A process and etchant solution for chemical wet etching of thin film metals in the presence of a protected metal. The etching solution has a pH range of about 2.7 to 4.0. The etching solution may include hydrogen peroxide, potassium sulfate, and potassium EDTA, and it reduces or eliminates the incidence of etch-resistant metal without damaging the protected metal.

Controlled Collapse Chip Connection (C4) is an advanced microelectronic chip packaging and connection technology. C4 is also known as "solder bump" and "flip chip." The basic idea of C4 is to connect chips, chip packages, or such other units by means of solder balls placed between two surfaces of the units. These tiny balls of electrically conductive solder bridge the gaps between respective pairs of metal pads on the units being connected. Each pad has a corresponding pad on the surface of the other unit so that the pad arrangements are mirror images. As the units are aligned and exposed to temperatures above the melting point of the solder, the solder balls on the pads of the first unit become molten and join to corresponding conductive pads (having no balls) on the second unit, making permanent connections between respective pads.
In C4, the solder balls typically are formed directly on the metal pads of the one surface. The bumps are electrically isolated from each other by the insulating material that surrounds each ball. The substrate might be undoped silicon (Si) or some other material. The bottom of the ball is electrically connected to the chip circuit. When the balls are aligned to metal pads on a second surface and reflowed, the liquid solder bumps wet the receiving pads. Upon cooling, relatively low-stress solder joints are formed. This process allows all of the connections to be made in one step, even with slight variations in the surfaces.
A major application of C4 is in joining semiconductor microchips (integrated circuits) to chip packages. Chips may be made in rectangular arrays on a monocrystalline slab of silicon, called a "wafer," which is a thin disc typically several inches across. Many chips may be formed on each wafer, then the wafer is diced into individual chips and the chips are "packaged" in units large enough to be handled. The C4 balls are placed on the chips while they are still in wafer form.
The wafers may be made as large as possible so as to reduce the number of wafers that must be processed to make a certain number of chips. For the same reason (among others), the chips may be made as small as possible. Thus, the best C4 fabrication system is one that can make thousands of very small, closely spaced solder balls each precisely placed over a large area.
C4 allows a very high density of electrical interconnections. Unlike earlier techniques which made connections around the perimeter of a chip or a chip package, C4 allows one or more surfaces of a chip or package to be packed with pads. The number of possible connections with C4 is roughly the square of the number that is possible with perimeter connection. Because the C4 balls can be made quite small, less than a hundredth of an inch in diameter, the surface density of C4 connections can be on the order of thousands per square inch.
Electrical engineers are constantly placing more and more circuits onto each chip, to improve performance and reduce cost. As the number of circuits on a chip grows, so does the number of connections needed. C4, which allows more connections in a small space than any other technique, is commercially important.
In addition to making area connection possible, C4 can also be used with perimeter connection techniques such as tape-automated bonding (TAB). In TAB, solder balls on a chip are pressed against a pattern of metal foil adhered on a plastic substrate of the chip package. These applications, too, are commercially important.
C4 solder bumps must be mechanically well-fastened to their substrates, or they may fail during the thermal stressing that is characteristic of routine device operation. A complex device such as a computer may have dozens of chips and hundreds or thousands of C4 solder ball connections. The entire device may be rendered useless if only one of the balls fails. Thus, the attachment of the C4 balls requires careful design. For this reason various carefully chosen layers may be placed between the solder bumps and substrate or wafer upon which they are built. The composition and characteristics of these interfacial layers, commonly referred to as the Ball Limiting Metallurgy or BLM, play an integral role in ensuring acceptable mechanical adhesion of the solder bump to the chip. In addition, these layers often act as a diffusion barrier between the solder and the chip metallurgy which may be composed of aluminum and/or copper. Without an adequate diffusion barrier, the solder will attack the chip wiring and destroy functionality.
There are several methods of forming solder bumps and BLM metal, one of which uses vacuum deposition. In this method, solder and BLM metal are evaporated in a vacuum chamber. The metal vapor coats everything in the chamber with a thin film of the evaporated metal. To form both metal pads and solder bumps on the wafer or substrate, the vapor is allowed to pass through holes in a metal mask held over the substrate. The vapor passing through the holes condenses onto the cool surface, forming discrete solder bumps. This method requires a high vacuum chamber to hold the substrate, mask, and flash evaporator.
In this approach, the mask is made specially with high-precision holes, or "vias," for locating the solder bumps. The mask will be heated as hot metal vapor released into the vacuum chamber condenses on it. To avoid misalignment of the vias due to thermal expansion, the masks may be made of special metals, and are geometrically compensated to optimize alignment. Even with this methodology, vacuum processing has limitations. After solder deposition, the metal mask cools and undergoes thermal contraction, and must be carefully removed without damaging the solder pads. Thus, this method cannot be used for extremely large wafers containing many chips.
An alternative technique for making solder bumps is electrodeposition, also known as electrochemical plating or electroplating. This method also uses a mask and forms solder bumps only at the selected sites, but this technique differs from the evaporation method in that the mask is created using photoprocessing. In addition, it requires a first preliminary step to create a continuous "seed layer" of conductive metal adhered onto the insulating substrate. The seed layer is needed to conduct the electricity which deposits solder. The seed layer is typically composed of several metal layers, which serve the additional purpose of forming the BLM metallurgy.
Examples of first layers used in this method include chromium (Cr), titanium-tungsten alloys (TiW), or any other metals which adhere well to the substrate at hand. This metal layer, which will function as part of the seed layer for electrodepositing solder balls, might be a ten-thousandth of a millimeter thick. On top of the first layer may be deposited a second layer, which may be an alloy of chromium-copper (CrCu) or nickel-vanadium (NiV). Finally, a third layer, usually of pure copper is deposited over the other layers. The thickness of the layers may vary, and is typically chosen to optimize the stress-thickness product, diffusion properties, and mechanical integrity.
The second preliminary step, after the seed layer is laid down, is to form a mask by photolithography. A layer of photoresist is laid onto the seed layer and exposed to light which cures the exposed photoresist. The unexposed photoresist remains uncured and can then be washed away to leave the cured photoresist behind as a mask, and, thus, the mask is complete. The complete mask has rows of holes where the solder bumps are to be deposited.
The third step is electrodeposition (electroplating) of lead or other solder alloy into the mask holes. An electrodeposited solder bump might be 0.25 millimeter high and contain a small amount of tin (Sn) and, thus, it will adhere well to the uppermost copper layer. Upon reflow, copper and tin react to form an "intermetallic" layer, Cu.sub.x Sn.sub.y (for example, Cu.sub.3 Sn), which creates a robust solder-to-BLM interface. It should be noted that plating processing is not subject to the same dimensional limitations as evaporation processing, and is extendible to very large wafers.
After the solder bumps are formed, the mask of cured photoresist is removed. The substrate is then covered with the continuous seed layer and numerous solder bumps.
After the seed layer is deposited over the substrate and the C4 bumps have been formed, the seed layer is removed from between the solder bumps to electrically isolate them. The removal can be accomplished by chemical etching, electroetching, or plasma etching. Removal of the seed layers leaves the solder bumps electrically isolated but mechanically fixed to the substrate. Regardless of the method used for seed layer removal, the solder bump protects the metal layers under it during processing. Thus, isolated BLM pads underneath the solder bumps are created. Finally, a solder ball can be formed by melting or reflowing, and it is then ready to join to a receiving substrate.
Alloys of titanium-tungsten (TiW; tungsten is also called "wolfram") have been used in the prior art as "barrier" layers to protect chip parts for a wide variety of applications. TiW is metallic and will conduct electricity. A thin film of TiW can be applied by conventional microelectronic techniques including sputtering. As discussed above, the use of TiW as a first layer in C4 fabrication by electroplating is one such employment. If TiW is used, it may be desirable to remove the TiW at some stage of fabrication. The problem of removing TiW has been addressed by several patents.
U.S. Pat. No. 5,130,275 teaches post-fabrication processing of semiconductor chips. Its method is intended for solder joining of chips to TAB packages, where the solder is flowed rather than crushed to make the connection. It employs a barrier metal layer, of 10% Ti and 90% W by weight, coated over aluminum (Al) or gold (Au) interconnect pads and a passivating layer of SiO.sub.2. A Cu or Au seed layer is coated over the barrier layer. The thickness of metal over the pads is increased by electrodeposition of Cu or Au bumps into holes in a photoresist mask. Solder containing Sn is deposited on. top of the Cu or Au. Subsequently, first the seed layer and then the barrier layer are etched away to leave the built-up pads ready for soldering.
The seed layer, if of gold, is removed by chemical etching in 10% potassium cyanide. This etchant attacks the bump as well, but this disclosure accepts the resulting bump damage and asserts that it is minimal, because the bump is 25 microns thick whereas the seed layer is only 0.3 microns thick.
Next, the TiW barrier is etched in an aqueous solution of 30% hydrogen peroxide. The disclosure notes (column 8, line 37) that peroxide can corrode the solder bead atop the Cu/Au bump. Prevention of corrosion is taught by adjusting the pH of the solution to between 9 and 11 (basic). The preferred solution is 7% oxidized ammonium persulfate and 1% to 2% hydrogen peroxide, with the pH adjusted to between 9 and 11 by adding ammonium hydroxide. Nevertheless, these etchants will attack aluminum.
U.S. Pat. No. 5,041,191 teaches a 10% Ti-90% W barrier layer. It uses the TiW layer to prevent undesirable intermetallics that form when Au, Cu, or Al contacts are deposited directly onto a thin-film resistor of nickel-chromium alloy. The TiW etchant is 5 grams of cupric sulfate (CuSO.sub.4), 10 ml ammonium hydroxide (NH.sub.4 OH), 100 ml glycerol, and 125 ml deionized water.
This solution does not affect the nickel chromium, according to the disclosure. Nevertheless, like the etchant of the '275 patent, this solution is alkaline and will attack aluminum.
U.S. Pat. No. 4,671,852 teaches an etchant comprised of hydrogen peroxide, ethylenediaminetetraacetic acid (EDTA), and ammonium hydroxide for removing a thin (0.05-0.10 microns) film of 10%-30% by weight Ti and 90%-60% by weight W. The device to be etched is a chemically sensitive Silicon Gate Field Effect Transistor (SGFET) structure with an internal cavity. Etchant is introduced into the cavity, which also contains a noble metal (platinum) and an aluminum oxide or silicon oxide "fugitive" layer. The etchant is intended to selectively etch the TiW film.
This etchant is 0.1 molar EDTA, 30% hydrogen peroxide, and concentrated ammonium hydroxide mixed in a respective volume ratio of 10:3:2. The disclosure states that the pH should be less than 11 (not too basic). It also teaches the use of other complexing agents in addition to EDTA, such as carboxylates, bipyridines, and the like, but no formulas or other details about these agents are provided. The etchant of this invention, too, will attack aluminum.
U.S. Pat. No. 4,814,293 also teaches chemical etching of 10% Ti-90% W. It notes that hydrogen peroxide causes inhomogeneous etching. In particular, features are irregularly undercut or under-etched when TiW films are layered between other metals. The agitation commonly used is ineffective in reducing the uneven results, and this disclosure advocates stagnant liquid etchants. The peroxide solution is buffered to a pH value between 1 and 6 (acidic). The preferred buffering compounds are acetic acid and ammonium acetate. Citric acid and sodium hydroxide are also used and the etch rate is varied with the pH. The solution of the '293 patent will severely attack lead-tin (PbSn) alloys such as solder. Moreover, the disclosure does not address selective etching of TiW in the presence of PbSn.
U.S. Pat. No. 4,554,050 teaches the use of Ti etchants in fabricating waveguides. Its etchant is composed of EDTA, water, hydrogen peroxide, and ammonium hydroxide. One formula presented is 2.5 g of disodium EDTA in 100 ml of deionized water (a 0.067 M solution) with 10 g hydrogen peroxide and 4.2 g ammonium hydroxide, having a pH of about 10.
The etch rate is controlled by varying the OH.sup.- concentration and the temperature. The solution was tested at 20 degrees C. (room temperature) and at 60 degrees C. The '050 patent disclosure indicates that its solution will etch aluminum. Moreover, its solution will also attack PbSn.
U.S. Pat. No. 5,462,638 discloses a chemical etchant used to remove thin TiW films and a method of forming the etchant. The preferred alloy to be removed is 10% Ti and 90% W, which is deposited on a substrate. Chromium and copper seed layers are deposited on the TiW layer and C4 solder bumps are formed.
The disclosed etchant comprises between 1 and 2 parts of 30% by weight aqueous hydrogen peroxide, between 1 and 2 parts of an aqueous EDTA solution of between 15 and 40 g/l, and between 100 and 200 grams of salt per liter of the mixture. The salt is described as passivating the protected metal with a protective coating so that the protected metal is not attacked by the etchant.
Previous etchant compositions and methods used to remove TiW seed layers for C4 applications have encountered difficulties such as residual metal on the wafer and significant undercutting beneath the solder pad. FIGS. 2A and 2B show a wafer 2 having C4 solder bumps 4 with residual metal 12 and areas of excessive undercutting 20. In addition, under certain conditions, parts of the metal film to be removed can become etch-resistant, thus leaving un-etchable parts of the metal film. Longer etch times are ineffective at removing these residuals. These defects have caused silicon wafers to be inefficiently produced or inoperative. A need remains, therefore, for an improved process which overcomes the shortcomings of the conventional etching processes.

Process improvements for titanium-tungsten etching in the presence of electroplated C4's

International Business Machines Corporation


Systems, methods, and computer-readable medium storing instructions can be used to predict insurance information. One of the methods includes obtaining information about an insured entity. The method includes providing the information to a machine learning system, the machine learning system trained to provide insurance information based on the provided information. The method includes in response to providing the information, receiving a prediction of the insurance information. The method also includes adjusting an insurance premium based on the prediction.

Insurance is a means of protection from financial loss. It is a form of risk management primarily used to hedge against the risk of a contingent, uncertain loss. Typical insurance transactions can involve the insured assuming a guaranteed and known relatively small loss in the form of payment to the insurer in exchange for the insurer's promise to compensate the insured in the event of a covered loss. The loss may or may not be financial, but it is generally reducible to financial terms, and involves something in which the insured has an insurable interest established by ownership, possession, or preexisting relationship.

This patent is subject to a terminal disclaimer.

United Services Automobile Association (USAA)


A rubber band driving device for two-propeller model plane, mainly comprising a power rubber band 1, a wooden skeletal bar 2, a rubber band winder 3, a rubber band locator 4, a power distributor 5, transmission bars 6, support bars 7, a left propeller gear box 8, a right propeller gear box 9, propeller blades 10 and 20, a propeller space locator 30, and a propelling direction adjuster 40, wherein the power rubber band 1 is connected to the rubber band winder 3 and the power distributor 5, and the power stored in the power rubber band 1 is transmitted, through the distributor 5 and the transmission bars 6, to the left and right propeller gear boxes 8 and 9, to set in motion their blades 10 and 20. The driving device disclosed in the present invention is reasonable in structure, stable in work, easy to maintain and repair, and is suitable for various kinds of two-propeller emulation model planes.

The present invention relates to a driving device for a model plane, particularly, to a rubber band driving device for a two-propeller model plane, in which the two propellers rotate in opposite directions at equal speed.
Model planes of various kinds are being developed in many a country the world over; and development on model planes driven by rubber band has a long lead, since such models are easy and quick to assemble, safe to use, involve a low cost, and have low requirements as to the environment for use. In addition, such model planes fly gracefully; they are, therefore, widely and much used for purposes of aeronautic education and scientific popularization. They also suit outdoor games and serve as children toys as well.
In recent years, rubber band driven model planes, particularly emulation planes, have been a big hit among the public. Nevertheless, the conventional rubber band driven emulation model planes are all of the single-propeller type, since the single-propeller device results in a simple transmission mechanism, and is easy to manufacture. It is, however, noted that in the past years it was still the two-propeller model that was most welcomed by the public and became marked in the history of model planes; and people have been eager to be provided with emulation model planes of this kind. In recollection of history, an example is the xe2x80x9cNo. 1 Flyerxe2x80x9d designed and test flown by the American Wright Brothers. That serves as a push for us to develop, as soon as possible, a rubber band driven two-propeller model plane.
Based on the above prior art, it is the object of the present invention to provide a rubber band driving device for a two-propeller emulation model plane, in which a single rubber band is used to drive two propellers to rotate at equal speed and in opposite directions, with a simple control switch and a rubber band winder suited for use with rubber bands of different powers. Another object of the present invention is to provide a rubber band driving device, reasonable in structure, simple to manufacture, and easy to maintain and repair, to be applied to various kinds of model planes. The driving device of the present invention comprises a power rubber band, a wooden skeletal bar, a rubber band winder, a rubber band locator, a power distributor, transmission bars, support bars, a left propeller gear box, a right propeller gear box, blades of the propellers, a propeller space locating bar, and a propelling direction adjuster; wherein the rubber band winder is connected to one end of the wooden skeletal bar, and on the wooden skeletal bar there are fitted a rubber band locator, a power distributor, and a propelling direction adjuster; said power rubber band being linked at one end to the rubber band winder, and to the power distributor at the other end. Two transmission bars and two support bars are connected, respectively, to the said power distributor, and further to the left and right propeller gear boxes. The propeller space locating bar is connected at both ends to the left and right propeller gear boxes, and form, together with the two support bars a triangular structure. Blades are fitted onto the left and right propellers.
In accordance with the present invention, in the preferred embodiment of the invention, there is provided a single rubber band driving device for an emulation model plane with two propellers. When a winding handle is inserted into a ratchet gearing box to wind up clockwise the said rubber band, the latter will store up power; and when a switch is pushed, by means of two drive screws, a driving torque will be transmitted from the rubber band to the gear boxes of both the right and the left propellers; and by means of different arrangement in the two gear boxes, the two propellers will rotate at equal speed but in opposite directions. As a switch is provided, unless it is pushed on, the dynamic power stored in the said rubber band will not be released.
The driving device for two-propeller model planes according to the present invention has the following advantages: 1) The emulation requirements for model planes are better met with, so that the quality of products, as well as amateursxe2x80x2 interest therein, are much raised and the sphere for emulation model planes is further developed. 2) As propelling direction adjusting in both longitudinal and transverse directions is possible, the propelling force can be kept stable, thus also stabling the flight of the model plane. 3) As two propellers are used which rotate in opposite directions, the gyro moment can be removed, thus also realizing stable flight. 4) As rubber bands of different kinds can be replaced, a variety of horsepower to weight ratios are available. 5) A rubber band winder and a switch adopted in the present invention make possible to store power, and flight can be easily manipulated. 6) A triangular structure formed by the propeller space locator and the two support bars, provides, together with the various connecting parts of the model plane, a robot driving device of very stable structure. 7) The driving device for a two-propeller model plane according to the present invention is easy and convenient to assemble and disassemble, and simple to maintain and repair.
The above advantages as well as others will be clearly seen in a detailed description below, in connection with the accompanying drawings.

Rubber band driving device for two-propeller model plane

Room 1002, 10/F, Singga Commercial Centre, 148-152 Connaught Road West


In a device for connecting several functional electric elements arranged on a transparent window, such as antennas for example, by a single flexible cord element and of its connection conductors to sets which follow, the contact faces (10) of the functional elements (3, 4) that are to be connected by means of this contact element (8) are distributed along the edge of the window (1), the contact element has a shape tailored to the edge of the window (1) and also acts as a support for circuit elements (9) arranged in close proximity to the contact faces (10) and is electrically connected thereto.

The present application is based on German patent application 100 02 777.6, filed Jan. 22, 2000, which is herein incorporated by reference in its entirety.
The invention relates to a device for connecting a window, particularly a window for a motor vehicle, with certain electrical functions.
Document DE-C1 195 36 131 discloses a diversity window antenna with connecting elements, which is preferably used for vehicles. The antenna elements and the antenna conductor structures, are deposited on the surface of a window by screen printing and are baked on when the window is heated before it is toughened. There are a number of antennas on the same window, so that incident transmitters having various directions of reception can be used, and the transmitter with the optimum field intensity is selected automatically each time.
In the configuration disclosed by that document, connection points of the individual antennas are grouped together locally at the edge of the window. A multiple contact element in the form of a length of special flat cable is placed at this point and, for each connection, comprises a mating contact in addition to the corresponding conductor. The electrical signals from the antennas are transmitted along these conductors to the respective amplifiers located remotely from the window.
Simple AM/FM antennas have been made in windscreens, side windows or rear screens for a number of years, either by placing metal wires in the laminated safety glass windscreen or by using conductive structures printed onto single-pane safety glass in the case of the side windows or rear window. It has also been known to use the heating area of rear screens to make an antenna. For connection to the sets (receivers), use is also frequently made of plug-in connectors or spring contacts.
It is also known (DE-GM 75 27 621) for a unit contacting the amplifier to be bonded onto the window glass so as to make a direct connection between an antenna amplifier and antenna conductors placed on a window glass. Two antenna conductors in conducting connection with one another inside the amplifier unit are connected directly to the input terminals of the amplifier and are also bonded to the window glass. On the output side, the amplifier is connected by a flat multicore cable to the on-board network (supply voltage) and the receiver apparatus.
DE-C2-43 04 788 discloses a multilayer conducting structure for connecting functional electric elements arranged on a car window, such as window antennas for example, and which can be connected to the on-board network of the vehicle using a connection element of the push-button type which is soldered onto an opaque edge region of the window.
Future development in vehicle driver information requirements, with the increase in traffic density, has led to the networking of various information systems with a view to intelligently managing the flow of vehicles in such a way that, for example, their position can be exactly determined using a global positioning system (GPS) in conjunction with automatic rotate planning, and stationary installations for measuring traffic flow can allow this objective to be pursued in the optimum way. Furthermore, there has been research into the automatic transmission of messages analyzing accidents and theft, video games in the passenger seat, ranging as far as Internet connections inside the vehicle. The future role of the vehicle driver as an active and passive participant in a broad wireless information and communications network entails the development of corresponding on-board receiver systems which activate the information systems in the vehicle. These receiver systems comprise the built-in antenna systems for the individual communications services including the electronics needed for the amplifiers and impedance matchers, respectively.
The information systems currently used in vehicles are AM and FM radio transmitters, UHF video transmitters, GSM telephones and GPS navigation aids. Hitherto, these have been connected to individual networks partially by separate stick-like, spherical or crescent-shaped antennas.
The fixture may conceivably, in addition to the networking of the systems, see developments in which bulletins giving weather and road conditions, DAB (digital radio), Internet connections, network monitoring in the form of accident or theft analysis or telesurveillance, etc. also communicate via a wireless connection with the occupants and respectively with the equipment of the vehicle.
Such a multitude of installed systems leads to a corresponding multitude of antennas. Installing these externally on the vehicle is undesirable both from an aesthetic point of view and for reasons associated with possible breakdowns due to damage. Development trends are therefore oriented towards invisible installation of antenna systems on electrically insulating regions of the bodywork such as parts made of glass or plastic, for example. The incorporation of complicated antenna structures in vehicle window glass is dictated because of the large expanse of glass or plastic surfaces and because of the ideal dielectric properties of glass or suitable plastics.
For vehicles with the engine at the front, positioning the antenna systems on the rear screen or rear window proves the optimum solution for reasons of electromagnetic compatibility, whereas such systems are preferably installed in the windscreen in vehicles with mid-rear-mounted engines and also those with convertible bodywork.
All the systems have to meet the requirement of panoramic reception with as little disturbance as possible. Using a two-dimensional antenna to secure this can be achieved only through the fact that, in each position of the vehicle, the optimum position of the antenna with the strongest signal is selected using a controller from a diverse multitude of antennas in various positions on the window (diversity system) and introduced into the on-board information systems. The number of individual diversity systems needed depends on the geometric configuration, on the specific electromagnetic compatibility of the vehicle, and on the possibility of obtaining high signal intensities by mixing signals (phase-amplitude sum).
The integration of numerous antenna systems into a car window, if appropriate, in conjunction with heating elements, requires suitable connections between the reception systems and the communication sets which follow. Conventional flat connection systems cannot be used as they are, because many car windows have a highly complex shape in which, in particular, the edges of the windows may be spherically curved and with relatively small radii. Furthermore, the connection systems to be used have to meet strict motor industry standards regarding stability with respect to inclement weather and with respect to temperature and ability to withstand vibration, etc.
The conventional technique of electrical connection by screen printing onto glass cannot be applied in all cases because of the porosity of the conducting structures thus produced, which may lead to the absorption of moisture from the environment of the vehicle and thus to electro-corrosion or even short circuits.
According to another requirement, the antenna amplifier and the impedance matcher ought to be positioned as close as possible to the individual antenna bases in order to guarantee reception which is as good as possible with a broad protection margin. In complicated systems of this type, the antenna bases ought to be located at relatively large distances from one another on the face of the window because, particularly in diversity systems, there is a strong dependency between the intensity of a field detectable on a window antenna and the direction of radiation of the transmitter concerned.
Window antenna systems are also known (DE-A1 39 11 178) in which electric components are placed directly on, in or in proximity to, a vehicle window, and all the antenna signals and supply voltages are supplied by a single wiring harness made up of high-frequency conductors and supply lines. It is necessary to have a window antenna which can be installed as a complete unit in the bodywork of the vehicle and which is electrically connected to the bodywork, and to the network associated with the bodywork, merely by a single multiple connection in the form of a wiring harness. Antenna amplifiers (of the quadripole type) of this system are, however, fixed directly to the window and soldered to the input and output lines made thereon by screen printing.
It is an object of the invention to provide a connecting device which makes it possible, in a simplified way, to connect electrical functions arranged on a window in a decentralized manner, particularly antenna elements.
According to the invention, this and other objects are advanced by a connecting device in a window unit comprising a transparent window and at least two functional electric elements mounted on said transparent window, each of the functional electric elements being provided with an electrical contact face arranged on the window near the edge of the window, the connecting device comprising a contact element in the form of a body mounted to the window at the edge of the window, the body covering the contact faces; at least two conductors insulated from one another and arranged in the body; and a circuit element supported by said body, wherein the conductors are positioned to make electrical connection with at least one of said electrical contact faces of said functional electric elements covered by said body and said circuit element.
Thus, the connection faces of the functional electric elements are distributed along the edge of the window, particularly in its corner regions. So the connection conductors can be shortened. Furthermore, the contact element has a shape tailored to the line of the edge of the window so that it can easily follow the curvature of the fixed window. Its mating contacts may be applied, in the mounted position, to the position of the connection faces connected to the window. Finally, on the contact element in close proximity to the mating contacts, there are circuit elements mounted electrically, such as electronic modules for example, particularly amplifiers. The body of the contact element is thus used not only as an insulation or sheath for the conducting tracks on lines which run through it, but also as a support for the circuit elements. The body of the contact element may be made up of a laminate of several layers.
In use on car window glass the dimensions of the contact element on the face of the window and, in particular, on the area of the edge thereof, are limited because the field of view through the window must not be impaired. The total length of the contact element is dimensioned according to requirements. It is possible to use not only contact elements in the form of bands extending along one of the upper and/or lower edge faces of the window, but also along one or two lateral edge faces and, if appropriate, also just along part of the edge faces, and finally also versions in the shape of an L or U. Their external dimensions are essentially predetermined by the number, arrangement and mutual distances of the connection or contact faces for functional elements in the region of the edge of the window.
Corner pieces along the line of the contact element may be made from a piece homogeneous therewith, or the conductor passing through this point may be produced by separate corner connectors which subdivide the contact element into several sections. Such corner connectors can be combined with the connection points needed between the conductors or the contacts element and the functional elements on the window.
As a preference, the application and connection regions provided in the contact element for the circuit elements (unit, electronic modules) are strengthened so as to allow them to be manufactured by robots as appropriate. Such strengthening may be achieved by local increased thicknesses of material, locally limited rigid inserts in the contact element which elsewhere is flexible, or by fitting rigid additional parts above or below them.
To assemble the contact element with the window, use is preferably made of a layer of adhesive. This may be a single layer which has been deposited on just one side on the underside of the contact element, which has to be applied to the window, respectively on the edge band thereof. In another embodiment, the layer of adhesive may be a piece of double-sided sticky tape, one side of which is bonded to the underside of the contact elements and the other side of which is bonded to the edge band. An isoprene or acrylate adhesive may be used as the adhesive.
Likewise, the individual mating contacts intended for the respective connection face on the window (for example the antenna bases) are preferably pre-equipped with solder or conducting adhesive, so as to simplify the making of the respective connections. If these have to be made by soldering, then the material of the support for the contact element or, respectively, the conducting sheet itself, will be made of a material which resists heat, for example the plastic polyimide. If the electrical contacts to the window are to be made by bonding, then there is less restriction in the choice of materials for the support sheet as far as temperature sensitivity is concerned.
It is also possible to provide appropriate positioning accessories on the contact element, these clearly defining in advance its orientation and its position on the edge of the window, and its distance from this edge, and thus assisting with mounting and making the latter easier. These accessories may for example be end-stops to be placed on the frontal edge face of the window. They may be assembled rigidly, possibly as a single piece with the body of the contact element. When the frontal edge faces of the window have to be unimpeded all the way around in the mounted state, these mounting accessories may be assembled with the contact element or with the matrix thereof, for example by means of ribs equipped with areas of lower strength. These can rapidly and easily be detached once the contact element has been definitively placed on the window, so as to remove the stops which have now become unnecessary.
The respective electrical contacts may also be made by means of mechanically joined assemblies, for example of the push-button type, which are also already known for this type of application. They may furthermore be used, on the one hand, as positioning accessories in the sense already mentioned and, on the other hand, do not preclude combined additional assembly by soldering or bonding.
In a particularly preferred embodiment of an application to a transparent window, the flexible contact element is bonded onto an edge region of the window, which region is covered with an opaque screen-printed area in the form of a surround. Such decorative surrounds are customary on all window glasses designed to be bonded directly onto the bodywork, to prevent the adhesive used from being seen and to prevent the adhesive from being degraded by UV radiation. When such a window is in the mounted state, this opaque coating is covered with interior trim elements towards the interior space of the vehicle, over a width such that the contact element is not visible from the inside. A preferred embodiment relates to a rear screen, which in its upper region has a screen-printed band more then 20 mm wide, which is suited to a pre-existing flexible conducting sheet.
In total, in the opaque printed region the edge of the window, it is possible to have a flexible structure entirely electrically integrated with conducted channels or bundle of cables, including all the electronics modules, which is entirely covered by the interior trim that is to be mounted later. This structure maintains a distance greater that 6 mm away from the edge of the window, this distance being predetermined by the deposition of the bead of adhesive for bonding the window into the bodywork, including any premounted surround.
Aside from its function of supporting the circuit elements, modules and conducting channels, the printed circuit may also, in special embodiments, itself constitute a support for other antenna structures. Such antenna structures on the face of the window could thus be greatly reduced or even disappear completely depending on the vehicle equipment. This structure of conducting channels could, for example, be produced on two planes of the flexible printed circuit so that the antenna structures are provided with contacts which run along on one plane, and so that the connecting conductors are provided on at least another plane, including the mounting of the circuit elements and modules.
Such technology would markedly increase the flexibility of the work for customer-specific solutions because changes in the layout of such a conducting sheet will be less expensive than the measures which are expensive overall, for example, involving altering a screen-printing stencil.
It is also possible, as part of the standardization of window types, to conceive of FM, AM and UHF antennas to be incorporated into the glass using screen printing technology, and for GHz antenna systems for GSM and GPS to be incorporated directly into or onto the printed circuit.
Another embodiment may additionally comprise electronic sensors on the printed circuit, such as a dew detector, for example, in the form of a printed sinuous structure or a breakage detector, for example in the form of a conducting loop, which can be powered with a standby current which is interrupted in the event of breakage.
There may also be incorporated into the plane of the conductors of the contact element the current pick-up bars for the heating conductors for rear screens made of single-pane safety glass, which may once again be connected directly to the AM or FM signal processing means.
The contact element will have output leads for connection to the functional sets and elements provided on the bodywork, particularly a diversity operating circuit. These leads are preferably brought together at an interface so that a multiple connector can be used for later correction. If need be, for example to avoid mutual influence of the various flows of signals or of currents, it may also be conceivable to provide several interfaces of this type. In particular, it is also possible to use electro-optical coupling or optical coupling in place of purely electrical coupling, the interface then having to be equipped with corresponding light waveguides and the contact element possibly having to be equipped with electro-optical converters.
The contact element thus formed can be offered in the form of a flexible printed circuit or printed circuit sheet like a premounted comb of cables for the window, and which can, to a large extent, corresponding to the respective configuration of the electrical and/or electronic circuit elements, incorporate functions such as amplification operation, tuning, signal conversion, voltage distribution, etc., and all the internal connections of the conductors for the antenna and control signals and also, as appropriate, the supply voltages.
Common conductors for the control signals and conducting bars for distributing the voltage and earthing terminals and possibly softening terminals may also be provided for example. Furthermore, there may also be provided, in place of, or in addition to, electrical conductors, light waveguides for optical transmission of signals, electro-optical converters, possibly being provided as other circuit elements connected to the contact element.
In consequence, by the placing, the fixing and the placing in electrical contact of the contact element already equipped with the prefabricated electronic components, a multitude of, or even all of, the connection faces on the window are all placed in contact at once even though they do not have to be closely spaced as they were in the state of the art discussed in the introduction.

Device for connecting a window with electrical functions


The present invention relates to the use of a 24-membered cyclodepsipeptide of the formula (I)

The present invention relates to the use of a 24-membered cyclodepsipeptide for controlling animal pests in agriculture, forests and the protection of materials, and to pesticides comprising this depsipeptide.
Cyclic depsipeptides, and their preparation and use as parasiticides against helminths, nematodes and trematodes in animals (endoparasiticides) have already been the subject of numerous publications.
Known is, for example, a cyclodepsipeptide with the name PF 1022A and its action against endoparasites (EP-A 382 173 and EP-A 503 538). Further cyclic depsipeptides (cyclooctadepsipeptides: WO 98/55 469; WO 98/43 965; WO 93/19 053; EP-A 634 408; WO 94/19 334; WO 95/07 272; EP-A 626 375; EP-A 626 376; EP-A 664 297; EP 634 408; EP-A 718 298; WO 97/09 331; cyclohexadepsipeptides: WO 93/25 543; WO 95/27 498; EP-A 658 551; cyclotetradepsipeptides: EP-A 664 297; dioxomorpholines: WO 96/38 165; JP 08 225 552) and open-chain depsipeptides (EP-A 657 171; EP-A 657 172; EP-A 657 173; WO 97/07 093) and their endoparasiticicidal action have been described.
Furthermore, it is already known that certain 24-membered cyclodepsipeptides, for example bassianolide and PF1022A, have insecticidal activity against silkworms (cf. M. Kanaoka et al., Agric. Biol. Chem. 43 (5), 1979, pp. 1079-83; JP 05 271 013).
However, the insecticidal activity of these prior-art compounds is, in particular at low application rates and concentrations, not entirely satisfactory in all areas of use.
The invention relates to a composition for controlling animal pests, characterized in that it comprises the compound of the formula (I)
The invention furthermore relates to the use of the compound of the formula (I) for controlling animal pests, in particular insects.
The cyclodepsipeptide of the formula (I) which can be used according to the invention and its preparation are known from EP-A 634 408 (WO 93/19 053) and EP-A 872 481 (WO 97/02 256).
Surprisingly, it has been found that the compound of the formula (I) is highly suitable for controlling animal pests in agriculture, in particular in crop protection, forestry and the protection of materials.
With good plant tolerability and favourable homoiothermic toxicity, the active compound is suitable for controlling animal pests, in particular insects, arachnids and nematodes, which are encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene sector. It is active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:
From the order of Isopoda, for example, Oniscus asellus, Armadillidium vulgare and Porcellio scaber.
From the order of the Diplopoda, for example, Blaniulus guttulatus.
From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec.
From the order of the Symphyla, for example, Scutigerella immaculata.
From the order of the Thysanura, for example, Lepisma saccharina.
From the order of the Collembola, for example, Onychiurus armatus.
From the order of the Orthoptera, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blatella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria.
From the order of the Dermaptera, for example, Forficula auricularia.
From the order of the Isoptera, for example, Reticulitermes spp.
From the order of the Anoplura, for example, Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.
From the order of the Mallophaga, for example, Trichodectes spp. and Damalinea spp.
From the order of the Thysanoptera, for example, Hercinothrips femoralis and Thrips tabaci.
From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.
From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.
From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp, Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and Tortrix viridana.
From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica.
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.
From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa.
From the order of the Siphonaptera, for example, Xenopsylla cheopis and Ceratophyllus spp.
From the order of the Arachnida, for example, Scorpio maurus and Latrodectus mactans.
From the order of the Acarina, for example, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.
The phytoparasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp. and Trichodorus spp.
The active compound of the formula (I) which can be used according to the invention is particularly distinguished by an excellent activity against phytopathogenic pests, in particular against lepidoptera such as the caterpillars of the owlet moth (Spodoptera frugiperda) and army worm (Heliothis virescens) larvae.
The active compound can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Suitable liquid solvents are essentially aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes of methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water.
As solid carriers there are suitable:
for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite and also synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifiers and/or foam-formers there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates and also protein hydrolysates; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methyl cellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and also natural phospholipids such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
The active compound according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations, as a mixture with other active compounds, such as insecticides, attractants, sterilizing agents, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas and substances produced by microorganisms.
Examples of particularly advantageous mixture components are the following compounds:
Fungicides:
2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2xe2x80x2,6xe2x80x2-dibromo-2-methyl-4xe2x80x2-trifluoromethoxy-4xe2x80x2-trifluoro-methyl-1,3-thiazole-5-carboxanilide; 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide; (E)-2-methoxyimino-N-methyl-2-(2-phenoxy-phenyl)-acetamide; 8-hydroxyquinoline sulphate; methyl (E)-2-{2-[6-(2-cyano-phenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate; methyl (E)-methoximino-[alpha-(o-tolyloxy)-o-tolyl]-acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
calcium polysulphide, captafol, captan, carbendazim, carboxin, quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine, drazoxolon,
edifenphos, epoxyconazole, ethirimol, etridiazole,
fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox,
guazatine,
hexachlorobenzene, hexaconazole, hymexazol,
imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione, isoprothiolane,
kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture,
mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil,
nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,
ofurace, oxadixyl, oxamocarb, oxycarboxin,
pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
quintozene (PCNB),
sulphur and sulphur preparations,
tebucanozole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
validamycin A, vinclozolin,
zineb, ziram.
Bactericides:
bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
Insecticides/Acaricides/Nematicides:
abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azamethiphos, azinphos A, azinphos M, azocyclotin,
Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, baculoviruses, Beauveria bassiana, Beauveria tenella, bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin, bifenazate, bifenthrin, bioethanomethrin, biopermethrin, BPMC, bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim, butylpyridaben,
cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, chlovaporthrin, cis-resmethrin, cisperrnethrin, clocythrin, cloethocarb, clofentezine, cyanophos, cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,
deltamethrin, demeton M, demeton S, demeton-S-methyl, diacloden, diafenthiuron, diazinon, dichlorvos, diflubenzuron, dimethoat, dimethylvinphos, diofenolan, disulfoton, docusat-sodium, dofenapyn,
eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp., esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox, etoxazole, etrimfos,
fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazinam, fluazuron, flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron, flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate, fubfenprox, furathiocarb,
granulosis viruses,
halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene,
imidacloprid, isazophos, isofenphos, isoxathion, ivermectin,
lambda-cyhalothrin, lufenuron,
malathion, mecarbam, metaldehyde, methamidophos, Metharhizium anisopliae, Metharhizium flavoviride, methidathion, methiocarb, methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, monocrotophos,
naled, nitenpyram, nithiazine, novaluron, nuclear polyhedrosis viruses,
omethoat, oxamyl, oxydemethon M,
Paecilomyces fumosoroseus, parathion A, parathion M, permethrin, phenthoat, phorat, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb, propoxur, prothiofos, prothoat, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen, pyriproxyfen,
quinalphos,
ribavirin,
salithion, sebufos, silafluofen, spinosad, sulfotep, sulprofos,
tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, temivinphos, terbufos, tetrachlorvinphos, theta-cypermethrin, thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate, triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb,
vamidothion, vaniliprole, Verticillium lecanii,
YI 5302,
zeta-cypermethrin, zolaprofos,
(1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]2,2-dimethylcyclopropanecarboxylate,
(3-phenoxyphenyl)-methyl 2,2,3,3-tetramethylcyclopropanecarboxylate,
1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,
2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydro-oxazole, 2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione,
2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,
2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,
3-methylphenyl propylcarbamate
4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,
4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,
4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)-methoxy]-3(2H)-pyridazinone,
4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,
Bacillus thuringiensis strain EG-2348,
[2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid,
2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-yl butanoate,
[3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,
dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde,
ethyl [2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,
N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine,
N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,
N-[(2-chloro-5-thiazolyl)methyl]-Nxe2x80x2-methyl-Nxe2x80x3-nitro-guanidine,
N-methyl-Nxe2x80x2-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,
N-methyl-Nxe2x80x2-2-propenyl-1,2-hydrazinedicarbothioamide,
O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate.
It is also possible to admix other known active compounds, such as herbicides, fertilizers and growth-regulating substances.
The active compound according to the invention can furthermore be present in its commercially available formulations and in the use forms prepared from these formulations, as a mixture with synergistic agents. Synergistic agents are compounds which increase the action of the active compounds without it being necessary for the synergistic agent added to be active itself.
The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.
The compounds are employed in a customary manner appropriate for the use forms.
When used against hygiene pests and pests of stored products, the active compound has excellent residual action on wood and clay and also good stability to alkali on limed substrates.
Furthermore, it has been found that the compound of the formula (I) according to the invention has potent insecticidal action against insects which destroy industrial materials.
The following insects may be mentioned by way of example and as being preferred, but without any limitation:
Beetles, such as
Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Emobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Zyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec., Dinoderus minutus.
Dermapterans, such as
Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.
Termites, such as
Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
Bristletails, such as Lepisma saccharina.
Industrial materials are to be understood as meaning, in the present context, non-live materials such as, preferably, synthetic materials, glues, sizes, paper and board, leather, wood and timber products, and paint.
The materials to be very particularly protected against attack by insects are wood and timber products.
Wood and timber products which can be protected by the composition according to the invention or mixtures comprising such a composition are to be understood as meaning, for example, construction timber, wooden beams, railway sleepers, bridge components, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wood lagging, windows and doors made of wood, plywood, particle board, joiner""s articles, or wood products which, quite generally, are used in the construction of houses or in joinery.
The active compounds can be used as such, in the form of concentrates or generally customary formulations, such as powders, granules, solutions, suspensions, emulsions or pastes.
The formulations mentioned can be prepared in a manner known per se, for example by mixing the active compounds with at least one solvent or diluent, emulsifier, dispersant and/or binder or fixative, water repellent, if appropriate desiccants and UV stabilizers and, if appropriate, colorants and pigments and other processing auxiliaries.
The insecticidal compositions or concentrates used for the protection of wood and wooden materials comprise the active compound according to the invention at a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.
The amount of the compositions or concentrates employed depends on the species and the occurrence of the insects and on the medium. The optimum rate of application can be determined upon use in each case by test series. However, in general, it suffices to employ 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.
The solvent and/or diluent used is an organochemical solvent or solvent mixture and/or an oily or oil-type organochemical solvent or solvent mixture of low volatility and/or a polar organochemical solvent or solvent mixture and/or water and, if appropriate, an emulsifier and/or wetting agent.
Organochemical solvents which are preferably employed are oily or oil-type solvents having an evaporation number of above 35 and a flashpoint of above 30xc2x0 C., preferably above 45xc2x0 C. Substances which are used as such oily and oil-type solvents which have low volatility and are insoluble in water are suitable mineral oils or their aromatic fractions, or mineral-oil-containing solvent mixtures, preferably white spirit, petroleum and/or alkylbenzene.
Substances which are advantageously used are mineral oils with a boiling range of 170 to 220xc2x0 C., white spirit with a boiling range of 170 to 220xc2x0 C., spindle oil with a boiling range of 250 to 350xc2x0 C., petroleum or aromatics of boiling range 160 to 280xc2x0 C., essence of turpentine and the like.
In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range of 180 to 210xc2x0 C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of 180 to 220xc2x0 C. and/or spindle oil and/or monochloronaphthalene, preferably xcex1-monochloronaphthalene, are used.
The organic oily or oil-type solvents of low volatility having an evaporation number of above 35 and a flashpoint of above 30xc2x0 C., preferably above 45xc2x0 C., can be partially replaced by organochemical solvents of high or medium volatility, with the proviso that the solvent mixture also has an evaporation number of above 35 and a flashpoint of above 30xc2x0 C., preferably above 45xc2x0 C., and that the insecticide/fungicide mixture is soluble or emulsifiable in this solvent mixture.
In a preferred embodiment, part of the organochemical solvent or solvent mixture is replaced by an aliphatic polar organochemical solvent or solvent mixture. Substances which are preferably used are aliphatic organochemical solvents having hydroxyl and/or ester and/or ether groups, such as, for example, glycol ether, esters and the like.
The organochemical binders used within the scope of the present invention are the synthetic resins and/or binding drying oils which are known per se and can be diluted with water and/or are soluble or dispersible or emulsifiable in the organochemical solvents employed, in particular binders composed of, or comprising, an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenol resin, hydrocarbon resin, such as indene/coumarone resin, silicone resin, drying vegetable and/or drying oils and/or physically drying binders based on a natural and/or synthetic resin.
The synthetic resin used as the binder can be employed in the form of an emulsion, dispersion or solution. Up to 10% by weight of bitumen or bituminous substances can also be used as binders. In addition, colorants, pigments, water repellents, odour-masking substances and inhibitors or anticorrosives known per se and the like can also be employed.
The composition or the concentrate preferably comprises, in accordance with the invention, at least one alkyd resin or modified alkyd resin and/or a drying vegetable oil as the organochemical binder. Preferably used according to the invention are alkyd resins with an oil content of over 45% by weight, preferably 50 to 68% by weight.
All or some of the abovementioned binder can be replaced by a fixative (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active compounds and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of binder employed).
The plasticizers are from the chemical classes of the phthalic esters, such as dibutyl phthalate, dioctyl phthalate or benzylbutyl phthalate, the phosphoric esters, such as tributyl phosphate, the adipic esters, such as di-(2-ethylhexyl) adipate, the stearates, such as butyl stearate or amyl stearate, the oleates, such as butyl oleate, glycerol ethers or relatively high-molecular-weight glycol ethers, glycerol esters and p-toluene-sulphonic esters.
Fixatives are chemically based on polyvinyl alkyl ethers, such as, for example, polyvinyl methyl ether, or ketones, such as benzophenone or ethylene benzophenone.
Particularly suitable as a solvent or diluent is also water, if appropriate as a mixture with one or more of the abovementioned organochemical solvents or diluents, emulsifiers and dispersants.
Particularly effective protection of wood is achieved by large-scale industrial impregnation processes, for example vacuum, double-vacuum or pressure processes.
If appropriate, the ready-to-use compositions can additionally comprise one or more other insecticides and, if appropriate, additionally one or more fungicides.
Suitable additional components which may be admixed are, preferably, the insecticides and fungicides mentioned in WO 94/29 268. The compounds mentioned in that document are expressly part of the present application.
Very particularly preferred components which may be admixed are insecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumuron, and fungicides, such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorofluanide, tolylfluanide, 3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.


A method and apparatus for detecting more than one fluorophore in a sample. A broad spectrum excitation light is passed through a shaping filter before illuminating the target sample with more than one fluorophore to be detected, where the optical density of the shaping filter changes based on the wavelength of the broad-spectrum excitation light passing through it.

The visualization of distinct molecular species represents an important challenge of bio-imaging research. In past decades, the development of multicolor fluorescent (FL) labels has greatly improved our ability to track biological analytes, paving the way for important advances in understanding the cell dynamics. It remains challenging, however, to visualize a large number of different fluorephores simultaneously. Owing to a spectrally broad absorption of fluorescent dyes, only up to five color categories can be resolved at once. Here, we demonstrate a general strategy for distinguishing between multiple fluorescent targets in acquired microscopy images with improved accuracy. The present strategy is enabled through spectral shaping of the excitation light with an optical filter that uniquely attenuates the light absorption of each fluorophore in the investigated sample. The resulting emission changes, induced by such excitation modulation, are therefore target-specific and can be used for identifying various fluorescent species. The technique is demonstrated through an accurate identification of 8 different CdSe dyes with absorption maxima spanning the 520-620 spectral range. It is subsequently applied for accurate measurements of the pH balance in buffers emulating a metabolism of tumor cells.

Shaped-excitation fluorescence (SEF) microscopy