Tropistic materials incorporating a class of adaptively configurable materials capable of real-time detection, tracking, and processing incident stimulus are provided. Incident stimulus can comprise any energetic emission or signals, such as electromagnetic waves, acoustics waves, or magnetic fields. The materials comprise a deformable stimuli-responsive material, which can adapt configuratively to a specific stimulus, and may further comprise a plurality of absorbers or photo-sensitive molecules configured to convert external incident stimuli to the specific stimulus type toward which the deformable material is responsive.

The capability to efficiently and simultaneously detect, track, and harvest or modulate signals (e.g., optical, electromagnetic, and acoustic) is vital for a broad range of optics, photonics, optoelectronics, energy-related technologies, and also national-security technologies. The current state of the art relies on tuning the physical properties of materials or employing electronics and computer programmed mechanical systems, which lack the ability to adaptively interact and engage with the signals. For example, tuning the refractive index of the coating layer of a photo-detecting panel to reduce the photon loss at the surface suffers from limited tenability and lacks the capability of directing the optical beam. Waveguides can direct signals but are normally cm-scale and made of rigid and heavy metallic materials. Other systems that can both detect and follow signals typically use a MEMS-based approach or pre-programmed electronics to mechanically lift and tilt a heavy photo-detecting panel or to fold an electromagnetic-receiving antenna towards the incident signals. While these systems attempt to combine the discrete processes of sensing and actuation, the capability comes with high fabrication and operation costs.
Further, enhancing the power density of incident energy is critical for most systems that require energy input maximization, such as emissive energy harvesting or remote signal sensing. A common problem for such systems is that light and many other electromagnetic waves often project on planar surfaces obliquely, causing a drop in input energy per area (power density) and significant energy loss.

Materials for autonomous tracking, guiding, modulating, and harvesting of energetic emissions

The Regents of the University of California


Systems, devices, and techniques for producing audio for, or adding audio capability to, a collection box for delivery items that includes a user-operated door for putting items into the collection box. The system can include a processing subsystem, an audio transducer, a trigger device that is connected to, or that is part of, the door of the collection device, and a sensor. The sensor detects the trigger device when the trigger device is in close proximity (e.g., in contact), and the sensor is positioned such that it is in close proximity with the trigger device when the door is closed. In response to the trigger device moving out of close proximity, the sensor generates a signal to the processing system. In response, the processing system generates an audio signal that is converted to sound by the audio transducer, which can be heard outside of the collection box.

Various agencies and companies provide delivery services, such as the U.S. Postal Service (USPS), the Federal Express Corporation (FedEx™), and the United Parcel Service Corporation (UPS™). Often, the items that are delivered by these services are placed in a collection box (e.g., a corner mail box) by the sender, and the delivery service (e.g., the USPS) retrieves the delivery items from the collection box according to a schedule (e.g., once daily) and places the delivery items into the delivery stream for sorting, routing, transporting, etc.
When a sender places an item(s) in a collection box, that person is standing in front of or is near the collection box for period of time that is from about two to four seconds, and that could be longer. During the time when the person is near the collection box, that person is not receiving any information or entertainment from the collection box, other than information that may be written on the collection box, if the person choses to read it.
It is thus desirable to provide new systems and devices that can provide information and/or entertainment to collection-box users, such as audio information, audio entertainment, and optionally illumination. It is also desirable to make such new systems and devices such that they can be easily added or retrofitted to existing collection boxes and provide them with a new audio capability.


An apparatus for efficiently cleaning a platen roller of a printer. A cleaning unit is attached to a main unit in place of a removal unit for an intermediate transfer sheet. A cam is turned by means of turning an arm UP/DOWN lever, and the arm is turned from an UP position to a DOWN position by means of the cam, to thus bring a cleaning pad on a leading end of the arm into contact with a platen roller and perform cleaning operation. When an operation mode is set to a cleaning mode and when attachment of the cleaning unit UC is detected, the platen roller is rotated, thereby allowing cleaning operation.

1. Technical Field
The present invention relates to a cleaning unit and a printer equipped with the cleaning unit, and more particularly cleaning of a platen roller for printing an image on a medium.
2. Related Art
A printer for printing a desired image on a medium plane of a CD, a DVD, or the like, (for label printing) has hitherto been known. In a case where, in such a printer, a full-color image is transferred onto an intermediate transfer sheet through use of a platen roller and where the intermediate transfer sheet is brought into close contact with a label plane of the medium, to thus print the image, the platen roller must be periodically cleaned.
Cleaning of the platen roller is usually performed along the following procedures.
(1) Set the printer to a cleaning mode by means of an operation panel.
(2) Open a door of the printer, and withdraw a removal unit (a ribbon cartridge) for the intermediate transfer sheet.
(3) Rotate the platen roller by means of the operation panel of the printer.
(4) Press a cleaning plate soaked with droplets of cleaning fluid against the platen roller and slowly move the cleaning plate back and forth several times, to thus remove stains.
(5) Stop the platen roller, and again attach the removal unit for the intermediate transfer sheet.
A basic configuration of the printer is described in JP 2005-132048 A. Further, JP 5-104841 A includes separately providing an ink ribbon with a plurality of ink-soaked zones classified by color and a cleaning zone; and wiping, in the cleaning zone of the ink ribbon, ink adhering to a ribbon mask that partitions an ink ribbon from a sheet. JP 7-1809 A includes providing a cleaning tape in place of an ink ribbon in a cartridge case and attaching the cartridge case, as it is, to a printer, thereby cleaning a print head. JP 10-76738 A describes a cleaning cassette that houses a cleaning tape formed by shaping, into the form of a tape, Japanese paper or a synthetic resin film whose both surfaces are thinly affixed with Japanese paper. The cleaning cassette is set on a thermal printer, and the cleaning tape is taken up by means of a take-up reel, thereby clearing dirt or stains from the print head and the platen roller. JP 2005-306007 A describes a cleaning cassette having a cleaning sheet for cleaning the surface of a thermal head and the surface of a platen roller by means of causing the cleaning sheet to travel between the thermal head and the platen roller.
Under a method for cleaning the platen roller by insertion of the cleaning plate, the cleaning plate must be inserted while attention is paid to the structure of surroundings of the platen roller, and low workability is attained. The platen roller may also be damaged. Further, an individual difference may also arise in connection with a cleaning effect.


A power converter with a negative current detection mechanism is provided. A negative current detecting circuit includes a first operational amplifier, a first transistor and a second transistor. A non-inverting input terminal of the first operational amplifier is connected to a second terminal of a sense resistor. An inverting input terminal of the first operational amplifier is connected to a first terminal of a first capacitor. Control terminals of the first and second transistors are connected to an output terminal of the first operational amplifier. A first terminal of the first transistor is connected to the second terminal of the sense resistor. A second terminal of the first transistor is grounded. A first terminal of the second transistor is connected to the inverting input terminal of the first operational amplifier and the first terminal of the first transistor. A second terminal of the second transistor is grounded.

A voltage converter plays an indispensable role in an electronic device. The voltage converter is used to convert a voltage and supply the converted voltage to the electronic device. A conventional detector circuit of the voltage converter detects a current flowing through a low-side switch, and calculates a voltage value based on the detected current and an on-resistance of the low-side switch. A controller circuit of the voltage converter controls a driver circuit to switch a high-side switch and the low-side switch according to the calculated voltage value. However, when the low-side switch of the voltage converter is replaced by a new low-side switch, an on-resistance of the new low-side switch may be different from the on-resistance of the low-side switch. Therefore, the conventional detector circuit must obtain an on-resistance of the new low-side switch and calculate a new voltage value based on the detected current and the on-resistance of the new low-side switch, such as to enable the driver circuit to appropriately switch the upper-bridge switch and low-side switch according to the new voltage value.

Power converter having negative current detection mechanism


A semiconductor device card receiving a circuit substrate (1) which has electronic component parts (2) assembled therein, comprises a pair of metal sheets (10, 10) forming a front and a back surfaces of the card and a pair of opposed resin-made frames (11, 12) surrounding peripheries of the respective metal sheets to be connected by embedding bent portions 100 of the peripheries of the metal sheets (10, 10) into the resin-made frames (11, 12), and the paired opposed frames are provided at their contact end portions with fusible projections (13) and grooves (14) adapted to engage with the projections (13) and are connected to each other by fusing at least a leading end of the projection (13) within the groove (14). A plurality of projecting portions (10a) are projected downward from the bent portions (100) of one of the paired metal sheets 10 and engaging portions (10b) adapted to engage with the projecting portions (10a) are formed in the bent portions (100) of the opposite metal sheet (10), so that the paired sheet metals can be electrically conducted to each other by the engagement between the projecting portions (10a) and the engaging portions (10b) and the connection of the opposed side frames can be reinforced. The connecting strength can be improved by employing an ultrasonic bonding. While the number of the components parts can be decreased, the connecting strength can be further improved.

1. Field of the Invention
The present invention relates to a semiconductor device card receiving a circuit substrate which has electronic component parts assembled thereon.
2. Description of the Related Art
Conventionally, in such a semiconductor device card, as shown in FIG. 10, various kinds of electronic component parts are assembled on a circuit substrate 1. This circuit substrate 1 is received in a card case composed of a pair of upper and lower frame members to form the semiconductor device card. Each of the frame members comprises a sheet metal 5 for forming an upper or lower card surface and a resin-made frame 6 or 7 molded to peripheries of the sheet metal 5 for forming a card side frame, and the resin-made frames 6, 7 are connected to each other by means of an adhesive agent. These sheet metals serve to shield external radio wave noises and to prevent charging of static electricity. Therefore, as shown in FIG. 11, the upper and lower sheet metals 5, 5 are electrically connected to each other by a helical spring 4 inserted into portions of the resin-made frames 6, 7 in their physically connected conditions. A connector 3 is provided at a side opening composed by a pair of said frames members for use in external electrical connection.
In this semiconductor device card, strong connection between the upper and the lower frame members is required. Therefore, there has been proposed that the sheet metals is provided at their peripheral edges with bent portions and the circuit substrate is provided at its periphery with a resin-made frame portion so that the bent portions can be embedded in the resin-made frame portion in the Japanese Unexamined Patent Publication (Tokkaihei) No. 3-96396.
There are, however, several problems associated with the above-mentioned semiconductor device card. That is, since it is necessary to force the bent portions to be embedded into the heated resin-made frame portions or to embed the bent portions in the resin-made frame portions simultaneously with the molding of the later, the circuit substrate tends to be badly affected and the assembly working would become complicated. Accordingly, the connection between the bent portion and the frame portion can't help having recourse to the adhesive agent. But, the connecting strength tends to decrease as their sizes get smaller.
On the other hand, such a semiconductor device card is required to decrease the number of component parts and the number of assembling procedures to a minimum simultaneously with the downsizing. As a trial to decrease the number of component parts, portions of the opposed sheet metals are bent so as to be brought into contact with each other to eliminate the helical spring in the Japanese Unexamined Patent Publication No. 2-111595.


The present invention is directed to novel 3-spirocyclic indolyl derivatives, pharmaceutical compositions containing them and their use in the treatment of disorders and conditions modulated by the ORL-1 receptor.

The ORL-1 (orphan opioid receptor) G-protein coupled receptor, also known as the nociceptin receptor, was first reported in 1994, and was discovered based on its homology with the classic delta- (OP-1), mu- (OP-3), and kappa- (OP-2) opioid receptors. The ORL-1 G-protein coupled receptor does not bind opioid ligands with high affinity. The amino acid sequence of ORL-1 is 47% identical to the opioid receptors overall, and 64% identical in the transmembrane domains. (Nature, 1995, 377, 532.)
The endogenous ligand of ORL-1, known as nociceptin, a highly basic 17 amino acid peptide, was isolated from tissue extracts in 1995. It was named both nociceptin, because it increased sensitivity to pain when injected into mouse brain, and orphanin FQ (OFQ) because of the terminal phenylalanine (F) and glutamine (Q) residues that flank the peptide on the N- and C-termini respectively. (PCT publication WO97/07212)
Nociceptin binding to ORL-1 receptors causes inhibition of cAMP synthesis, inhibition of voltage-gated calcium channels, and activation of potassium conductance. In vivo, nociceptin produces a variety of pharmacological effects that at times oppose those of the opioids, including hyperalgesia and inhibition of morphine-induced analgesia. Mutant mice lacking nociceptin receptors show better performance in learning and memory tasks. These mutant mice exhibited normal responses to painful stimuli.
The ORL-1 receptor is widely distributed/expressed throughout the human body, including in the brain and spinal cord. In the spinal cord, the ORL-1 receptor exists in both the dorsal and ventral horns, and precursor mRNA has been found in the superficial lamina of the dorsal hom, where primary afferent fibers of nociceptors terminate. Therefore, the ORL-1 has an important role in nociception transmission in the spinal cord. This was confirmed in recent studies wherein nociceptin, when given to mice by i.c.v. (intra-cerebro-ventricular) injection, induced hyperalgesia and decreased locomotor activity. (Brit. J. Pharmacol. 2000, 129, 1261.)
We now describe novel small molecule modulators of the ORL-1 receptor, useful for the treatment of disorders and conditions mediated by the ORL-1 receptor, such as anxiety, depression, panic, dementia, mania, bipolar disorder, substance abuse, neuropathic pain, acute pain, chronic pain, migraine, asthma, cough, psychosis, schizophrenia, epilepsy, hypertension, obesity, eating disorders, cravings, diabetes, cardiac arrhythmia, irritable bowel syndrome, Crohn's disease, urinary incontinence, adrenal disorders, attention deficit disorder (ADD), attention deficit hyperactivity disorders (ADHD), Alzheimer's disease, for improved cognition or memory and for mood stabilization.

3-spirocyclic indolyl derivatives useful as ORL-1 receptor modulators


A method of setting a cycle of a low-duty mode in a femto base station is provided. The cycle of the low-duty mode has a pattern in which an available interval and an unavailable interval repeatedly appear, and the available interval is set to include a paging listening interval of a paging cycle. A method of setting a cycle of a low-duty mode in a femto base station having a service area overlapping with that of a macrocell is provided. An unavailable interval is set by taking the overlapping degree of the service area of the femto base station with the macrocell into consideration. A method of setting a cycle of a low-duty mode in a plurality of femto base stations operated in the low-duty mode is provided. The same cycle can be set for a plurality of base stations.

(a) Field of the Invention
The present invention relates to a method of low-duty mode operation in a femto base station.
(b) Description of the Related Art
A femto base station refers to an ultra-small base station that manages a femtocell having a smaller service area than a macrocell. The femtocell serves to improve speech quality in an indoor space which the coverage of the macrocell cannot reach, and to share the load of the macrocell, and is able to reduce communication cost. However, the femtocell may degrade the performance of mobile stations MS in the femtocell and the macrocell due to interference with the macrocell. To solve this problem, the femto base station supports a low-duty mode LDM as well as a normal mode.
The femto base station enters the low-duty mode if there is no mobile station attached in the femto base station or all the mobile stations present in the femtocell are in an idle or sleep mode. The cycle of the low-duty mode has a pattern (hereinafter, referred to as a "low-duty mode cycle pattern") in which an available interval AI and an unavailable interval UAI alternately appear. The femto base station operates in the low-duty mode cycle pattern. During an available interval, the femto base station may become active on the air interface for synchronization with a mobile station, paging, ranging, or data traffic transmission. During an unavailable interval, it does not transmit on the air interface.

Method of low-duty mode operation of femtocell base station

Electronics and Telecommunications Research Institute


An output current of a constant current source formed of a gate potential control circuit and a p channel MOSFET is determined only by the sub threshold swing value of a p channel MOSFET and a resistance of a resistor. A signal out 1 controlling the operation of a ring oscillator circuit is switched at a predetermined potential corresponding to the sum of the threshold value of n channel MOSFETs through which the output current flows. Since the output current has no power supply voltage dependency and increases in proportion to the temperature, the predetermined potential is independent of the power voltage. The temperature dependency is also small since the temperature dependency of the output current value and the threshold value cancel each other. Therefore, the substrate potential can be controlled at a stable level unsusceptible to variation in the external operating conditions.

1. Field of the Invention
The present invention relates to substrate potential generation circuits, and more particularly, to a structure of a circuit for controlling a substrate bias potential within a predetermined voltage range required for an integrated circuit device such as a semiconductor memory.
2. Description of the Background Art
The source and drain regions of an MOSFET forming an integrated circuit such as a semiconductor memory form a pn junction with the substrate to have a junction capacitance that cannot be neglected in the circuit operation. This junction capacitance becomes the cause of degrading the operation rate of circuitry. The pn junction capacitance can be reduced in proportion to an applied bias in a reverse direction.
Furthermore, under shooting of noise and external signals such as under shooting of the potential of an n.sup.+ drain region of an MOSFET causes a pn junction to be biased in the forward direction, whereby a small amount of carriers are introduced into the substrate. This introduction of carriers induce the possibility of latch up of a COOS circuit and damage of data stored in a memory cell in a DRAM.
An internal circuit that intentionally applies a reverse bias to the substrate is typically incorporated to solve such a problem.
FIG. 18 is a circuit diagram showing a structure of a conventional substrate potential generation circuit. Referring to FIG. 18, the substrate potential generation circuit mainly includes a substrate potential level detection circuit 100, an oscillator circuit 200, and a charge pump circuit 300.
In substrate potential level detection circuit 100, a p channel MOSFET 102 operating as a current source is connected to a substrate via diode-connected n channel MOSFETs 106 and 108 connected in series to each other, and an n channel MOSFET 104 connected in series to MOSFETs 106 and 108 and having its gate grounded.
When the threshold voltage of n channel MOSFETs 104, 106 and 108 is V.sub.thn, the potential difference across the gate and source of n channel MOSFET 104 is: EQU .vertline.V.sub.o .vertline.=.vertline.V.sub.BB +2V.sub.thn .vertline.(1)
where V.sub.BB is a negative value. When substrate potential V.sub.BB is sufficiently low and .vertline.V.sub.o .vertline. is greater than the threshold voltage of n channel MOSFET 104, n channel MOSFET 104 attains an ON state, and the potential of a node n1 attains an L (Logical Low) level.
Conversely, when substrate bias potential V.sub.BB is high and potential difference .vertline.V.sub.o .vertline. is smaller than threshold voltage V.sub.thn of n channel MOSFET 104, n channel MOSFET 104 is cut off. In this case, the potential of node n1 is pulled up to an H (Logical High) level by the potential supplied from p channel MOSFET 102 which is ON.
More specifically, substrate potential level detection circuit 100 provides a signal of an L level and an H level to node nl when the level of substrate bias potential V.sub.BB is lower and higher, respectively, than a predetermined potential level (in this case, -3.times.V.sub.thn).
The potential of node n1 is applied to one input terminal of an NAND circuit 202 in oscillator circuit 200. The output of NAND circuit 202 is applied to the other input terminal of NAND circuit 202 via a series of an even number of stages of inverters 204, 206, . . . , 208.
Therefore, when the potential of node nl attains an L level, the potential of a node n2 which is the output of NAND circuit 202 is fixed to an H level, so that oscillation does not occur. That is to say, the substrate potential generation circuit is "inactive".
When the substrate bias potential V.sub.BB rises and the potential of node nl is pulled up to an H level, oscillator circuit 200 is activated to initiate oscillation, whereby charge pump circuit 200 is driven. In other words, the substrate potential generation circuit is "active", whereby substrate bias potential V.sub.BB begins to be lowered.
According to the above-described operation, the substrate bias potential is maintained at a predetermined potential.
The structure of the above-described substrate potential generation circuit is not sufficient by reasons set forth in the following when the substrate potential is greatly shifted to the negative side than the predetermined potential due to variation of the power supply potential.
When the substrate potential is shifted towards the negative side, the time constant T for that potential to be restored is T=R.multidot.C which is the product of capacitance C of a substrate and impedance R of a substrate. The value of the substrate impedance is generally great since it is determined by leakage current or the like of the pn junction formed at the substrate. This means that time constant T is also increased to result in a longer time period for the substrate potential to be restored.
Variation of the substrate potential will affect the threshold voltage of each transistor formed on the same substrate. It will directly influence the circuit operation characteristics, such as the operation margin. If the time required for the substrate potential to attain the stable state after variation is appreciable, the operation of each element formed on a substrate will become unstable.
A conventional substrate potential clamp circuit 400 for addressing this problem is shown in FIG. 19.
Referring to FIG. 19, a plurality of diode-connected n channel MOSFETs 402-408 are connected in series. These MOSFETs serve to couple the substrate with the ground potential. When the substrate potential become lower than -4.times.V.sub.thn where V.sub.thn is the threshold voltage of an n channel MOSFET, the substrate is connected to ground, whereby the substrate potential is pulled up. More specifically, the substrate potential greatly shifted towards the negative side is restored to V.sub.BB =-4.times.V.sub.thn at a short time constant. Thus, this circuit includes the clamping function to suppress the absolute value of the substrate potential from exceeding 4.times.V.sub.thn.
Since the substrate potential directly affects the operation characteristics of circuitry, a stable value must be constantly maintained. It is necessary that the substrate potential generation circuit operates even during stand-by. In other words, power consumption of the substrate potential generation circuit is an important factor that determines the power consumption of the entire circuit during stand-by.
Particular attention must be paid in the case where a DRAM incorporated in a substrate potential generation circuit is operated by a battery.
In the substrate potential generation circuit of FIG. 18, oscillator circuit 200 consumes the greatest power. FIG. 20 shows a detail circuit diagram thereof.
At the first stage, a NAND circuit 202 receiving an output signal out4 of substrate potential detection circuit 100 (FIG. 18) is provided. A ring oscillator circuit is formed with an even number of stages of CMOS inverters connected.
The conventional substrate potential generation circuit of the above-described structure has problems set forth in the following.
Firstly, there was a problem that the power supply voltage dependency of the pull up current is great since p channel MOS transistor 102 having its gate potential grounded is used as the current supply circuit of the pull up side in substrate potential level detection circuit 100.
When the power supply voltage is increased to result in a greater pull up current, the level of the substrate potential at which oscillation circuit operation control signal out4, from substrate potential level detection circuit 100, switches becomes lower. Therefore, the absolute value of substrate potential V.sub.BB is increased together with the rise of the power supply voltage as shown by the dotted line of FIG. 17(A).
Secondly, the absolute value of the potential that causes switching of oscillation circuit operation control signal out4 (referred to as predetermined potential hereinafter) is reduced since the threshold voltage of the MOSFET determining the predetermined potential becomes lower in proportion to a rise in temperature. Therefore, the absolute value of the substrate potential controlled by the substrate potential generation circuit is reduced as the temperature becomes higher as shown in the dotted line in FIG. 17(B).
The third problem is that the operation of clamping the potential is too slow. This is because the current value flowing through the conventional clamp circuit changes its level in a relatively slow manner in the proximity of the threshold voltage at which a clamping operation is initiated when the substrate potential is greatly shifted towards the negative stop side than the predetermined potential. Control by the conventional clamp circuit is only effective when the difference between the predetermined potential and substrate potential is sufficient.
Thus, the conventional substrate potential generation circuit has the disadvantage that the controllability is poor with respect to variation in the external environment and external operation condition according to the above-described three points.
Fourthly, power consumption of the circuitry incorporating ring oscillator 200 is increased during stand-by since ring oscillator 200 consumes a great amount of current. Therefore, the operation margin is limited by external operation conditions such as the power source, or the operating condition of the mounted circuit is limited.

Substrate potential generation circuit that can suppress variation of output voltage with respect to change in external power supply voltage and environment temperature


Disclosed are heterocyclic heteroaromatic macrocyclic ether compounds of Formula (I):

Receptor tyrosine kinases (RTKs) are cell surface enzymes that receive outside signals, such as whether to grow and divide, and transmit those signals in the cell through kinase activity. Many RTKs are proto-oncogenes; aberrant RTK activity can drive cell survival, growth and proliferation leading to cancer and related disorders. This aberrant kinase activity can be caused by mutations such as activating mutations in the kinase domain, gene rearrangements that result in fusion proteins containing the intact kinase domain, amplification and other means. RTK proto-oncogenes include ROS1, anaplastic lymphoma kinase (ALK), NTRK1 (encodes TRKA), NTRK2 (encodes TRKB), and NTRK3 (encodes TRKC).
ROS1 is an RTK proto-oncogene, with ROS1 rearrangements detected in non-small cell lung cancer (NSCLC), glioblastoma, inflammatory myofibroblastic tumor (IMT), cholangiocarcinoma, ovarian cancer, gastric cancer, colorectal cancer, angiosarcoma, and spitzoid melanoma. Oncogenic ROS1 gene fusions contain the kinase domain of ROS1 (3′ region) fused to the 5′ region of a variety of partner genes. Examples of ROS1 fusion partner genes observed in NSCLC include SLC34A2, CD74, TPM3, SDC4, EZR, LRIG3, KDELR2, CEP72, CLTL, CTNND2, GOPC, GPRC6A, LIMA1, LRIG3, MSN, MYO5C, OPRM1, SLC6A17 (putative), SLMAP, SRSF6, TFG, TMEM106B, TPD52L1, ZCCHC8 and CCDC6. Other fusion partners include CAPRIN1, CEP85L, CHCHD3, CLIP1 (putative), EEF1G, KIF21A (putative), KLC1, SART3, ST13 (putative), TRIM24 (putative), ERCI, FIPIL1, HLAA, KIAA1598, MYO5A, PPFIBP1, PWWP2A, FN1, YWHAE, CCDC30, NCOR2, NFKB2, APOB, PLG, RBP4, and GOLGB1.
ALK is an RTK proto-oncogene, with ALK rearrangements detected in many cancers, including NSCLC, anaplastic large cell lymphoma (ALCL), IMT, diffuse large B-cell lymphoma (DLBCL), esophageal squamous cell carcinoma (ESCC), renal medullary carcinoma, renal cell carcinoma, breast cancer, colon cancer, serous ovarian carcinoma, papillary thyroid cancer, and spitzoid tumors, and ALK activating mutations detected in neuroblastoma. Oncogenic ALK gene fusions contain the kinase domain of ALK (3′ region) fused to the 5′ region of more than 20 different partner genes, the most common being EML4 in NSCLC and NPM in ALCL. Other partner genes include TMP1, WDCP, GTF2IRD1, TPM3, TPM4, CLTC, LMNA, PRKAR1A, RANBP2, TFG, FN1, KLC1, VCL, STRN, HIP1, DCTN1, SQSTM1, TPR, CRIM1, PTPN3, FBXO36, ATIC and KIF5B.
NTRK1, NTRK2 and NTRK3 are RTK proto-oncogenes that encode TRK-family kinases, with NTRK1, NTRK2 and NTRK3 chromosomal rearrangements detected at low frequency in many cancers. For treatment of ROS1-positive or ALK-positive patients, however, TRK inhibition, particularly in the central nervous system (CNS), has been associated with adverse reactions, including dizziness/ataxia/gait disturbance, paraesthesia, weight gain and cognitive changes.
Agents in the prior art used to treat oncogenic ROS1 and ALK have substantial deficiencies. These deficiencies may represent one or more of the following: associated TRK inhibition, limited CNS activity, and inadequate activity against resistance mutations. Treatment of ROS1-positive or ALK-positive patients accompanied by TRK inhibition is associated with adverse reactions, particularly in the CNS, including dizziness/ataxia/gait disturbance, paraesthesia, weight gain and cognitive changes. Additionally, there is a need for CNS-penetrant and TRK-sparing inhibitors of the wild type ROS1 kinase domain and ROS1 with acquired resistance mutations occurring either individually or in combination, including G2032R, D2033N, S1986F, S1986Y, L2026M, L1951R, E1935G, L1947R, G1971E, E1974K, L1982F, F2004C, F2004V, E2020K, C2060G, F2075V, V2089M, V2098I, G2101A, D2113N, D2113G, L2155S, L2032K, and L2086F. Likewise, there is a need for CNS-penetrant and TRK-sparing inhibitors of ALK with acquired resistance mutations. A variety of ALK drug resistance mutations, occurring either individually or in combination, have been reported, including G1202R, L1196M, G1269A, C1156Y, I1171T, I1171N, I1171S, F1174L, V1180L, S1206Y, E1210K, 1151Tins, F1174C, G1202del, D1203N, S1206Y, S1206C, L1152R, L1196Q, L1198P, L1198F, R1275Q, L1152P, C1156T, and F1245V.

Heteroaromatic macrocyclic ether chemotherapeutic agents

Abstract: pharmaceutically acceptable salts of the compounds and pharmaceutical compositions thereof. The disclosure further relates to methods of treating or preventing cancer using the heterocyclic heteroaromatic macrocyclic ether compounds, pharmaceutically acceptable salts of the compounds and pharmaceutical compositions thereof.


It is intended to provide an ultrasonic probe permitting a reduction of a number of switching components while transmitting and receiving signals with the picture quality level held capable of being maintained. An ultrasonic the probe comprises transducers, transducer side cables which number is equal to a number of said transducers and are connected to the transducers, apparatus body side cables which number is less than a number of the transducer side signal lines and are connected to an apparatus body, switching units for switching connections of a transducer side cables of groups A and C which is connected to the apparatus body side cables of group D, and resistors provided between the transducer side cables of group B and the apparatus body side cables of group E.

The present invention relates to an ultrasonic probe and an ultrasonic diagnostic apparatus.
An ultrasonic diagnostic apparatus whose system has less number of channels than the number of transducer elements is known (e.g. JP-A No. 2004-358105). For instance in an electron scanning type ultrasonic diagnostic apparatus, since every transducer transmits and receives ultrasonic waves all the time, the number of channels on the system side can be less than the number of transducers. In such an ultrasonic diagnostic apparatus, by disposing multiplexer ICs between transducers and system channels for instance, transmission and reception with fewer system channels than the transducers is realized.
However, in such an ultrasonic apparatus, though a multiplexer is connected to every transducer, ON/OFF switching is not performed in every multiplexer. In an electron scanning system for instance, the multiplexer connected to the transducer arranged at the center of a probe may be used in a mode of being kept ON all the time. And since multiplexer ICs are generally expensive, the presence of unused multiplexers might invite an undue cost increase.
On the other hand, since multiplexer ICs also have resistance components such as ON resistors, indiscreet dispensation with a multiplexer IC used in a mode of being kept ON all the time would be detrimental to the uniformity of picture quality. For instance, dispensation with a multiplexer IC would invite an increased signal intensity due to a drop in resistance between the transducer and the system channel and accordingly partially greater brightness of the image.

Ultrasonic probe and ultrasonic diagnostic apparatus

GE Medical Systems Global Technology Company, LLC


A device comprising a display unit which is configured to display, on a screen of the cockpit of the aircraft, a pitch bar illustrating a pitch order and means for adapting the direct gain of the pitch law used to the effective manual behavior of the pilot in order to obtain a homogeneous response from the aircraft.

The present invention relates to a method and a device for displaying in real time a pitch instruction on an aircraft, in particular a transport airplane, during piloting in manual mode.
The invention relates to the field of flight control systems and provides adaptation in real time for the calculation of values of the flight director of the FD type.
In modern aircraft, the flight director generally displays steering orders on primary flight screens of the PFD type (Primary Flight Display) and in a similar manner on HUD type displays (Head-Up Display). These steering orders are calculated by steering control laws based on selected steering targets in an FMS type system (Flight Management System) or directly on an FCU type unit (Flight Control Unit). If no automatic pilot system of the aircraft is engaged, the crew can manually pilot the aircraft by following the orders of the flight director and by manually carrying out the piloting that the automatic pilot system would carry out if it were engaged.
On the flight detector, a pitch bar and a roll bar indicate, respectively, the pitch and roll steering orders. The aircraft follows these steering orders when it is piloted in such a manner that these instruction bars of the flight director are centered on the attitude of the aircraft (generally illustrated at the center of the PFD/HUD display when a vertical mode is engaged in flight).
Generally, the pitch law relating to the PFD screen is controlled so as to withstand the variations in behavior of the pilot. Consequently, the response of the aircraft to the manual inputs of the pilot is not ideal since each pilot has his own operating dynamic (resulting from personal biological dynamics) when he follows a pitch bar displayed on the flight director.
That is to say, for the same pitch steering order (which is provided via the pitch instruction bar), the actuation of the pitch control handle, for example, a mini-handle, may have a different dynamic in accordance with the pilot operating it, or with the manner in which the same pilot carries out the actuation. The response of the aircraft may thus be different to that which it would be if the automatic pilot system were engaged and applied the pitch order automatically and precisely.

Method and device for displaying in real time a pitch instruction on an aircraft during manual piloting


Methods and apparatus related to determining non-textual reply content for a reply to an electronic communication and providing the non-textual reply content for inclusion in the reply. Some of those implementations are directed to determining, based on an electronic communication sent to a user, one or more electronic documents that are responsive to the electronic communication, and providing one or more of those electronic documents for inclusion in a reply by the user to the electronic communication. For example, the electronic documents may be automatically attached to the reply and/or link(s) to the electronic documents automatically provided in the reply.

Users are often inundated with electronic communications such as emails, SMS communications, and social networking communications. Many electronic communications that are sent to a user explicitly solicit that the user reply with non-textual reply content or otherwise contain information to which the user may wish to reply with non-textual reply content. For example, an email that contains "Can you send me a copy of your slide deck from yesterday's meeting" may explicitly solicit a reply that includes non-textual reply content (i.e., an electronic document that is the slide deck). An email that contains "How is the home remodel progressing?" may not explicitly solicit a reply with non-textual reply content, but a user that receives the email may still wish to include non-textual reply content (e.g., a picture showing the current status of the home remodel) in a reply to the email. To include non-textual reply content in a reply, users must recognize that non-textual reply content is appropriate for the reply, manually browse for the non-textual reply content via a computing device of the user, and select the non-textual reply content via a user interface input device of the computing device to include the content in the reply.

This patent is subject to a terminal disclaimer.

Methods and apparatus for determining non-textual reply content for inclusion in a reply to an electronic communication


Methods of obtaining faithful expression libraries from tissue samples comprise extraction of RNA from intact tissue cultured in three-dimensional sponge-gel based histocultures.

There is an extensive history of the use of histocultured tumor samples for use in prognosis of tumor development and as a tool for predicting responsiveness to drugs. These histochemical techniques, which are the basis of histoculture drug response assay (HDRA™), have an extensive literature. The general features of this technique are described, for example, in a recent paper by Singh, B., et al., Head and Neck (2002) 24:437-442. As described in this paper, briefly, biopsied tissue is washed and cut into 1 to 2 mm3 fragments and placed onto 0.5 cm2 pieces of collagen sponge-gel (Gel Foam, Pharmacia & Upjohn, Inc.) in equal quantities. The sponge-gel cultures are then placed into DMEM/Ham's F12 medium with 10% fetal calf serum and gentamicin (50 μg/ml). The cultures are then incubated for 24 hours at 37° C. and 5% CO2. Modifications of this technique are also permissible, provided the three-dimensional nature of the sample is preserved.
It has now been found that in addition to their usefulness as prognostic and drug-screening tools, such cultures are also useful as sources for messenger RNA as a substrate for expression profiling. This is significant in view of the problems associated with providing reliable expression libraries, in particular when derived from patient samples where extraction of high-quality, non-degraded RNA is difficult in view of the necrotic areas present in tumors and in view of the need to transport tumor tissue from a treatment or diagnosis center to a laboratory capable of performing the profiling analysis. By maintaining non-necrotic portions of the tumor in a three-dimensional histoculture, the expression profile of the tumor in situ is effectively preserved.

Expression profiling based on histocultures


A balance weight for a two-wheeled vehicle includes a weight made from iron and a clip made from spring steel. The weight includes a first axial end, a second, opposite axial end, a transversely extending intermediate surface, and a first laterally extending groove for holding the clip therein having a groove bottom portion and a groove inlet portion which is smaller in width than the groove bottom portion. The clip includes a pair of arms, a connecting portion, an engaging portion formed in the connecting portion, a bent portion bent from the connected portion toward a space between the pair of arms, and an obliquely extending portion extending obliquely in a direction away from the transversely extending intermediate surface of the weight.

This application is based on, and claims priority from, Japanese Patent Application No. 2001-9764, filed on Jan. 18, 2001, and Japanese Patent Application No. 2001-327963, filed on Oct. 25, 2001, the content of which is incorporated herein by reference.
1. Field of the Invention
The present invention relates to a balance weight for a two-wheeled vehicle.
2. Description of Related Art
In order to keep a rotational balance of a wheel of a two-wheeled vehicle, a balance weight is mounted to the wheel at a nipple of a spoke, i.e., a tension adjusting portion.
A conventional balance weight for a two-wheeled vehicle is made from lead. The conventional balance weight has a substantially cylindrical outside configuration with a lateral groove, concaved from an outside surface toward a center of the balance weight, which extends over an entire length of the balance weight. The balance weight is fixed to the nipple by inserting the nipple into the groove, and then pressing to deform both side portions of the groove from an outside surface so that the nipple cannot exit from the groove.
However, the conventional balance weight poses an environmental problem because it is made from lead.
If another metal other than lead, for example, iron, is used while maintaining the configuration of the conventional balance weight, the rigidity of the weight will be too great for the weight to be deformed when it is fixed to the nipple, which makes the fixing of the balance weight to the nipple difficult.
An object of the present invention is to provide a balance weight for a two-wheeled vehicle, which is made from iron (for example, cast iron) in substitution for lead, and can be stably fixed to a wheel, and easily mounted to the wheel.
The above object can be performed by a balance weight for a two-wheeled vehicle according to the present invention, as follows:
A balance weight for a two-wheeled vehicle according to the present invention includes a weight made from iron and a clip made from spring steel.
The weight comprises an outside surface, a first axial end, a second, opposite axial end, a transversely extending intermediate surface located between the first end and the second end, a first axially extending portion located between the first end and the intermediate surface, a second axially extending portion located between the second end and the intermediate surface, a first laterally extending groove for holding the clip, formed in the first axially extending portion, and having a groove bottom portion and a groove inlet portion, the groove inlet portion being smaller in width than the groove bottom portion, and a second laterally extending groove formed in the second axially extending portion so as to recede from the outside surface.
The clip includes a pair of arms, a connecting portion connecting the pair of arms and which is disposed within and held by the first laterally extending groove, an engaging portion formed in the connecting portion and raised in a direction opposite to said pair of arms, a bent portion connected to the connecting portion at one width end proximate to the transversely extending intermediate surface of the weight and bent from the one width end toward a space between the pair of arms, and an obliquely extending portion connected to the bent portion and extending axially obliquely in a direction away from the transversely extending intermediate surface of the weight.
When the balance weight is mounted to the two-wheeled vehicle, the pair of arms and the obliquely extending portion of the clip elastically contact or hold a nipple of a spoke of the two-wheeled vehicle, whereby the clip is fixed to the nipple. The first laterally extending groove holds the clip, and the engaging portion is pressed to the weight, whereby the weight is fixed to the clip.
With the balance weight for a two-wheeled vehicle according to the present invention, since the balance weight is made from iron, the balance weight is environmentally friendly, unlike the conventional balance weight made from lead.
The balance weight is mounted to a wheel of a two-wheeled vehicle at a nipple (a spoke adjusting portion) of the wheel. The nipple is inserted into the second laterally extending groove of the weight, while the pair of arms of the clip is widened to receive the nipple in the clip. The pair of arms and the obliquely extending portion of the clip are elastically pressed to the nipple whereby the balance weight is fixed to the clip. The clip cannot exit from the first laterally extending groove of the weight whereby the weight is fixed to the clip. In this instance, since the pair of arms and the obliquely extending portion of the clip elastically hold the nipple, the balance weight can be mounted to the nipple stably. Further, since the balance weight can be mounted to the wheel only by pushing the balance weight to the nipple, the mounting of the balance weight to the wheel is easy.

Balance weight for a two-wheeled vehicle


A method for simulating running a software application having a plurality of processes on a computer system being tested. The method includes providing a number of work daemons on the test system, with the number being chosen to be substantially equal to the number of processes in the simulated software application. The method continues with configuring each of the work daemons with a static portion that performs functions on or exercises memory of the test system when the work daemon is run. Each of the work daemons is also configured with a dynamic portion including text segments that are selectively executable when the work daemon is run. The static and dynamic portions simulate operations performed by a corresponding one of the modeled software application processes. The method includes running at least a portion of the configured work daemons on the test system and monitoring performance of the test system.

1. Field of the Invention
The present invention relates, in general, to testing computer hardware such as part of a quality assurance process, and, more particularly, to a method and corresponding system for testing and analyzing a computer device or network of devices during running of one or more software applications by simulating loads, e.g., memory, communication, and processing loads, created by applications intended to be run on the tested device or network or devices.
2. Relevant Background
Within the computer industry, an ongoing problem is providing adequate testing and quality assurance of computer devices, systems, and networks prior to initial use and installation by customers. As with other consumer products, it is typically desirable to run a new product or product configuration through a battery of tests to insure that the product performs as expected without performance degradation or without serious problems or errors. With new computer devices, this can be a relatively simple task when testing a standalone computing device such as a personal computer, but testing and quality assurance tasks quickly become very complicated and difficult when applied to large computer devices or systems of networked devices.
Customers in the computer industry often run very sophisticated and large suites of applications to perform their data processing and communicating operations. For example, in the telecommunications industry, telephony customers or businesses that manage the infrastructure for a cellular network have applications that control and manage large numbers of cellular or wireless calls on an ongoing basis. Telephony switching and/or call processing applications generate huge processing, memory, and communication loads within a computer system that far exceeds relational database applications (e.g., another example of applications that can place large loads on computer systems). During operation of such large applications, huge amounts of binary text segments that represent compiled code are executed, memory is accessed, and both inter and intra process communications take place between systems on a particular computing network. Developers and manufacturers often create computer devices and systems to meet the demands of particular customers and as a result, there is a need for being able to test the newly created computer devices and systems under the load or operating conditions for which they are being designed, i.e., under the load conditions their customers will place the machines by running their particular applications and processing their business-specific data.
One useful technique for testing a computer system or network of computer devices is to install the system or network of devices on the customer's premises, such as in an onsite customer-controlled laboratory. In such a setting, the customer makes available their programs or applications and the system or network of devices can be configured to process customer data to provide an accurate and realistic test under the operating conditions intended for the computer system. In this manner, the application(s) or program(s) specific characteristics, such as spatial and execution characteristics, can be tested during operation of the computer system to determine how these effect performance. For example, theoretical performance gains for new computer systems or devices are often much higher than what is actually experienced when the new computer systems or devices are installed on a customer's site to run their applications, e.g., increases in processor clock speed that would tend to indicate a particular increase in performance may not necessarily provide such an improvement due to the particular spatial and execution characteristics of the customer's applications.
Testing of a computer system or network of computer devices can be accomplished effectively with the assistance of the customer, which may include installing equipment on their facilities. However, such testing is often difficult to arrange and schedule and can quickly become a bottleneck when testing indicates problems that may need iterative testing to correct problems. To date, the computer industry has not been able to provide adequate quality assurance and testing of a computer system or its configuration without having the customer's application itself and, in some cases, the customer's data flow. Attempts to run the actual application have not proven successful or have been determined too costly as it is very difficult and time consuming to write programs of the size required to emulate complex customer software suites, e.g., software applications that include or generate millions of lines of code that result in binary text segments that are proportionally large to the amount of compiled code.
Hence, there remains a need for a method and system for testing computer devices and systems under conditions, e.g., spatial and execution characteristics, similar to those created by a particular set of applications or programs to be implemented by an intended customer or end user. Preferably, such a method and system would enable the computer industry to design and build machines to run particular applications before an application(s) is available or without requiring use of the actual application(s).

State machine simulator for testing computer systems


A pigment-comprising formulation for coating substrates, comprising:

The present invention relates to pigment-comprising formulations which comprise as binder at least one aqueous polymer dispersion whose polymer is functionalized with phosphonate groups.
Pigmented formulations are employed widely in the form of emulsion paints, synthetic-resin-bound plasters (dispersion plasters), sealing compounds or filling compositions for purposes of architectural protection or for decorative purposes. Pigmented formulations generally include as binder a film-forming polymer, at least one inorganic pigment with or without one or more inorganic fillers, and also customary auxiliaries. The quality of the coatings formed from pigmented formulations depends critically on the ability of the film-forming polymer to bind, equally, the nonfilm-forming constituents, the pigments and inorganic fillers.
A low pigment-binding capacity leads to poor mechanical stability of the coating, which is manifested, for example, in a low wet abrasion resistance. The desire, however, is for high wet abrasion resistance, especially in the case of washable emulsion
The pigment-binding capacity of the binder plays a particularly important part in formulations having a high content of inorganic pigments and fillers which is generally reflected in a pigment volume concentration (p.v.c.) of  greater than 40%. The p.v.c. is usually defined as the percentage quotient of the overall volume of the solid inorganic constituents (pigment+fillers) divided by the overall volume of the solid inorganic constituents and of the polymer particles of the aqueous binder polymer dispersion; see Ullmanns Enzyklopxc3xa4die der technischen Chemie, 4th Edition, Volume 15, p. 668.
In the case of exterior applications in particular, the coating compositions should be stable to environmental influences such as sunlight, moisture and fluctuations in temperature. In addition, the coating composition must adhere well to a variety of substrates, which again depends on the chosen binder polymer.
Another property dependent on the binder polymer is the blocking resistance of the coatings.
EP-A-184 091 describes coating compositions based on aqueous polymer dispersions which have a low film-forming temperature and form films of high blocking resistance. The polymer dispersions disclosed therein may also comprise, in copolymerized form, monomers having a crosslinking action. The coating materials described include only small amounts of inorganic substances and pigments.
EP-A-327 006 and EP-A-327 376 describe aqueous polymer dispersions comprising siloxane-functional monomers in copolymerized form. Such monomers, however, are expensive, with even a small amount pushing up the binder preparation costs sharply. It must also be reckoned that hydrolysis of the siloxane groups will alter the properties of the binder in the course of storage.
U.S. Pat. No. 4,219,454 describes binders for coating materials which are based on aqueous polymer dispersions comprising, in copolymerized form, urea-functional monomers for improving the adhesion of the coatings in the moist state. The coatings described therein, however, have only low pigment contents. The problem of the wet abrasion resistance of coating materials is not adequately solved by the polymers described therein.
GB 1,189,560 discloses latex paints (=emulsion paints) to which low molecular mass alkyl phosphates or alkyl phosphonates are added to improve the dispersion of the inorganic pigments.
EP-A-625 541 and WO 93/11181 disclose titanium dioxide-containing formulations comprising as binder aqueous polymer dispersions whose polymers have phosphate groups. The phosphate groups improve the adsorption of the latex particles on the surface of the pigment particles. The storage life of the formulations disclosed therein, however, leaves much to be desired, since their viscosity increases over the course of time.
U.S. Pat. No. 4,110,285 proposes polymers containing phosphate groups as binders for high-gloss emulsion paints. Here too, the problem of storage life arises.
The prior art binders are able to go only some of the way toward meeting the requirements that are placed on coating materials.
It is an object of the present invention to provide pigmented formulations possessing a high pigment-binding capacity, and hence a high wet abrasion resistance, good wet adhesion to a very wide variety of substrates, and good blocking resistance. These properties must also be retained at relatively high pigment volume concentrations, ie. p.v.c.  greater than 40%. In addition, the formulations are required to be stable on storage; in other words, their viscosity should show little or no increase even on prolonged storage.
We have found that this object is achieved by using, for the formulations, binders based on aqueous dispersions whose polymers have been modified with phosphonate groups.
The present invention accordingly provides formulations for coating substrates, comprising
i) at least one polymer P which has phosphonate groups, as binder,
ii) at least one inorganic pigment,
iii)if desired, one or more inorganic fillers, and
iv) customary auxiliaries.
The phosphonate-functional polymers P to be used in the formulations of the invention are in principle obtainable in a variety of ways. For instance, the phosphonate groups can be generated in a conventional polymer by means of polymer-analogous reaction. The sole prerequisite for this is that the polymer has reactive functional groups that are amenable to a polymer-analogous reaction. One possible procedure, for example, is to react a reactive functional group of the polymer in a polymer-analogous reaction with a phosphonate-functional compound which in turn possesses a reactive functional group that is complementary to the reactive group on the polymer. An example is the reaction of polymers having glycidyl groups with compounds that contain phosphonate groups and additionally have amino groups, and vice versa. The reaction of phosphonate groups can take place, for example, in the manner of a Moedritzer reaction (Moedritzer et al., J. Org. Chem. 31 (1966) 1603) by reacting amino-containing polymers with phosphorous acid in the presence of formaldehyde.
The preparation of phosphonate-functional polymers P, and the preparation of appropriate prepolymers, which are converted only subsequently by polymer-analogous reaction into the phosphonate-functional polymers P, can in principle take place by all known polymerization techniques for ethylenically unsaturated monomers, such as bulk, solution, precipitation, suspension or emulsion polymerization. Preparation takes place preferably by means of emulsion polymerization. This is particularly appropriate when the phosphonate groups are introduced by copolymerizing appropriate phosphonate-functional monomers into the polymer P.
In general, the polymers P are used in the form of aqueous dispersions in the pigmented formulations of the invention. It is not least for this reason that free-radical aqueous emulsion polymerization is advisable for preparing the polymers P. Polymers P obtainable in another way can be converted to aqueous dispersions by means of suitable measures that are known from the prior art (and are then known as secondary dispersions).
Preferably, the aqueous polymer dispersions employed in the formulations of the invention are obtainable by free-radical aqueous emulsion polymerization of ethylenically unsaturated monomers, in which at least one monomer a and at least one different monomer b of the formula I
where
R1 is hydrogen, C1-C4-alkyl, COOH, xe2x80x94CO2-Alk-OH or xe2x80x94CO2-Alk-P(O)(OH)2 and
R2 is hydrogen, alkyl, xe2x80x94CH2xe2x80x94CO2H, xe2x80x94CH2xe2x80x94CO2-Alk-OH or CH2xe2x80x94CO2-Alk-P(O)(OH)2, in which
Alk is C1-C4-alkylene,
X is a single bond, alkylene, arylene, xe2x80x94R3xe2x80x94Zxe2x80x94Oxe2x80x94R4xe2x80x94 or xe2x80x94R3xe2x80x94Zxe2x80x94NHxe2x80x94R4xe2x80x94, in which
R3 is attached to a carbon of the double bond and is a single bond, alkylene or arylene,
R4 is alkylene or arylene and
Z is CO or SO2
or a salt thereof are reacted with one another.
In the text below alkyl is preferably linear or branched C1-C12-alkyl, especially C1-C8-alkyl, such as methyl, ethyl, n-propyl, i-propyl, 1-butyl, 2-butyl, i-butyl, t-butyl, 1-pentyl, 2-pentyl, 3-pentyl, 1-hexyl or 2-ethylhexyl. Cycloalkyl is preferably cyclopentyl or cyclohexyl. Aryl is preferably phenyl or naphthyl unsubstituted or substituted by 1 to 4 substituents selected independently from C1-C4-alkyl, especially methyl or ethyl, C1-C4-alkoxy, such as methoxy or ethoxy, hydroxyl, which can also if desired be ethoxylated, and halogen. Alkylene is a divalent alkyl, preferably a C1-C12-alkyl, such as methylene, 1,1- or 1,2-ethylene, 1,1-, 1,2-, 1,3- or 2,2-propylene, 1,4-butylene, 2-methyl-1,2-propylene, 1,6-hexylene and 1,8-octylene. Arylene is a divalent aryl, preferably 1,2- or 1,4-phenylene. Aralkyl is an aryl attached to the respective center via an alkylene. Oxyalkylene is an alkylene attached to the polymer via an oxygen, and hence polyoxyalkylene denotes alkylene units each attached to one another by way of oxygens.
In the formula I R1 is preferably hydrogen. R2 is preferably hydrogen or methyl. X is preferably a single bond, C1-C4-alkylene, especially methylene, or is arylene, especially 1,2-, 1,3- or 1,4-phenylene. Alternatively, X is preferably a group xe2x80x94R3xe2x80x94Zxe2x80x94NHxe2x80x94R4xe2x80x94 where R3 is a single bond and Z is a carbonyl function. R4 in this case is preferably C1-C4-alkylene, especially 1,2-ethylene and 2-methyl-1,2-propylene. Examples of suitable phosphonate-functional monomers of the formula I include vinylphosphonic acid, allylphosphonic acid, xcex1-phosphonostyrene, 2-acrylamido-2-methylpropanephosphonic acid, 2-methacrylamido-2-methylpropanephosphonic acid and salts thereof, examples being their alkali metal salts.
Particularly preferred monomers b are vinyl phosphonate and allyl phosphonate, and their salts, especially their sodium salts. The phosphonate-functional monomers b make up preferably from 0.1 to 10% by weight, in particular from 0.2 to 5% by weight and, with particular preference, from 0.5 to 3% by weight of the total monomer amount.
Suitable monomers a are selected from vinylaromatic monomers such as styrene, xcex1-methylstyrene, ortho-chlorostyrene or vinyltoluenes, vinyl esters of C1-C18 and preferably C1-C12 monocarboxylic acids, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl decanoate, vinyl laurate, vinyl stearate and vinyl Versatate(copyright) (vinyl esters of branched, aliphatic carboxylic acids having 6 to 11 carbons, which are in commerce as Versatic(copyright) X acids from Shell). Also suitable are esters of xcex1,xcex2-ethylenically unsaturated C3-C8 mono- or C4-C8 dicarboxylic acids, preferably with C1-C12- and, in particular, C1-C8-alkanols or C5-C8-cycloalkanols. Examples of suitable C1-C12-alkanols are methanol, ethanol, n-propanol, i-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, n-hexanol and 2-ethylhexanol. Examples of suitable cycloalkanols are cyclopentanol or cyclohexanol. Particularly suitable are esters of acrylic acid, of methacrylic acid, of crotonic acid, of maleic acid, of itaconic acid, of citraconic acid or of fumaric acid. Specifically these are methyl, ethyl, n-butyl, isobutyl, 1-hexyl and 2-ethylhexyl (meth)acrylate, dimethyl maleate or di-n-butyl maleate. Also suitable are nitriles of xcex1,xcex2-monoethylenically unsaturated C3-C8 carboxylic acids, such as acrylonitrile or methacrylonitrile. It is also possible to employ C4-C8 conjugated dienes, such as 1,3-butadiene, isoprene or chloroprene, as monomers a. Said monomers make up preferably from 80 to 99.9% by weight, in particular from 90 to 99.9% by weight and, especially, from 95 to 99.7% by weight, based on the overall weight of the monomers employed. The monomers a preferably include at least two different monomers a1 and a2. Preferred monomers a1 and a2 are the C1-C12-alkyl esters of acrylic acid and of methacrylic acid, vinylaromatic monomers, especially styrene and xcex1-methylstyrene, and the vinyl esters of aliphatic C1-C12 carboxylic acids, preferably vinyl acetate and vinyl propionate, which are employed alone or in combination with vinyl chloride and/or ethylene, with vinyl Versatates or with C1-C8-alkyl acrylates as monomers a.
The binder polymers P preferably also comprise monomers c in copolymerized form, which enhance the wet adhesion of the formulations of the invention. Such monomers include ethylenically unsaturated compounds having urea groups (monomers c) examples being N-vinyl- and N-allylurea and derivatives of imidazolidin-2-one, such as N-vinyl- and N-allylimidazolidin-2-one, N-vinyloxyethylimidazolidin-2-one, N-(2-(meth)acrylamidoethyl)imidazolidin-2-one, N-(2-(meth)acryloxyethyl)imidazolidin-2-one, N-[2-((meth)acryloxyacetamido)ethyl]imidazolidin-2-one, etc. The monomers c are preferably used in amounts of from 0.1 to 10% by weight, in particular from 0.5 to 5% by weight, based on the total monomer amount.
The polymer P may also include monomers d in copolymerized form, the homopolymers of which are of increased solubility or swellability in water. These monomers are preferably copolymerized in amounts of  less than 5% by weight, and preferably  less than 2% by weight, based on the total monomer amount. Such monomers raise the stability of the polymer dispersions. They include monomers containing acidic groups (monomers d1), such as xcex1,xcex2-monoethylenically unsaturated mono- and dicarboxylic acids of 3 to 10 carbons, and also ethylenically unsaturated sulfonic acids, and the water-soluble salts thereof. Examples of monomers d1 having acidic groups are the above-mentioned ethylenically unsaturated carboxylic or dicarboxylic acids, especially acrylic and methacrylic acid, and also vinyl- and allylsulfonic acid, (meth)acrylamidoethanesulfonic acid, methacrylamido-2-methyl-propanesulfonic acid and the alkali metal salts of the sulfonic acids, especially their sodium salts. It should be noted here, however, that a high content of acid groups in the binder polymer reduces the water resistance of coatings. Other than the phosphonate-functional monomers b of the invention the polymer P preferably contains no other monomers which possess an acidic group. The monomers d also embrace neutral or nonionic, modifying monomers d2, examples being the amides, N-alkylolamides or hydroxyalkyl esters of the above-mentioned carboxylic acids, such as acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.
Furthermore, bifunctional monomers e can be employed in preparing the polymer P. Where desired these monomers e are copolymerized in a minor amount, generally from 0.1 to 5% by weight and in particular up to 1% by weight, based on the total monomer amount. They preferably comprise monomers having two nonconjugated, ethylenically unsaturated bonds, examples being the diesters of dihydric alcohols with xcex1,xcex2-monoethylenically unsaturated C3-C8 carboxylic acids, such as glycol bisacrylate, or esters of xcex1,xcex2-unsaturated carboxylic acids with alkenols, such as bicyclodecenyl (meth)acrylate. Preferred polymers P contain no copolymerized monomers e.
The binder polymers can of course also include monomers which are known to improve the pigment-binding power. Examples of these include siloxane-functional monomers, such as the vinyltrialkoxysilanes, vinyltrimethoxysilane for example, the alkylvinyldialkoxysilanes or the (meth)acryloxyalkyltrialkoxysilanes, such as (meth)acryloxyethyltrimethoxysilane or (meth)acryloxypropyltrimethoxysilane. These monomers can be used in amounts of up to 1% by weight, preferably from 0.05 to 0.5% by weight, based on the total monomer amount.
The character of the formulations of the invention is also dependent on the glass transition temperature (DSC, midpoint temperature, ASTM D 3418-82) of the binder polymer P. If Tg is too low, the coating is not very strong and tears when subjected to a mechanical load. If it is too high, the polymer no longer forms a film and the coating thus exhibits a reduced wet abrasion resistance. The glass transition temperature Tg of the binder polymers P in question is therefore generally below 80xc2x0 C., preferably below 60xc2x0 C. and, with particular preference, below 400xc2x0 C. In general, however, it is above xe2x88x9260xc2x0 C., preferably above xe2x88x9210xc2x0 C. and, in particular, above 0xc2x0 C. In this context it proves useful to estimate the glass transition temperature of the dispersed polymer. According to Fox (T. G. Fox, Bull. Am. Phys. Soc. (Ser. II) 1 [1956] 123 and Ullmanns Enzyklopxc3xa4die der technischen Chemie, Weinheim (1980) p. 17, 18) the glass transition temperature of copolymers at high molar masses is given in good approximation by       1          T      g        =                    X        1                    T        g        1              +                  X        2                    T        g        2              +          ⋯                    xe2x80x83                                    X          n                          T          g          n
where X1, X2, . . . , Xn are the mass fractions of the monomers 1, 2, . . . , n and Tg1, Tg2, . . . , Tgn are the glass transition temperatures of the homopolymers of 1, 2, . . . , n, in kelvins. These temperatures are known, for example from Ullmann""s Encyclopedia of Industrial Chemistry, VCH, Weinheim, Vol. A 21 (1992) p. 169 or from J. Brandrup, E. H. Immergut, Polymer Handbook 3rd ed., J. Wiley, New York 1989.
From what has been said above it is clear that the glass transition temperature of a polymer can be adjusted both by choosing an appropriate principal monomer a having a glass transition temperature within the desired range and by combining at least one monomer a1 with a high glass transition temperature and at least one monomer a2 with a low glass transition temperature, the latter procedure being preferred.
In a preferred embodiment of the present invention the monomers a making up the polymer P include at least one monomer a1 whose homopolymer for the limiting case of a very high (infinite) molecular mass, has a glass transition temperature Tg of  greater than 30xc2x0 C., and at least one monomer a2 whose homopolymer has a glass transition temperature Tg of  less than 20xc2x0 C. Monomers a1 suitable for this purpose are, for example, styrene, xcex1-methylstyrene, methyl methacrylate, ethyl methacrylate, n- and isopropyl methacrylate, n-, iso- and tert-butyl methacrylate, tert-butyl acrylate and vinyl acetate, and also acrylonitrile and methacrylonitrile, the two nitriles preferably making up not more than 30% by weight of the monomers a1. Examples of suitable monomers a2 for this purpose are the C1-C12-alkyl acrylates, butadiene, vinyl Versatates, and especially ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate. Particular preference is given to monomer combinations a1/a2 which comprise styrene and/or methyl methacrylate and also n-butyl acrylate with or without 2-ethylhexyl acrylate.
In a particularly preferred embodiment of the present invention the binder polymer P is composed of:
i) from 20 to 80% by weight, preferably from 35 to 70% by weight, of monomers a1, especially styrene and/or methyl methacrylate,
ii) from 20 to 80% by weight, preferably from 30 to 65% by weight, of monomers a2, especially n-butyl acrylate and/or ethylhexyl acrylate,
iii)from 0.2 to 5% by weight, preferably from 0.5 to 3% by weight, of at least one monomer b, especially vinyl phosphonate, allyl phosphonate and/or 2-methacrylamido-2-methylpropanephosphonic acid or the sodium salts thereof,
iv) from 0.5 to 5% by weight, preferably from 1 to 3% by weight, of monomers c having at least one urea group, especially an ethylenically unsaturated derivative of imidazolidin-2-one,
the proportions by weight of monomers a1, a2, b and c adding up to 100% by weight.
It has additionally proven advantageous if the polymer particles in the binder polymer dispersion have a ponderal median polymer particle diameter in the range from 50 to 1000 nm (determined by means of an ultracentrifuge or by photon correlation spectroscopy; regarding the determination of particle size by ultracentrifuge see, for example, W. Mxc3xa4chtle, Makromolekulare Chemie 185 (1984) 1025-1039 and Angew. Makromolekulare Chemie 162 (1988) 35-42). In the case of binder dispersions having high solids contents, such as  greater than 50% by weight, based on the overall weight of the binder dispersion, it is advantageous on grounds of viscosity for the ponderal median particle diameter of the polymer particles of the dispersion to be xe2x89xa7250 nm. The median particle diameter will generally not exceed 1000 nm and preferably will not exceed 600 nm.
The aqueous polymer dispersions employed in accordance with the invention are preferably prepared by free-radical aqueous emulsion polymerization of the above-mentioned monomers in the presence of at least one free-radical polymerization initiator, with or without a surface-active substance.
Suitable free-radical polymerization initiators are all those capable of triggering a free-radical aqueous emulsion polymerization. They can be peroxides, for example alkali metal peroxodisulfates, or azo compounds. As polymerization initiators it is common to use redox initiators, which are composed of at least one organic reducing agent and at least one peroxide and/or hydroperoxide, examples being tert-butyl hydroperoxide with sulfur compounds, such as the sodium salt of hydroxymethanesulfinic acid, sodium sulfite, sodium disulfite, sodium thiosulfate or acetone bisulfate, or hydrogen peroxide with ascorbic acid. Use is also made of combined systems which comprise a small amount of a metal compound which is soluble in the polymerization medium and whose metal component can exist in a plurality of valence states, an example of such a system being ascorbic acid/iron (II)sulfate/hydrogen peroxide, where the ascorbic acid is frequently replaced by the sodium salt of hydroxymethanesulfinic acid, acetone bisulfite, sodium sulfite, sodium hydrogen sulfite or sodium bisulfite and the hydrogen peroxide by organic peroxides, such as tert-butyl hydroperoxide, or by alkali metal peroxodisulfates and/or ammonium peroxodisulfate. Initiators which are likewise preferred are peroxodisulfates, such as sodium peroxodisulfate. The amount of the free-radical initiator systems that are employed, based on the overall amount of the monomers to be polymerized, is preferably from 0.1 to 2% by weight.
Surface-active substances suitable for conducting the emulsion polymerization are the emulsifiers and protective colloids commonly employed for this purpose. The surface-active substances are normally employed in amounts of up to 10% by weight, preferably from 0.5 to 5% by weight, and in particular, from 1 to 4% by weight, based on the monomers to be polymerized.
Examples of suitable protective colloids are polyvinyl alcohols, starch and cellulose derivatives, or vinylpyrrolidone copolymers. An exhaustive description of further suitable protective colloids is given in Houben-weyl, Methoden der organischen Chemie, Volume XIV/1, makromolekulare Stoffe (Macromolecular substances), Georg-Thieme-Verlag, Stuttgart 1961, pp. 411-420. Mixtures of emulsifiers and/or protective colloids can also be used. As surface-active substances it is preferred to employ exclusively emulsifiers, whose relative molecular weights, unlike those of the protective colloids, are usually below 2000. They can be anionic, cationic or else nonionic in nature. The anionic emulsifiers include alkali metal and ammionium salts of alkyl sulfates (alkyl: C8-C12), of sulfuric monoesters of ethoxylated alkanols (EO units: 2 to 50, alkyl: C12 to C18) and of ethoxylated alkylphenols (EO units: 3 to 50, alkyl: C4-C9), of alkylsulfonic acids (alkyl: C12-C18) and of alkylarylsulfonic acids (alkyl: C9 to C18). Further suitable emulsifiers are given in Houben-Weyl, loc. cit., pp 192-208).
The anionic surface-active substances also include compounds of the formula II
where R1 and R2 are hydrogen or C4-C24-alkyl but are not both hydrogen, and X and Y can be alkali metal and/or ammonium ions. In the formula II R1 and R2 are preferably linear or branched C6-C18-alkyls or hydrogen, and in particular have 6, 12 or 16 carbons but are not both hydrogen. X and Y are preferably sodium, potassium or ammonium, with sodium being particularly preferred. Particularly advantageous compounds II are those in which X and Y are sodium, R1 is a branched alkyl of 12 carbons and R2 is hydrogen or is the same as R1. Use is frequently made of technical-grade mixtures which have a proportion of from 50 to 90% by weight of the monoalkylated product, an example being Dowfax(copyright) 2A1 (trademark of Dow Chemical Company). The compounds II are widely known, for example from U.S. Pat. No. 4,269,749, and are obtainable commercially.
In addition to these anionic emulsifiers it is also possible to use nonionic emulsifiers. Suitable nonionic emulsifiers are araliphatic or aliphatic nonionic emulsifiers, examples being ethoxylated mono-, di- and trialkylphenols (EO units: 3 to 50, alkyl: C4-C9), ethoxylates of long-chain alcohols (EO units: 3 to 50, alkyl: C8-C36), and also polyethylene oxide/polypropylene oxide block copolymers. Preference is given to ethoxylates of long-chain alkanols (alkyl: C10-C22, mean degree of ethoxylation: 3 to 50) and, of these, particular preference to those based on naturally occurring alcohols or oxoalcohols having a linear or branched C12-C18-alkyl radical and a degree of ethoxylation of from 8 to 50. It is preferred to use anionic emulsifiers, or combinations of at least one anionic and one nonionic emulsifier.
The molecular weight of the polymers can be adjusted by adding small amounts, generally up to 2% by weight based on the monomers to be polymerized, of one or more molecular weight regulators, examples being organic thio compounds, silanes, allyl alcohols or aldehydes.
The emulsion polymerization can be conducted either continuously or by the batch procedure, preferably by a semicontinuous procedure. In this case the monomers to be polymerized can be supplied continuously, including by a stepwise or gradient procedure, to the polymerization batch.
In addition to the seed-free preparation method it is also possible, in order to establish a defined polymer particle size, to conduct the emulsion polymerization by the seed latex process or in the presence of seed latex prepared in situ. Processes for this purpose are known and can be taken from the prior art (see EP-B 40419, EP-A-614 922, EP-A-567 812 and literature cited therein, and also xe2x80x98Encyclopedia of Polymer Science and Technologyxe2x80x99, Vol. 5, John Wiley and Sons Inc., New York 1966, p. 847).
The polymerization is preferably conducted in the presence of from 0.01 to 3% by weight, and in particular from 0.05 to 1.5% by weight, of a seed latex (solids content of the seed latex, based on total monomer amount), preferably with a seed latex included in the initial charge (initial-charge seed). The latex generally has a weight-average particle size of from 10 to 100 nm and, in particular, from 20 to 50 nm. Its constituent monomers are, for example, styrene, methyl methacrylate, n-butyl acrylate and mixtures thereof, and to a minor extent it may also include monomers d, preferably less than 10% by weight based on the overall weight of the polymer particles in the seed latex, in copolymerized form.
The pressure and temperature of polymerization are of minor importance. It is normal to operate at between room temperature and 120xc2x0 C., preferably at from 40 to 95xc2x0 C. and, with particular preference, at from 50 to 90xc2x0 C.
Following the actual polymerization reaction it is possible if desired to render the aqueous polymer dispersions of the invention substantially free from odoriferous substances, such as residual monomers and other volatile organic constituents. This can be done physically in a manner known per se, by distillative removal (especially by steam distillation) or by stripping with an inert gas. The residual monomer content can also be lowered chemically by means of free-radical postpolymerization, especially under the action of redox initiator systems, as are set out, for example, in DE-A 44 35 423, DE-A 44 19 518 and DE-A 44 35 422. The postpolymerization is preferably conducted with a redox initiator system comprising at least one organic peroxide and one organic sulfite.
By the method of emulsion polymerization it is possible in principle to obtain dispersions having solids contents of up to about 80% by weight (polymer content based on the overall weight of the dispersion). For practical reasons it is generally preferred to use polymer dispersions having solids contents in the range from 40 to 70% by weight for the formulations of the invention. Particular preference is given to dispersions having polymer contents of  greater than 50% by weight. Dispersions having lower solids contents are of course also suitable in principle for the formulations of the invention.
In accordance with the invention the phosphonate-functional polymers P are employed in the form of their aqueous polymer dispersions as binders in pigmented formulations that are used to coat substrates. Examples of what are meant by such formulations include polymer dispersion plasters, tile adhesives, paints and varnishes, or sealants (sealing compounds), especially for porous components.
A preferred embodiment of the present invention concerns formulations in the form of emulsion paints.
The formulations of the invention, preferably emulsion paints, generally contain from 30 to 75% by weight and, preferably, from 40 to 65% by weight of nonvolatile constituents. By these are meant all those constituents of the formulation except for water, but at least the total amount of binder, filler, pigment and solvents of low volatility, such as plasticizers, and polymeric auxiliaries. Of these, the amounts accounted for by each class of constituent are
from 5 to 90% by weight, preferably from 10 to 60% by weight, by solid binder constituents (=polymer P),
ii from 5 to 85% by weight, preferably from 10 to 60% by weight, by at least one inorganic pigment,
iii from 0 to 85% by weight, preferably from 20 to 70% by weight, by inorganic fillers, and
iv from 0.1 to 40% by weight, preferably from 0.5 to 15% by weight, by customary auxiliaries.
The p.v.c. of the formulations is generally above 10%, for example from 15 to 75%. In one preferred embodiment of the invention it is in the range from 15 to 25%. In another preferred embodiment of the invention the p.v.c. is in the range from  greater than 40% to 60% by weight, for example about 45% by weight. In another preferred embodiment of the invention the p.v.c. is  greater than 60%, preferably  greater than 70%, and can be up to 85%.
Typical pigments for the formulations of the invention, especially for emulsion paints, are, for example, titanium dioxide, preferably in the rutile form, barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide, and lithopones (zinc sulfide +barium sulfate). However, the formulations may also comprise color pigments, such as iron oxides, carbon black, graphite, luminescent pigments, zinc yellow, zinc green, ultramarine, manganese black, antimony black, manganese violet, Paris blue or Schweinfurter green. In addition to the inorganic pigments the formulations of the invention may also include organic color pigments, examples being sepia, gamboge, Cassel brown, toluidine red, para red, Hansa yellow, indigo, azo dyes, anthraquinonoid and indigoid dyes, and also dioxazine, quinacridone, phthalocyanine, isoindolinone and metal complex pigments.
Suitable fillers include, basically, alumosilicates, such as feldspars, silicates, such as kaolin, talc, mica, magnezite, alkaline earth metal carbonates, such as calcium carbonate, in the form of calcite or chalk, for example, magnesium carbonate, dolomite, alkaline earth metal sulfates, such as calcium sulfate, silicon dioxide, etc. The fillers can be employed as individual components. In practice, however, filler mixtures have proven especially suitable, such as calcium carbonate/kaolin and calcium carbonate/talc. Dispersion plasters may also include relatively coarse aggregates, such as sands or sandstone granules. In emulsion paints, of course, finely divided fillers are preferred.
To increase the hiding power and to save on the use of white pigments it is common to employ finely divided extenders, such as finely divided calcium carbonate or mixtures of various calcium carbonates with different particle sizes, in the preferred emulsion paints. To adjust the hiding power, the shade and the depth of color it is preferred to employ blends of color pigments and extenders.
The customary auxiliaries iv include wetting agents or dispersions, such as sodium or potassium polyphosphates, alkali metal salts of polyacrylic acids, alkali metal salts of polymaleic acid, polyphosphonates, such as sodium 1-hydroxyethane-1,1-diphosphonate, and also naphthalenesulfonic acid salts, especially their sodium salts. The dispersants or wetting agents are generally employed in an amount of from 0.1 to 0.6% by weight, based on the overall weight of the emulsion paint.
The auxiliaries iv may also include thickeners, examples being cellulose derivatives, such as methylcellulose, hydroxyethylcellulose and carboxymethylcellulose, and also casein, gum arabic, tragacanth gum, starch, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylates, water-soluble copolymers based on acrylic and methacrylic acid, such as acrylic acid/acrylamide and methacrylic acid/acrylate copolymers, and associative thickeners, such as styrene-maleic anhydride polymers or, preferably, hydrophobically modified polyether urethanes, as are described, for example, by N. Chen et al. in J. Coatings Techn., Vol. 69, No. 867, 1997, p. 73 and by R. D. Hester et al., J. Coatings Technology, Vol. 69, No. 864, 1997, 109. The disclosure content of these documents is hereby incorporated in its entirety by reference.
Examples of hydrophobically modified polyether urethanes are polymers of the formula III
where Rf is a hydrophobic radical, preferably a linear or branched alkyl of 10 to 20 carbons, Et is 1,2-ethylene, Sp is C2-C10-alkylene, cycloalkylene or arylene, k is from 50 to 1000 and l is from 1 to 10, the product kxc3x97l preferably being from 300 to 1000.
Inorganic thickeners, such as bentonites or hectorite, can also be used. Thickeners are generally used in amounts of from 0.1 to 3% by weight, preferably from 0.1 to 1% by weight, based on the overall weight of the aqueous formulation. In addition, the auxiliaries iv generally include defoamers, preservatives or hydrophobicizing agents, biocides, fibers or other constituents.
In addition, in order to establish the film-forming properties of the binder polymers, the coating materials may also comprise what are known as film-forming consolidating agents (plasticizers), examples being ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, alkyl ethers and alkyl ether esters of glycols and polyglycols, for example diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, hexylene glycol diacetate, propylene glycol monoethyl ether, propylene glycol monophenyl ether, monobutyl ether and monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol mono-n-butyl ether, and the acetates of the abovementioned monoalkyl ethers, for example butoxybutyl acetate, and also alkyl esters of aliphatic mono- and dicarboxylic acids, for example Texanol from Eastman, or technical-grade mixtures of dibutyl esters of succinic acid, glutaric acid and adipic acid, and also hydrocarbons and/or mixtures thereof, with or without aromatic constituents, such as white spirits in the boiling range of from 140 to 210xc2x0 C. Film-forming auxiliaries are customarily employed in amounts of from 0.1 to 20% by weight, based on the polymer P present in the formulation, so that the formulation has a minimum film-forming temperature of  less than 15xc2x0 C. and preferably from 0 to 10xc2x0 C.
Furthermore, the formulations employed in accordance with the invention may also include crosslinking additives. Additives of this kind can be: aromatic ketones, such as alkyl phenyl ketones unsubstituted or with one or more substituents on the phenyl ring, or benzophenone and substituted benzophenones, as photoinitiators. Photoinitiators suitable for this purpose are known, for example, from DE-A-38 27 975 and EP-A-417 568. Other suitable crosslinking compounds are water-soluble compounds having at least two amino groups, examples being dihydrazides of aliphatic dicarboxylic acids in accordance with DE-A-39 01 073, if the copolymer P comprises carbonyl-containing monomers in copolymerized form.
The formulations of the invention are stable fluid systems which can be used to coat a large number of substrates. Accordingly, the present invention also provides a method of coating substrates. Examples of suitable substrates are wood, concrete, metal, glass, ceramics, plastic, plaster, wallpaper and coated, primed or weathered substrates. The formulation is applied to the target substrate in a manner dependent on the form of the formulation. Depending on the viscosity and pigment content of the formulation and on the substrate application may take place by means of rolling, brushing, knife coating or spraying.
The coatings produced using the formulations of the invention are notable for high wet abrasion resistance and good adhesion in the wet state. The improved wet abrasion resistancexe2x80x94in other words, an improved mechanical stability of the coatings to abrasive influences in the wet statexe2x80x94is favorable for the weathering stability of the coatings and also provides them with washability. Moreover, the coatings are not tacky, and feature a high blocking resistance.
The advantageous properties of the polymer P as binder relative to prior art binder polymers, and especially its improved wet abrasion resistance, is equally in evidence in the case of pigmented formulations having a p.v.c. of  less than 40% and with formulations having a p.v.c. of  greater than 40% or a p.v.c. of  greater than 60%. The advantages of the invention become particularly evident if the formulations have a p.v.c. of  greater than 40% and up to 85%, for example a p.v.c. of about 45% or a p.v.c. of from 70 to 80%. Accordingly, the present invention also provides for the use of the polymers P for improving the wet abrasion resistance of pigment-comprising formulations.

Pigmented formulations based on aqueous polymer dispersions

Abstract: (i) an aqueous dispersion of at least one water-insoluble polymer P which has phosphonate groups, as a binder, said polymer P having a glass transition temperature Tg in the range of xe2x88x9260xc2x0 to 80xc2x0 C.,

Abstract: (ii) at least one inorganic pigment,

Abstract: (iii) optionally, one or more inorganic fillers, and

Abstract: (iv) at least one auxiliary,

Abstract: wherein water-insoluble polymer P is obtained by free-radical aqueous emulsion polymerization of ethylenically unsaturated monomers comprising:

Abstract: 90 to 99.9% by weight of at least one monomer a, which is selected from the group consisting of vinylaromatic monomers, the esters of acrylic acid with C1-C12-alkanols, the vinyl esters of aliphatic C1-C12-monocarboxylic acids, ethylene and vinylchloride, and

Abstract: 0.1 to 10% by weight of at least one phosphonate group containing monomer.


An indexing mechanism with positive ON and OFF positions for a motor starter switch mounted in an NEMA 3R enclosure. The indexing mechanism includes a shaft having longitudinally extending projections coupled in fixed relationship to a handle, an index element coupled to the shaft, and a yoke having a pin positioned to engage the index element to positively position the shaft to the first or the second position.

An electrical device, such as an electrical motor, typically requires a switch mechanism to control power to the device. The switch mechanism may include an electrical switch coupled to a user accessible mechanical actuator such as a handle. If the switch mechanism is used in an industrial environment, it may be mounted in an enclosure to provide personnel safety and equipment protection. An example of an enclosure is a type 3R enclosure specified by the national electrical manufacturers association (NEMA) which provides a forum for the standardization of electrical equipment. However, the switch mechanism may exhibit "play" as it is rotated to a first or second position (e.g., ON or OFF).
What is needed is a switch mechanism that provides a positive index or "feel" when it is moved between positions.