass transition temperature (Tg) of the resistive material and can cause loss of the material""s mechanical properties, which adversely affect signal output.
A prior art resistor composition is as follows:
One way to improve mechanical properties of a resistive film is to incorporate fillers, such as short fibers, in these films. The presence of fibers of relatively large dimension creates an electrically heterogeneous surface. This results in non-linear electrical output in contact sensor applications. Even when the size of the fibers is in the order of a few microns, the surface is still electrically and mechanically heterogeneous. A dither motion at high frequency on a surface region where these fibers are absent can create large wear. Another problem with using fibers with greater than 10 volume percentage is that it can significantly wear the metallic contactor. This wear is accelerated if these fibers are protruding from the surface. Therefore, there is a need in the art for resistor elements with enhanced mechanical and thermal properties while exhibiting homogeneous surface electrical characteristics.
According to a preferred embodiment of the invention, a resistive composition for screen printing onto a substrate is provided. The resistive composition, based on total composition, has a) 5-30 wt. % of polymer resin, b) greater than 0 up to and including 10 wt. % of thermosetting resin, c) 10-30 wt. % conductive particles selected from the group consisting of carbon black, graphite and mixtures thereof, and d) 1-20 wt. % carbon nanoparticles, wherein all of (a), (b), (c) and (d) are dispersed in a 60-80 wt. % organic solvent.
The present invention relates to an improved nanocomposite resistive composition comprising a polymeric resin and dispersed nanomaterials having conductive fillers and potentially anti-friction additives, with the dispersed nanomaterials being present in an amount less than 30% by weight of the cured nanocomposite films. The nanomaterials are preferably selected from carbon nanotubes, vapor grown nanofibers, milled carbon fibers, nanoclays, and molecular silica.
The invention provides increased mechanical, wear, electrical, and thermal properties of the resistor materials by incorporating the nanomaterials into the resistive composition. The large surface to volume ratio of the materials imparts significant interfacial strength to the composites. The functions of nanoparticles and nanofibers are to increase the polymer-filler interactions. The large surface area of these nanomaterials significantly interacts with functional groups in the macromolecular chains. These interactions in the molecular and nanoscale increases the microhardness and nano-hardness properties of these materials. These micro and nanohardness properties are very important for the sliding contact applications. The homogeneity of the nanocomposite film increases the toughness and hardness uniformly. Forming a resistor surface with molecularly dispersed fibers or other so called nanomaterials of submicron size in accordance with the invention can create an electrically and mechanically homogeneous surface which enables a consistent and durable electrical output to be established. The molecular silica materials and nanoclay can provide increased thermal properties. The carbon fibrils provide increased electrical and mechanical properties. A composition containing carbon nanofibers and molecular silica materials provide enhanced wear resistance, enhanced thermal properties, and enhanced electrical properties.
The invention provides a decrease in contactor wear by either avoiding the use of relatively large carbon fibers or by using a very small concentration of very finely milled carbon fibers in conjunction with nanoparticles and nanofibers. Due to the large surface to volume ratio, nanoparticles and nanofibers need to be used in less than 5 volume percentage. This significantly reduces the tendency of the contactor to prematurely wear.
The invention creates a resistor surface with a homogeneous electrical and mechanical surface in nanoscale. During a high frequency small stroke dither test, the contactor will always be sliding on a mechanically tough nanocomposite surface. In contrast, the high frequency small stroke dither test on a composition of prior art can gouge and pit a resistor surface where the carbon fibers are absent.
The invention decreases the coefficient of thermal expansion (CTE) of the resistor material. Wear of resistor materials typically is significantly increased at high temperature. One of the reasons for this phenomenon is the increased expansion of the material. By incorporating molecular silica, nanoclay, and nanofibers, molecular scale interactions with the polymer matrix are achieved. These strong interactions in nanoscale decrease the CTE of the material. In contrast, significantly large amount of fibers would be needed to be added to a polymer matrix to decrease the matrix""s thermal expansion coefficient. As mentioned earlier, adding a large amount of carbon fibers to the matrix can significantly wear the associated metallic contactor.
The invention uses high glass transition temperature polymers, which form secondary bonding with the nanomaterials. The polymer matrix resin is selected from any high performance thermoplastic or thermosetting resins. The functional groups in the polymers should have good interactions with the nanoparticles. For instance, polyimide, polyamideimide, phenolic, Diallyl Isophthalate (DAIP), Epoxy, Bismaleimide, etc can be used in acccordance with the invention.
Additional objects, features and advantages of the invention will become more readily apparent from the following detailed description of preferred embodiments thereof.
According to preferred embodiment of the invention, a resistive composition for screen printing onto a substrate will now be described. In particular, the composition includes polymer components, nanomaterials components, electrically conductive components and other additives. The composition is carried by an organic vehicle. The details of all these components, its method of preparation, and associated printing procedures are discussed below.
Polymers with functional groups capable of forming secondary bonding with nanoparticles and nanofibers are preferred for these compositions. In addition to the functional groups, they should also have a high glass transition temperature. It is critical for some high temperature applications, such as automotive applications, that these materials maintain a high storage modulus during the use and lifetime of the materials. The polymer components used in the present invention comprise 5-30 wt. % of a high Tg polymer selected from polyimides, polyamide imides, polysulfones, polyphenylenes, polyether sulfones, polyarylene ethers, polyphenylene sulfides, polyarylene ether ketones, phenoxy resins, polyether imides, polyquinoxalines, polyquinolines, polybenzimidazoles, polybenzoxazoles, polybenzothiazoles, phenolic, epoxy, diallyll isophthalate copolymers thereof, and mixtures thereof, etc based upon total composition. In addition to this polymer, 0-10% of another thermosetting polymer can be used. The choice of the second polymer depends on the application, as will be discussed more fully below. The second polymer can be selected from aromatic cyanate ester, epoxy, phenolic, diallyl isophthalate, bismaleimide, polyimide, etc. The polymers are dissolved in an organic solvent. The percentage compositions are based upon total composition.
In the electrically resistive composition of the present invention, the polymer is used in the range of 5-30 wt. % by weight of the conductive composition, with a more preferred range of 15-20 wt. %. If less than 5 wt. % resin is used, the resulting conductive composition has been found to have poor screen printing properties, as well as weak mechanical properties and poor adhesion. If more than 30 wt. % is used, the resulting composition has a lower than desirable electrical conductive property.
An optional second polymer is sometimes added to increase the interfacial bonding between nanomaterials and the matrix resin. The second polymer is preferably a high temperature thermosetting polymer and is used in the range of 0-10 wt. %. The amount of this resin in the composition is determined by the application requirements. Increasing the amount of the second thermosetting polymer decreases flexibility, but improves temperature performance at high temperature. Depending on the amount of the second polymer, the cured film can either behave as a molecular composite, a semi-interpenetrating network, or an immiscible blend. This versatility in morphology can be judiciously chosen for a given application.
The mechanical and thermal properties of these resistive films can be increased by incorporating materials of nanodimensions in the resistive compositions. The nanoparticles and nanofibers of the present invention can be selected from carbon nanotubes, vapor grown carbon nanofibers, milled carbon fibers, molecular silica, nanoclay, and the like. Nanoparticles and nanofibers may be pretreated or preprocessed to obtain better dispersion of these materials. The particle size of these materials can be sometimes tailored for a given application. One of the methods to reduce and control particle size of vapor grown carbon fibers and milled carbon fibers is by milling them in a ball mill using a steel media. The medium for milling can be judiciously chosen to get very small particle size and to control particle size. The nanoparticles and nanofibers can be pretreated by using suitable materials in the milling medium. The medium for milling can also be monomers, oligomers, surface active agents, surface active chemicals, solvents, etc. The nanoparticles are used in the range of 0.025-20 wt % of the composition. A preferred range is 0.1-7 wt %.
In accordance with the invention, resistive nanocomposite compositions are polymer thick film compositions for which at least one dimension of the dispersed particles is in the nanometer range. Carbon nanotubes are strand-like fibers. Individual single-walled carbon nanotubes (SWNT) have a typical diameter in the range of 1-2 nm. Vapor grown carbon fiber (VGCF) is highly crystalline fine carbon fiber synthesized by the vapor-phase method. VGCF is similar to fullerene tubes in the nanoscale domain of initial formation and the highly graphitic structure of the initial fibril. VGCF is produced as a mass of tangled fibers, each of which has a diameter of about 100 nanometer and a length ranging from 50 to 100 microns or longer. Milled carbon fibers are random short length fibers made from PAN or pitch which are 5-8 xcexcm in diameter and have an average length of about 30 xcexcm. The particle size of these milled fibers can be fibers can be reduced to submicron range by ball milling. The nanoclay particles are layered silicates, wherein the layer thickness is around 1 nanometer and the lateral dimension of the layers vary from 0.3 nanometers to several microns. Molecular silica is derived from a class of chemicals known as polyhedral oligomeric silsesquioxanes (POSS) and polyhedral oligomeric silicates. POSS molecules are physically large with an approximate size range of 0.7 to 50 nm.
The electrically conductive component of the present invention comprises finely divided particles of electrically conductive materials such as carbon black, graphite, silver, copper, nickel or mixtures thereof. This includes mixtures of the metallic and carbon powders. The preferred particles are carbon black. The preferred conductive particles comprise 1-25 wt. % of the conductive composition, with a most preferred range of 1-10 wt. %. The preferred carbon black is commercially available from Degusaa Corporation.
Antifriction additives such as fluoropolymers and graphite are preferably used to decrease the friction between the resistive nanocomposite film surface and the sliding contact. The antifriction additives comprise 1-20 wt. % of the resistive composition, with a preferred range of 5-10 wt. %. The preferred fluropolymer is commercially available from Dupont.
Wetting agents such as fluorinated oligomers may be added to the composition for wettability and leveling properties. Up to 1 wt. % of a fluorinated surfactant may be used. The fluorinated oligomers are commercially available from 3M Corporation.
An organic solvent of 20-40 wt. % is used to dissolve the resistive composition. The preferred solvent used is N-methyl pyrrolidone. The selection of the solvent is based on the good solubility of the polymer in this solvent. This solvent also has a high boiling point. Low evaporation of the solvent is preferred for continuous printing operation where no change in viscosity of the composition due to loss of solvent is desired. The polymer is dissolved completely in the organic vehicle prior to blending with the other components. N-methyl pyrrolidone is commercially available from BASF Corporation.
In the preparation of an exemplary composition of the present invention, a polymer solution is made by mixing 10-20 wt. % of a polymer and 0-10 wt. % thermosetting resin in 60-80 wt. % N-methyl pyrrolidone based upon total composition. The polymer is mixed with both the conductive and nano-particles to form a paste with fine particle size. At this point, surfactants and rheological additives may be added if desired to modify the properties of the resistive composition. The paste is mixed in a ball mill for several hours. Other methods of mixing could be used, such as employing high-speed shear to thoroughly blend the particles in the polymer binder. However, ball milling is preferred for preparing resistive composition with uniform particle size. The particle size range and viscosity of the paste is monitored to get a resistive paste suitable for application in position sensors. The milling time and milling quantity on the ball mill determines the final particle distribution, size and resulting rheology.
The resulting component sizes are as follows:
The resistive paste thus prepared is applied to substrates such as polyimide, ceramic and fiber reinforced phenolic substrates by conventional screen printing processes. A preferred substrate is polyimide. The wet film thickness typically used for position sensor application is 40 microns. The wet film thickness is determined by the screen mesh and screen emulsion thickness. A preferred screen mesh of 250 is used for obtaining smooth resistive film on a polyimide substrate for position sensors. The paste is then air dried and cured resulting in a resistive film on the substrate.


In a projection arrangement with a projector and a deflecting mirror in which the image projection, proceeding from a projection direction along a principal projection axis impinges on the deflecting mirror which is supported so as to be movable in two spatial direction and whose mirror surface deflects a projected light bundle at an elevation angle and at an azimuth angle onto a projection surface standing on the ground the image projection is effected from the direction of a zenith at an angle xcex2 which is less than 60xc2x0 in relation to a vertical line from the zenith and the deflecting mirror is arranged at the ground wherein the projected light bundle can be deflected toward the projection surface so that an image can be generated on the projection surface and moved on the latter.

a) Field of the Invention
This application was published under PCT Article 21(2) in the German language with an English abstract: this is a request for a CPA application under 37 C.F.R. 1.53(d) (continued prosecution application) of pending prior application 09/582,814 filed Nov. 4, 1999 as PCT/EP99/08445 claiming foreign priority to DE 198 51 000.4 filed Nov. 5, 1998 to which priority is hereby claimed. The invention is directed to an arrangement with a projector and a deflecting mirror in which the image projection proceeding from a projection direction impinges on the deflecting mirror which is mounted so as to be movable in two spatial directions and whose mirror surface deflects the projection beams at an elevation angle and an azimuth angle. A projection arrangement of this type can also be called a drawing projector, since a static or moving image is generated, projected onto a projection surface, and moved on the latter.
b) Description of the Related Art
For front projection, the projection surface is a wall (e.g., projection screen) or, in the case of rear projection, a screen (e.g., ground glass screen). The projector is not limited to a certain type of image generation. Projectors which write the image by means of a brightness-modulated and/or color-modulated light beam can be used. These projectors are also known as laser projectors. However, image-forming projectors which generate an image proceeding from an object plane internal to the device as is known, for example, in CRT, LCD, DMD or slide projectors can also be used.
A deflecting device for an image generated by a laser beam is known from U.S. Pat. No. 5,365,288 DEWALD. The image is rotatable by itself by means of a K-mirror arrangement and is then deflected in such a way by a mirror mounted on two axes that the generated image can be deflected in a defined spatial area. The arrangement of the elements for the image deflection is carried out in such a way that the image is generated in a device standing on the floor and is directed to the deflecting mirror proceeding from this floor position.
In relation to a horizontal plane through the axis of rotation of the deflecting mirror, the practical useful deflection angle area resulting from this arrangement
is limited toward the floor due to the required device dimensions and can be, at most, approximately 45xc2x0 without substantial image shadowing, and
can be at most 30xc2x0 in practice toward the zenith due to the mirror dimensions increasing toward infinity.
Therefore, the observer is only afforded limited viewing possibilities which are more sharply limited in the direction of the zenith than in the direction of the floor. However, this conflicts with the customary mode of observing images that are generally projected xe2x80x9cskywardxe2x80x9d, another reason for this being to prevent shadowing caused by other observers or by structural parts. It is impossible to generate images in the vicinity of the zenith with this arrangement.
It is the primary object of the invention to increase the area of possible image presentation on a given projection surface in an arrangement of the type mentioned above. The area in which a comparatively small image can be presented within a projection surface which is large in proportion to the image size, especially in a projection dome, is to be expanded. The position of the display area should correspond to the normal viewing habits of the observer and it should also be possible to display an image in the vicinity of the zenith and in the zenith. In this respect, a high-quality monochromatic, black-and-white, or color image can be displayed at relatively little expense and, at the same time, can be moved on the projection surface, in particular, fast enough so that the observer can substantially follow the movement of the image. Further, an arrangement of a plurality of projectors is possible, wherein mutual shadowing is also minimized in this case and the area in which it is possible to display images is maximized for all projectors.
According to the invention, a projection arrangement with a projector and a deflecting mirror are suggested, wherein the image projection, proceeding from a projection direction along a principal projection axis, impinges on the deflecting mirror which is supported so as to be movable in two spatial direction and whose mirror surface deflects a projected light bundle at an elevation angle and at an azimuth angle onto a projection surface standing on the ground, wherein the image projection is effected from the direction of a zenith at an angle xcex2 which is less than 60xc2x0 in relation to a vertical line from the zenith, and the deflecting mirror is arranged on the ground, wherein, further, the projected light bundle can be deflected toward the projection surface and an image can therefore be generated on the projection surface and moved on the latter.
By xe2x80x9czenithxe2x80x9d is meant the zenith of the dome of the sky or the zenith of an artificial dome, e.g., in a planetarium. When it is stated that the deflecting mirror is arranged on the ground, this does not mean that it must lie directly on the ground. It can be arranged far above the surface of the ground by means of a holder or can be fastened to a wall above the surface of the ground or can also be suspended from a ceiling. However, it is essential that the projection is carried out proceeding from the direction of the zenith onto the mirror surface of the deflecting mirror. The indicated quantity of angle xcex2 signifies that the direction of the light bundle impinging on the deflecting mirror comes from the direction of the zenith. By means of the arrangement according to the invention, a surface region that is substantially larger compared to the prior art is achieved, for example, in a projection dome of a planetarium, when an image is displayed, and the image display on the projection surface is not disturbed by shadowing.
Further, the shadowing caused by projectors, other installed items or observers can be minimized. In particular, the display of the image reaches the surface region around the zenith without restrictions and without shadowing.
In an advantageous development of the invention, an image is generated by the projected light bundle only in a partial region of the projection surface and is then movable within the entire area of this projection surface. The movement can be carried out comparatively quickly because the relatively massive projector is stationary and only the comparatively small mass of the deflecting mirror must be moved.
The image should not fill up the entire projection surface statically as is the case, for example, in a cinema, but, rather, should be movable within the display area on the projection surface. The image can be equal to or greater than the projection surface for some applications. In this case, portions of the image cannot be displayed during the movement of the image. For many applications, however, it is sufficient when the size of the moving image is less than 90% in relation to the size of the projection surface. This is advantageous, for example, for image tracking for displaying set designs in entertainment applications when images are to be projected on backdrop arrangements. In this case, the image contents can always be displayed in their entirety. In many applications, the image is a comparatively small image, for example, of a planet or aircraft, that is moved on the projection surface, e.g., over the dome of the sky. However, the size of the image to be displayed by the projector can also be less than 1% of the projection surface.
The image size can be continually adjusted through the realization of a zoom function, so that, for example, an approaching or receding vehicle can be simulated in a realistic manner. This zoom function can be realized by means of known zoom optics or in an image-generating computer.
The control of the deflecting mirror can advantageously be carried out relatively simply when the axis of rotation for adjusting the elevation angle extends vertical to the principal projection axis and the axis of rotation for adjusting the azimuth angle coincides with the principal projection axis. In this case, no image distortions occur as a result of the deflection of the image by the deflecting mirror. It is particularly advantageous when the direction of the principal projection axis to the deflecting mirror is a line parallel to the vertical line from the zenith. In this case, angle xcex2 is 0xc2x0. One of the axes of rotation of the deflecting mirror then contributes only one movement component to the azimuth position and to the elevation position of the image. This enables a particularly simple correlation of the image position in the area of the projection surface.
When the direction of the principal projection axis onto the deflecting mirror lies in the vertical line from the zenith of a spherical projection dome, a movement of the image by 360xc2x0 can be realized particularly favorably. A particularly advantageous arrangement is achieved when the projector is arranged in the zenith of a projection dome and the deflecting mirror is arranged on the floor of projection dome, wherein the axis of rotation for the adjustment of the azimuth angle coincides with the vertical line from the zenith. The projector is then located outside of the projection dome and the coupling in of radiation is carried out through a small opening in the zenith of the projection dome. In this case, only the deflecting mirror is still arranged inside the projection dome. Another advantageous arrangement is achieved when the deflecting mirror is arranged in the center of a spherical projection dome. The projection distance from all areas of the projection dome is identical in this case. The size of the image is then identical at all angle positions without further steps.
In particular, this arrangement facilitates image generation by means of image-forming projectors, for example, slide projectors, LCD projectors or DLP projectors, since the possible area of the depth of focus of projectors of these types is only relatively small and no additional steps are required in this case for adjusting or producing the image focus. When projection is carried out with projectors of these types from outside the spherical center or the image is directed onto an aspherical projection wall, a readjustment of the image focus as a function of the image position is compulsory. With larger images, partial areas of the image can also be out of focus.
This problem does not occur when using a projector which works with a writing, essentially parallel, laser light bundle. Images generated in this manner are focused within a very large area amounting to several meters at any projection distance. Such projectors are known as xe2x80x9claser projectorsxe2x80x9d.
It has been shown in practice that the image size is perceived by the observer as stationary when the deflecting mirror is arranged in relation to the projection surface in such a way that the projection distance from every point of the projection surface deviates from an average projection distance by less than +/xe2x88x9210%. This result is achieved especially when the observer lacks a comparison scale. A zoom function of the projector for readjusting the image size is not absolutely necessary. However, for subordinate applications, a deviation of +/xe2x88x9220% is also acceptable.
The size of the area in which a good-quality image is movable on the projection surface without shadowing by a deflecting mirror that is not too large depends first on the overall size of the projector or its subassemblies located in the projection dome. As will be shown subsequently in the embodiment examples of the invention, this factor can be minimized absolutely. The size of the projection surface that can be utilized for image projection is further determined by the position of the axes of rotation of the deflecting mirror relative to the projection surface. The height of the deflecting mirror in relation to the horizon given, for example, in a projection dome, is a critical determinant for the size of the accessible area for displaying the image. When the axis of rotation generating the elevation angle lies above the horizon, the display area is reduced; when it lies below the horizon, the area in which it is possible to display the image is increased. In extreme cases, the projection dome is a sphere, the projector is located at the zenith and the deflecting mirror is located opposite the zenith on the ground. There are virtually no restrictions with respect to the shape of the projection surface, especially with a laser projector, because of the virtually unlimited depth of focus. The projection surface can be the inner surface or the outer surface of a sphere, a part of a sphere, or a layer of a sphere, or an aspherically curved surface corresponding to the basic shapes mentioned above. However, it can also be a plane surface or can be formed of a plurality of parts of such a surface, or can be shaped in a completely irregular manner and/or be moved dynamically.
A particularly favorable use of space and a very practical construction are achieved when a stationary path-folding or reflection mirror which deflects the light bundle proceeding from the projector is arranged relative to the projector. The choice of how and where the projector is arranged in relation to the projection surface is relatively open. It is only necessary to meet the condition that the light bundle travels from the direction of the zenith after deflection through the reflection mirror.
In an image-forming projector, the reflection mirror is arranged behind the projection objective in the direction of radiation. With a laser projector with a writing light bundle, the reflection mirror is provided behind the deflecting device for scanning lines in the image or behind the angle-transforming transformation optics that are used in most cases. The reflection mirror is advisably fixedly connected with the projector. Owing to the simplicity of control with angular coordinates, it is further advisable when the stationary reflection mirror is at an angle of 45xc2x0 to the principal projection axis from the projector. In this regard, it is particularly advantageous when the projector itself is at an angle of 90xc2x0 to the azimuthal axis of rotation of the deflecting mirror. However, the reflection mirror can also be movable in order to generate special image effects. For example, the light bundle which is directed to the deflecting mirror can be redirected to another deflecting mirror with a different mirror position by means of a controllable reflection mirror. In this way, sudden image movements can be generated, for example, when changing between the two deflecting mirrors which are arranged next to one another and have different mirror positions.
A laser projector comprises at least one brightness-modulated and/or color-modulated laser radiation source and a deflecting device for scanning the light bundle in two dimensions. For the use of laser projectors in projection rooms, it is particularly advantageous when the brightness-modulated and/or color-modulated laser radiation source and the projection head are optically connected with one another in a projector of this type by a light-conducting fiber. The laser radiation source is a monochrome laser radiation source or a red-green-blue laser radiation source by which light can be efficiently coupled into a light-conducting fiber. The spatial separation of the light source and projection head which is made possible by the light-conducting fiber connection provides many design possibilities with respect to how the installation of the projector can be carried out, for example, in a projection dome.
The spatial separation of the subassemblies or component groups does not cause any problems with respect to the setup of a contemporary, relatively heavy and large laser beam source adjacent to or under the projection dome or with respect to the arrangement of the comparatively small projection head in the projection dome or on the projection dome. Even arranging the projection head in the zenith of a projection dome does not cause problems in this case. As subassemblies become smaller and lighter with progressing development, it will become easier to mount the projection system in a housing.
The projection head contains a horizontal-line mirror and a vertical-line mirror for scanning the light beam. Further, transformation optics which increase the scanning angle are arranged downstream in the direction of light when required by the projection ratios (the image size to be achieved at a given projection distance). These transformation optics can also contain a controllable zoom function when the image size is to be adjusted or varied during the image display. The electronic control of the zoom factor is carried out as a function of the desired image size on the projection surface, wherein changes in the image size due to changes in the projection distance can also be compensated for.
But the invention can also be realized using image-forming projectors, for example, with a film projector, a slide projector, an LCD projector or a CRT projector. In projectors of the types mentioned above, a projection objective is generally used in order to be able to adjust the desired image size. In this case, temperature radiators are conventionally used as light sources. The projector can also be divided up into the subassemblies of light source and projection head in this case. In contrast to the laser projector, the projection head contains the object plane with a projection objective associated with the latter.
The optical connection between the subassemblies can also be produced via a light-conducting fiber or bundled light-conducting fibers. The advantage that the heat output occurring during operation of a temperature radiator need not be given off in the projection space is applied in particular in this case.
However, a laser radiation source can also be used in image-forming projectors, although it must be expanded for illuminating the object field. In this case, the light transmission from the laser light source to the object field is likewise provided via a light-conducting fiber. With a stationary installation, the possibility of light transmission between the light source and projection head in free space, irrespective of the type of projector, is also a particularly advantageous variant; in this case, when the light source is set up outside of the projection space, the light must be guided through an opening in the projection screen or in the projection dome.
The projection systems described above can be combined with a pilot laser for training purposes and measurement purposes. In this connection, the wavelength of the pilot laser beam is not the same as the wavelengths of the projection beams. The pilot laser beam can be coupled into the beam path in such a way that it represents a fixed point in the deflected image and is movable together with the image. The reflection mirror is particularly suitable for coupling in the pilot laser beam; this reflection mirror is transparent for light of the wavelength of the pilot laser beam and reflects all other wavelengths. However, the pilot laser beam can also be coupled into the beam path of the projection arrangement at another location, for example, via an additional coupling-in mirror, wherein coupling in should be carried out subsequent to the deflecting system and transformation optics because of the wavelengths of the pilot laser beam which lie outside of the range of visible light. The direction of the pilot laser beam can also correspond to the position of the principal projection axis in particular or can be correlated to a determined object in the projected image.
The movement of the image can be tracked by a direction-sensitive receiver that is adjusted to the wavelength of the pilot laser beam, or an automatic or manual image tracking can be detected and evaluated.
The above description of the projection arrangement working with a projector and a deflecting mirror also shows advantages when more than one projector is set up in a projection space. For example, a first projector can project a scene filling up the projection surface and a second projector, by means of the deflecting mirror, supplies a comparatively small image which is movable within the scene and which can be displayed completely independent from this scene.
In another variant, a plurality of projectors are directed to a projection surface with respective associated deflecting mirrors. Accordingly, for example, three images showing different objects can be moved over the projection surface independently from one another. Each of the images can show an aircraft, for example. In so doing, the deflecting mirrors can be arranged next to one another in horizontal direction, wherein the directions of the light bundles impinging on the mirror surfaces of the deflecting mirrors also proceed from the direction of the zenith in this case.
The deflecting mirrors can also be arranged one above the other in vertical direction. In addition, the deflecting mirrors can lie next to one another. However, it is advisable when projectors with reflection mirrors are used and the directions of the principal projection axes of the light bundles coincide following the beam deflection through the respective associated reflection mirrors.
All deflecting mirrors are accordingly arranged at a short distance exactly one above the other. In this way, the projection ratios are virtually identical for all projectors, since the projection of all images is effected proceeding from virtually the same location. In this case, the condition that the projection distances of the projectors from the average projection distance is less than +/xe2x88x9210% can easily be satisfied.
The enlarged angular range in which images can be displayed without any shadowing is particularly advantageous compared with known projection arrangements. This advantage comes into play particularly when more than one projector must be arranged in a projection space. Moreover, the position of the angular area, for example, in relation to a position of the projector in a projection dome, is more favorable because now images can be displayed in the area of the zenith until far below the horizon. When using a projector working with a writing laser light bundle, the advantages that images produced in this way have a virtually unlimited depth of focus and that a very extensive correction of image errors can be carried out are particularly useful.
In the following, the invention will be described more fully by way of example with reference to the drawings.

Projection system with projector and deflection mirror

LTD GmbH and Co. Laser-Display-Technologie KG


An improvement is described in compositions which are especially effective in disinfecting the surface being cleaned and in the removal of oily and greasy soil without leaving streaks which contains a mixture of at least one nonionic surfactant, a cationic surfactant, an anionic surfactant and a hydrocarbon ingredient, a water soluble solvent, and water.

This invention relates to an improved multi purpose liquid cleaner in a form, in particular for cleaning and disinfecting hard surfaces and which is effective in sanitizing surfaces, in removing grease soil in removing lime scale and soap scum and also dries fast leaving the surfaces streak free.
Disinfectant composition based on cationic and nonionic are well known. However, these compositions while very efficient in disinfecting surfaces, generally do not remove grease and oil as desired; hence, leaving residues and streaks on surfaces. Addition of an efficient anionic surfactant cleaner, to the cationic surfactant, either creates instability problems or deactivates the disinfectant behavior of the cationic. Anionic and nonionic mixtures have a good grease removal properties, but do not perform at all to sanitize the surface being cleaned.
Acidic composition to remove lime scale also exist. Usually they provide some disinfecting behavior and some of them are highly effective in removing lime scale but they are not performing in grease removal and leave streaks and residues.
In one aspect, the invention generally provides a stable, clear multi purpose, hard surface cleaning composition having a pH of about 2.5 to 4.5 which is especially effective in disinfecting the surface being cleaned and in the removal of lime scale and greasy oil. These compositions also have a fast drying out time and does not leave streaks on the surface being cleaned. The compositions include approximately, on a weight basis:
0.1% to 8% of an anionic sulfonate surfactant;
0.1% to 10% of a nonionic surfactant formed from the condensation product of a C9-C18 alkanol, ethylene oxide and propylene oxide;
from 0 to 8%,more preferably 0.5% to 6% of at least one nonionic surfactant formed from the condensation product of a C9-C18 alkanol and ethylene oxide;
from 0.1 to 10% of at least one disinfecting agent;
0 to 10% of at least one water soluble glycol ether solvent;
0.1% to 2.5% of a fatty acid;
0 to 10%, more preferably 0.1% to 6% of an ethoxylated alkyl ester nonionic surfactant;
0 to 8%, more preferably 0.1% to 6% of an ethoxylated alcohol;
0.05% to 3.0%, more preferably 0.1% to 1% of a perfume, water insoluble organic compound or essential oil; and
the balance being water.
The present invention relates to a stable hard surface cleaning composition comprising approximately by weight:
0.1% to 8% of an anionic surfactant;
0.1% to 10% of a nonionic surfactant formed from the condensation product of a C9-C18 alkanol, ethylene oxide and propylene oxide;
0 to 8%, more preferably 0.5% to 6% of at least one nonionic surfactant formed from the condensation product of a C9-C18 alkanol and ethylene oxide;
0 to 8%, more preferably 0.1% to 6% of an ethoxylated alcohol;
0.1% to 10% of at least one disinfecting agent such as a cationic surfactant,
0.1% to 2.5% of a fatty acid,
0 to 10%, more preferably 0.1% to 6% of an ethoxylated alkyl ester nonionic surfactant;
0 to 10% of at least one water soluble glycol solvent;
0.05% to 3.0%, more preferably 0.1% to 1% of a water insoluble organic compound, essential oil, or a perfume, and
the balance being water, wherein the composition does not contain a pyrrolidone compound or a C4-C12 alcohol ester of a sulfosuccinic acid, an amphoteric surfactant, a dialkanol amine, trialkanol amine or an alkali metal hydroxide.
Excluded from the instant composition are ethoxylated glycerol type compounds, alkyl and/or alkenyl oligoglycoside of formula:
R1xe2x80x94Oxe2x80x94[G]p
in which R1 represents a linear or branched alkyl or alkenyl group with 8 to 22 carbon atoms, [G] represents a glycose unit with 5 or 6 carbon atoms, preferably a glucose unit, and p represents a number from 1 to 10, and an alkyl ether of formula:
in which R2 represents a linear or branched aliphatic alkyl and/or alkenyl group with 8 to 18, preferably 8 to 14 carbon atoms, x represents 0 or a number of up to 3, preferably up to 2, and y represents a number from 1 to 15, preferably 2 to 12, especially 2.5 to 10.
As used herein and in the appended claims the term xe2x80x9cperfumexe2x80x9d is used in its ordinary sense to refer to and include any non-water soluble fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flower, herb, blossom or plant), artificial (i.e., mixture of natural oils or oil constituents) and synthetically produced substance) odoriferous substances. Typically, perfumes are complex mixtures of blends of various organic compounds such as alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils (e.g., terpenes) such as from 0% to 80%, usually from 10% to 70% by weight, the essential oils themselves being volatile odoriferous compounds and also serving to dissolve the other components of the perfume.
In the present invention the precise composition of the perfume is of no particular consequence to cleaning performance so long as it meets the criteria of water immiscibility and having a pleasing odor. Naturally, of course, especially for cleaning compositions intended for use in the home, the perfume, as well as all other ingredients, should be cosmetically acceptable, i.e., non-toxic, hypoallergenic, etc.
The water insoluble organic compound, essential oil or perfume is present in the composition in an amount of from 0.05% to 3% by weight, preferably from 0.1% to 1% by weight.
Furthermore, although superior grease removal performance will be achieved for perfume compositions not containing any terpene solvents, it is apparently difficult for perfumers to formulate sufficiently inexpensive perfume compositions for products of this type (i.e., very cost sensitive consumer-type products) which includes less than 20%, usually less than 30%, of such terpene solvents.
The water insoluble saturated or unsaturated organic compound is selected from the group consisting of water insoluble hydrocarbons containing a cycloalkyl group having 5 to 10 carbon atoms, wherein the alkyl or cycloalkyl group can be saturated or unsaturated and the cycloalkyl group can have one or more saturated or unsaturated alkyl groups having 1 to 20 carbon atoms affixed to the alkyl or cycloalkyl group and one or more halogens, alcohols, nitro or ester group substituted on the cycloalkyl group or alkyl group; aromatic hydrocarbons; water insoluble ethers; water insoluble carboxylic acids, water insoluble alcohols, water insoluble amines, water insoluble esters, nitropropane, 2,5dimethylhydrofuran, 2-ethyl2-methyl 1,3dioxolane, 3-ethyl 4-propyl tetrahydropyran, N-isopropyl morpholine, alpha-methyl benzyldimethylamine, methyl chloraform and methyl perchlorapropane, and mixtures thereof. Typical hydrocarbons are cyclohexyl-1 decane, methyl-3 cyclohexyl-9 nonane, methyl-3 cyclohexyl-6 nononane, dimethyl cycloheplane, trimethyl cyclopentane, ethyl-2 isopropyl-4 cyclohexane. Typical aromatic hydrocarbons are bromotoluene, diethyl benzene, cyclohexyl bromoxylene, ethyl-3 pentyl-4 toluene, tetrahydronaphthalene, nitrobenzene, and methyl naphthalene. Typical water insoluble esters are benzyl acetate, dicyclopentadienylacetate, isononyl acetate, isobornyl acetate and isobutyl isobutyrate. Typical water insoluble ethers are di(alphamethyl benzyl) ether, and diphenyl ether. A typical alcohol is phenoxyethanol. A typical water insoluble nitro derivative is nitro propane.
Suitable essential oils are selected from the group consisting of: Anethole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand, Balsam (Peru), Basil oil (India), Black pepper oil, Black pepper oleoresin 40/20, Bois de Rose (Brazil) FOB, Borneol Flakes (China), Camphor oil, White, Camphor powder synthetic technical, Cananga oil (Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) BP, Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil, Clove leaf, Coriander (Russia), Coumarin 69xc2x0 C. (China), Cyclamen Aldehyde, Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil, Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Ginger oleoresin (India), White grapefruit oil, Guaiacwood oil, Gurjun balsam, Heliotropin, Isobornyl acetate, Isolongifolene, Juniper berry oil, L-methyl acetate, Lavender oil, Lemon oil, Lemongrass oil, Lime oil distilled, Litsea Cubeba oil, Longifolene, Menthol crystals, Methyl cedryl ketone, Methyl chavicol, Methyl salicylate, Musk ambrette, Musk ketone, Musk xylol, Nutmeg oil, Orange oil, Patchouli oil, Peppermint oil, Phenyl ethyl alcohol, Pimento berry oil, Pimento leaf oil, Rosalin, Sandalwood oil, Sandenol, Sage oil, Clary sage, Sassafras oil, Spearmint oil, Spike lavender, Tagetes, Tea tree oil, Vanilin, Vetyver oil (Java), Wintergreen, Allocimene, Arbanex(trademark), Arbanol(copyright), Bergamot oils, Camphene, Alpha-Campholenic aldehyde, I-Carvone, Cineoles, Citral, Citronellol Terpenes, Alpha-Citronellol, Citronellyl Acetate, Citronellyl Nitrile, Para-Cymene, Dihydroanethole, Dihydrocarveol, d-Dihydrocarvone, Dihydrolinalool, Dihydromyrcene, Dihydromyrcenol, Dihydromyrcenyl Acetate, Dihydroterpineol, Dimethyloctanal, Dimethyloctanol, Dimethyloctanyl Acetate, Estragole, Ethyl-2 Methylbutyrate, Fenchol, Fernlol(trademark), Florilys(trademark), Geraniol, Geranyl Acetate, Geranyl Nitrile, Glidmint(trademark) Mint oils, Glidox(trademark), Grapefruit oils, trans-2-Hexenal, trans-2-Hexenol, cis-3-Hexenyl Isovalerate, cis-3-Hexanyl-2-methylbutyrate, Hexyl Isovalerate, Hexyl-2-methylbutyrate, Hydroxycitronellal, Ionone, Isobornyl Methylether, Linalool, Linalool Oxide, Linalyl Acetate, Menthane Hydroperoxide, I-Methyl Acetate, Methyl Hexyl Ether, Methyl-2-methylbutyrate, 2-Methylbutyl Isovalerate, Myrcene, Nerol, Neryl Acetate, 3-Octanol, 3-Octyl Acetate, Phenyl Ethyl-2-methylbutyrate, Petitgrain oil, cis-Pinane, Pinane Hydroperoxide, Pinanol, Pine Ester, Pine Needle oils, Pine oil, alpha-Pinene, beta-Pinene, alpha-Pinene Oxide, Plinol, Plinyl Acetate, Pseudo Ionone, Rhodinol, Rhodinyl Acetate, Spice oils, alpha-Terpinene, gamma-Terpinene, Terpinene-4-OL, Terpineol, Terpinolene, Terpinyl Acetate, Tetrahydrolinalool, Tetrahydrolinalyl Acetate, Tetrahydromyrcenol, Tetralol(copyright), Tomato oils, Vitalizair, Zestoral(trademark), HINOKITIOL(trademark) and THUJOPSIS DOLABRATA(trademark).
The anionic sulfonate surfactants which may be used in the detergent of this invention are water soluble and include the sodium, potassium, ammonium and ethanolammonium salts of linear C8-C16 alkyl benzene sulfonates; C10-C20 paraffin sulfonates, alpha olefin sulfonates containing about 10-24 carbon atoms and C8-C18 alkyl sulfates and mixtures thereof. The preferred anionic sulfonate surfactant is a C12-18 paraffin sulfonate present in the composition at a concentration of about 0.1% to 8wt. %, more preferably 0.25% to 6%.
The paraffin sulfonates may be monosulfonates or di-sulfonates and usually are mixtures thereof, obtained by sulfonating paraffins of 10 to 20 carbon atoms. Preferred paraffin sulfonates are those of C12-18 carbon atoms chains, and more preferably they are of C14-17 chains. Paraffin sulfonates that have the sulfonate group(s) distributed along the paraffin chain are described in U.S. Pat. Nos. 2,503,280; 2,507,088; 3,260,744; and 3,372,188; and also in German Patent 735,096. Such compounds may be made to specifications and desirably the content of paraffin sulfonates outside the C14-17 range will be minor and will be minimized, as will be any contents of di- or poly-sulfonates.
Examples of suitable other sulfonated anionic detergents are the well known higher alkyl mononuclear aromatic sulfonates, such as the higher alkylbenzene sulfonates containing 9 to 18 or preferably 9 to 16 carbon atoms in the higher alkyl group in a straight or branched chain, or C8-15 alkyl toluene sulfonates. A preferred alkylbenzene sulfonate is a linear alkylbenzene sulfonate having a higher content of 3-phenyl (or higher) isomers and a correspondingly lower content (well below 50%) of 2-phenyl (or lower) isomers, such as those sulfonates wherein the benzene ring is attached mostly at the 3 or higher (for example 4, 5, 6 or 7) position of the alkyl group and the content of the isomers in which the benzene ring is attached in the 2 or 1 position is correspondingly low. Preferred materials are set forth in U.S. Pat. No. 3,320,174, especially those in which the alkyls are of 10 to 13 carbon atoms.
The nonionic surfactants which are used at a concentration of 0.1 to 10 wt. % are the water-soluble condensation products of a C8-C20 alkanol with a heteric mixture of ethylene oxide and propylene oxide wherein the weight ratio of ethylene oxide to propylene oxide is from 2.5:1 to 4:1, preferably 2.8:1 to 3.3:1, with the total of the ethylene oxide and propylene oxide (including the terminal ethanol or propanol group) being from 60-85%, preferably 70-80%, by weight. Such surfactants are commercially available from BASF-Wyandotte and a particularly preferred surfactant is a C10-C16 alkanol condensate with ethylene oxide and propylene oxide, the weight ratio of ethylene oxide to propylene oxide being 3:1 and the total alkoxy content being about 75% by weight.
The Plurafac nonionic surfactants are condensation products of a primary alkanol having 9 to 18 carbon atoms with 1 to 5 moles of ethylene oxide and 1 to 5 moles of propylene oxide. Preferred is Plurafac LF300 which is formed from the condensation product of hexanol with 5 moles of ethylene oxide and 1 mole of propylene oxide.
The water soluble nonionic surfactants utilized in this invention at a concentration of 0 to 8 wt. %, more preferably 0.5 to 8 wt. % are commercially well known and include the primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates and alkylphenol ethoxylates. The nonionic synthetic organic surfactants generally are the condensation products of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups. Practically any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a water-soluble nonionic detergent. Further, the length of the polyethenoxy chain can be adjusted to achieve the desired balance between the hydrophobic and hydrophilic elements.
The nonionic detergent class includes the condensation products of a higher alcohol (e.g., an alkanol containing about 9 to 18 carbon atoms in a straight or branched chain configuration) condensed with about 5 to 30 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with about 16 moles of ethylene oxide (EO), tridecanol condensed with about 6 to moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to about 14 carbon atoms in length and wherein the condensate contains either about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.
A preferred group of the foregoing nonionic surfactants are the Neodol ethoxylates (Shell Co.), which are higher aliphatic, primary alcohol containing about 9-15 carbon atoms, such as C9-C11 alkanol condensed with 2.5 TO 10 moles of ethylene oxide (NEODOL 91-2.5 OR -5 OR -6 OR -8), C12-13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C12-15 alkanol condensed with 12 moles ethylene oxide (Neodol 25-12), C14-15 alkanol condensed with 13 moles ethylene oxide (Neodol 45-13), and the like.
An especially preferred nonionic system comprises the mixture of a nonionic surfactant formed from a C9-C11 alkanol condensed with 2 to 3.5 moles of ethylene oxide (C9-11 alcohol EO 2 to 3.5:1) with a nonionic surfactant formed from a C9-C11 alkanol condensed with 7 to 9 moles of ethylene oxide (C9-C11 alcohol EO 7 to 9:1), wherein the weight ratio of the C9-C11 alcohol EO 7 to 9:1 to the C9-C11 alcohol EO 2 to 3.5:1 is from 4:1 to 1:1 from preferably 3.5:1 to 2:1.
Additional satisfactory water soluble alcohol ethylene oxide condensates are the condensation products of a secondary aliphatic alcohol containing 9 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide. Examples of commercially available nonionic detergents of the foregoing type are C11-C15 secondary alkanol condensed with either 9 EO (Tergitol 15-S-9) or 12 EO (Tergitol 15-S-12) marketed by Union Carbide.
Other suitable nonionic detergents include the polyethylene oxide condensates of one mole of alkyl phenol containing from about 8 to 18 carbon atoms in a straight- or branched chain alkyl group with about 5 to 30 moles of ethylene oxide. Specific examples of alkyl phenol ethoxylates include nonyl phenol condensed with about 9.5 moles of EO per mole of nonyl phenol, dinonyl phenol condensed with about 12 moles of EO per mole of phenol, dinonyl phenol condensed with about 15 moles of EO per mole of phenol and di-isoctylphenol condensed with about 15 moles of EO per mole of phenol. Commercially available nonionic surfactants of this type include Igepal CO-630 (nonyl phenol ethoxylate) marketed by GAF Corporation.
The ethoxylated alkyl ester nonionic surfactant has the structure of:
wherein n is a number from 2 to 18, preferably 3 to 15 and x is a number from 6 to 12, preferably 8 to 10. Preferred ethoxylated alkyl esters are Genagen(trademark) 24 and Genagen(trademark) 81.
The major class of compounds found to provide highly suitable water soluble solvent for the composition are water-soluble polyethylene glycols having a molecular weight of 150 to 1000, polypropylene glycol of the formula HO(CH3CHCH2O)nH wherein n is a number from 2 to 18, mixtures of polyethylene glycol and polypropyl glycol (Synalox) and mono and di C1 -C6 alkyl ethers and esters of ethylene glycol and propylene glycol having the structural formulas R(X)nOH R1(X)nOH R(X)nOR and R1(X)nOR1 wherein R is C1-C6 alkyl group, R1 is C2-C4 acyl group, X is (OCH2CH2) or (OCH2(CH3)CH) and n is a number from 1 to 4, diethylene glycol, triethylene glycol, an alkyl lactate, wherein the alkyl group has 1 to 6 carbon atoms, 1 methoxy-2-propanol, 1 methoxy-3-propanol, and 1 methoxy 2-, 3- or 4-butanol.
Representative members of the polypropylene glycol include dipropylene glycol and polypropylene glycol having a molecular weight of 150 to 1000, e.g., polypropylene glycol 400. Other satisfactory glycol ethers are ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monobutyl ether, mono, di, tri propylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, mono, di, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, propylene glycol tertiary butyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monopentyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monopentyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monopentyl ether, triethylene glycol monohexyl ether, mono, di, tripropylene glycol monoethyl ether, mono, di tripropylene glycol monopropyl ether, mono, di, tripropylene glycol monopentyl ether, mono, di, tripropylene glycol monohexyl ether, mono, di, tributylene glycol mono methyl ether, mono, di, tributylene glycol monoethyl ether, mono, di, tributylene glycol monopropyl ether, mono, di, tributylene glycol monobutyl ether, mono, di, tributylene glycol monopentyl ether and mono, di, tributylene glycol monohexyl ether, ethylene glycol monoacetate and dipropylene glycol propionate. These glycol type water soluble solvents are at a concentration of about 0 to about 10weight %, more preferably about 0.5weight % to about 8%. Additional water soluble solvent useful in the instant compositions are C1-C3 alcohols such as methanol, ethanol and isopropanol which can be used in blend with above mentioned glycol ethers blends weight ratios of glycol ethers and alcohol are 1:5 to 5:1, more preferably 1:1.
The instant invention can contain 0 to 8 wt. %, more preferably 0.1 wt. % to 6% of an ethoxylated alcohol selected from the group consisting of C5-C7 alkyl ethoxylates having from 1 to 6 EO groups and C5-C7 alkyl ethoxylate-propoxylates having 1 to 6 EO groups and 0.5 to 3 PO groups.
Generally, amounts of water soluble solvents in the range of from 0.1 wt. % to 10wt. %, preferably from about 0.5 wt. % to 8 wt. % provide stable compositions for the above-described levels of primary surfactants and water insoluble hydrocarbon, perfume or essential and any other additional ingredients as described below.
The instant compositions contain about 0.1 to about 10 wt. %, more preferably 0.25 to 8 wt. % of a disinfectant agent selected from the group consisting of C8-C16 alkyl amines, C8-C16 alkyl benzyl dimethyl ammonium chlorides, C8-C16 dialkyl dimethyl ammonium chlories, C8-C16 alkyl, C8-C14 alkyl dimethyl ammonium chloride and chlorhexidine and mixtures thereof. Some typical disinfectant agent useful in the instant compositions are manufactured by Lonza, S. A. They are: Bardac 2180 (or 2170) which is N-decyl-N-isonoxyl-N, N-dimethyl ammonium chloride; Bardac 22 which is didecyl dimethyl ammonium chloride; Bardac LF which is N,Ndioctyl-N, N-dimethyl ammonium chloride; Bardac 114 which is a mixture in a ratio of 1:1:1 of N-alkyl-N, N-didecyl -N, N-dimethyl ammonium chloride/N-alkyl-N, N-dimethyl-N-ethyl ammonium chloride; and Barquat MB-50 which is N-alkyl-N, N-dimethyl-N-benzyl ammonium chloride.
Another disinfecting agent is dimethyl benzyl alkonium chloride (BASF).
An essential ingredient in the inventive compositions having improved interfacial tension properties is water. The proportion of water in the compositions generally is in the range of 10% to 97%, preferably 70% to 97% by weight.
In addition to the above-described essential ingredients, the compositions of this invention may often and preferably do contain one or more additional ingredients which serve to improve overall product performance.
The instant compositions can include from 0 to 2.5%, preferably from 0.1% to 2.0% by weight of the composition of a C8-C22 fatty acid or fatty acid soap as a foam suppressant.
The addition of fatty acid or fatty acid soap provides an improvement in the rinseability of the composition whether applied in neat or diluted form. Generally, however, it is necessary to increase the level of cosurfactant to maintain product stability when the fatty acid or soap is present. If more than 2.5 wt. % of a fatty acid is used in the instant compositions, the composition will become unstable at low temperatures as well as having an objectionable smell.
As example of the fatty acids which can be used as such or in the form of soap, mention can be made of distilled coconut oil fatty acids, xe2x80x9cmixed vegetablexe2x80x9d type fatty acids (e.g. high percent of saturated, mono-and/or polyunsaturated C18 chains); oleic acid, stearic acid, palmitic acid, eiocosanoic acid, and the like, generally those fatty acids having from 8 to 22 carbon atoms being acceptable.
The multi purpose liquid cleaning composition of this invention may, if desired, also contain other components either to provide additional effect or to make the product more attractive to the consumer. The following are mentioned by way of example: Colors or dyes in amounts up to 0.5% by weight, 2,6-di-tert.butyl-p-cresol, etc., in amounts up to 2% by weight; and pH adjusting agents, such as sulfuric acid or sodium hydroxide, as needed. Furthermore, if opaque compositions are desired, up to 4% by weight of an opacifier may be added.
In their final form, the multi purpose liquids are clear compositions and exhibit stability at reduced and increased temperatures. More specifically, such compositions remain clear and stable in the range of 5xc2x0 C. to 50xc2x0 C., especially 10xc2x0 C. to 43xc2x0 C. and the compositions exhibit a pH in the neutral to the alkaline range.
The compositions are directly ready for use as desired and only minimal rinsing is required and substantially no residue or streaks are left behind. Furthermore, because the compositions are free of detergent builders such as alkali metal polyphosphates they are environmentally acceptable and provide a better xe2x80x9cshinexe2x80x9d on cleaned hard surfaces.
When intended for use in the neat form, the liquid compositions can be packaged under pressure in an aerosol container or in a pump-type sprayer for the so-called spray-and-wipe type of application. The composition can also be dispensed from a non woven or fabric towel which can be used once and discarded or reused several times with adequate rinsing between usage.
Because the compositions as prepared are aqueous liquid formulations, the compositions are easily prepared simply by combining all the ingredients in a suitable vessel or container. The order of mixing the ingredients is not particularly important and generally the various ingredients can be added sequentially or all at once or in the form of aqueous solutions of each or all of the primary detergents and cosurfactants can be separately prepared and combined with each other and with the perfume. It is not necessary to use elevated temperatures in the formation step and room temperature is sufficient.
The instant formulas explicitly exclude alkali metal silicates and alkali metal builders such as alkali metal polyphosphates, alkali metal carbonates, alkali metal phosphonates and alkali metal citrates because if these builders were used in the instant composition, they would cause the composition to have a high pH as well as leaving residue on the surface being cleaned.

Antimicrobial multi purpose containing a cationic surfactant