The present invention discloses peptide aldehydes which are potent and specific inhibitors of thrombin, their pharmaceutically acceptable salts, pharmaceutically acceptable compositions thereof, and methods of using them as therapeutic agents for disease states in mammals characterized by abnormal thrombosis.

Normal hemostasis is the result of a complex balance between the processes of clot formation (blood coagulation) and clot dissolution (fibrinolysis). The complex interactions between blood cells, specific plasma proteins and the vascular surface, maintain the fluidity of blood unless injury and blood loss occur.
Blood coagulation is the culmination of a series of amplified reactions in which several specific zymogens of serine proteases in plasma are activated by limited proteolysis. Nemerson, Y. and Nossel, H. L., Ann. Rev. Med., 33: 479 (1982). This series of reactions results in the formation of an insoluble fibrin matrix which is required for the stabilization of the primary hemostatic plug. The interaction and propagation of the activation reactions occurs through the extrinsic and intrinsic pathways of coagulation.
These pathways are highly inter-dependent and converge in the formation of the serine protease, Factor Xa. Factor Xa catalyzes the penultimate step in the blood coagulation cascade which is the formation of the serine protease thrombin. This step occurs following the assembly of the prothrombinase complex which is composed of factor Xa, the non-enzymatic co-factor Va and the substrate prothrombin assembled on the surface of adhered, activated platelets or systemically circulating membranous microparticles.
Proteolytic activation of zymogen factor X to its catalytically active form, factor Xa, can occur by either the intrinsic or extrinsic coagulation pathways.
The intrinsic pathway is referred to as "intrinsic" because everything needed for clotting is in the blood. Saito, H., "Normal Hemostatic Mechanisms", Disorders of Hemostasis, pp. 27-29, Grune & Stratton, Inc. (O. D. Ratnoff, M. D. and C. D. Forbes, M. D. edit. 1984). This pathway is comprised of the zymogen serine proteases, factors IX and XI, and the non-enzymatic co-factor, factor VIII. The initiation of the intrinsic pathway results in the activation of factor XI to XIa. Factor XIa catalyzes the activation of factor IX to factor IXa which in combination with the activated form of factor VIII on an appropriate phospholipid surface, results in the formation of the tenase complex. This complex also catalyzes the formation of the serine protease, factor Xa, from its zymogen, factor X which subsequently results in clot formation.
The extrinsic pathway is referred to as "extrinsic" because the tissue factor which binds to and facilitates the activation of factor VII comes from outside the blood. Saito, Id. The major components of this pathway are the zymogen serine protease, factor VII, and the membrane bound protein, tissue factor. The latter serves as the requisite non-enzymatic co-factor for this enzyme. The initiation of this pathway is thought to be an autocatalytic event resulting from the activation of zymogen factor VII by trace levels of activated factor VII (factor VIIa), both of which are bound to newly exposed tissue factor on membrane surfaces at sites of vascular damage. The factor VIIa/tissue factor complex directly catalyzes the formation of the serine protease, factor Xa, from its zymogen, factor X. Exposure of blood to injured tissue initiates blood clotting by the extrinsic pathway.
The formation of thrombin is catalyzed by factor Xa following the assembly of the catalytic prothrombinase complex as reviewed by Mann, K. G. et al., "Surface-Dependent Reactions of the Vitamin K-Dependent Enzyme Complexes", Blood, 76: 1-16 (1990). This complex is composed of factor Xa, the non-enzymatic co-factor Va and the substrate prothrombin all assembled on an appropriate phospholipid surface. The requirement of a macromolecular complex for efficient catalysis results in the protection of factor Xa from natural anticoagulant mechanisms such as heparin-antithrombin III mediated inhibition. Teite, J. M. and Rosenberg, R. D., "Protection of Factor Xa from neutralization by the heparin-antithrombin complex", J. Clin. Invest., 71: 1383-1391(1983). In addition, sequestration of factor Xa in the prothrombinase complex also renders it resistant to inhibition by exogenous heparin therapy which also requires antithrombin III to elicit its anticoagulant effect.
Thrombin is the primary mediator of thrombus formation. Thrombin acts directly to cause formation of insoluble fibrin from circulating fibrinogen. In addition, thrombin activates the zymogen factor XIII to the active transglutaminase factor XIIIa which acts to covalently stabilize the growing thrombus by crosslinking the fibrin strands. Lorand, L. and Konishi, K., Arch. Biochem. Biophys., 105: 58 (1964) Beyond its direct role in the formation and stabilization of fibrin rich clots, the enzyme has been reported to have profound bioregulatory effects on a number of cellular components within the vasculature and blood. Shuman, M. A., Ann. NY Acad. Sci., 405: 349 (1986).
It is believed that thrombin is the most potent agonist of platelet activation, and it has been demonstrated to be the primary pathophysiologic-mediator of platelet-dependent arterial thrombus formation. Edit, J. F. et al., J. Clin. Invest., 84: 18 (1989). Thrombin-mediated platelet activation leads to ligand-induced inter-platelet aggregation principally due to the bivalent interactions between adhesive ligands such as fibrinogen and fibronectin with platelet integrin receptors such as glycoprotein IIb/IIIa which assume their active conformation following thrombin activation. Berndt, M. C. and Phillips, D. R., Platelets in Biology and Pathology, pp 43-74, Elsevier/North Holland Biomedical Press (Gordon, J. L. edit. 1981). Thrombin-activated platelets can also support further thrombin production through the assembly of new prothrombinase and tenase (factor IXa, factor VIIIa and factor X) catalytic complexes on the membrane surface of intact activated platelets and platelet-derived microparticles, following thrombin-mediated activation of the non-enzymatic cofactors V and VIII, respectively. Tans, G. et al., Blood, 77: 2641 (1991). This positive feedback process results in the local generation of large concentrations of thrombin within the vicinity of the thrombus which supports further thrombus growth and extension. Mann, K. G. et al., Blood, 76: 1 (1990).
In contrast to its prothrombotic effects, thrombin has been shown to influence other aspects of hemostasis. These include its effect as an important physiological anticoagulant. The anticoagulant effect of thrombin is expressed following binding of thrombin to the endothelial cell membrane glycoprotein, thrombomodulin. This is thought to result in an alteration of the substrate specificity of thrombin thereby allowing it to recognize and proteolytically activate circulating protein C to give activated protein C (aPC). Musci, G. et al., Biochemistry, 27: 769 (1988). aPC is a serine protease which selectively inactivates the non-enzymatic co-factors Va and VIIIa resulting in a down-regulation of thrombin formation by the prothrombinase and tenase catalytic complexes, respectively. Esmon, C. T., Science, 235: 1348 (1987). The activation of protein C by thrombin in the absence of thrombomodulin is poor.
Thrombin has also been shown to be a potent direct mitogen for a number of cell types, including cells of mesenchymal origin such as vascular smooth muscle cells. Chen, L. B. and Buchanan, J. M., Proc. Natl. Acad. Sci. USA, 72: 131 (1975). The direct interaction of thrombin with vascular smooth muscle also results in vasoconstriction. Walz, D.A. et al., Proc. Soc. Expl. Biol. Med., 180: 518 (1985). Thrombin acts as a direct secretagogue inducing the release of a number of bioactive substances from vascular endothelial cells including tissue plasminogen activator. Levin, E. G. et al., Thromb. Haemost., 56: 115 (1986). In addition to these direct effects on vascular cells, the enzyme can indirectly elaborate potent mitogenic activity on vascular smooth muscle cells by the release of several potent growth factors (e.g., platelet-derived growth factor and epidermal growth factor) from platelet a-granules following thrombin-induced activation. Ross, R., N. Engl. J. Med., 314: 408 (1986).
Many significant disease states are related to abnormal hemostasis. With respect to the coronary arterial vasculature, abnormal thrombus formation due to the rupture of an established atherosclerotic plaque is the major cause of acute myocardial infarction and unstable angina. Moreover, treatment of an occlusive coronary thrombus by either thrombolytic therapy or percutaneous transluminal coronary angioplasty (PTCA) is often accompanied by an acute thrombotic reclosure of the affected vessel which requires immediate resolution. With respect to the venous vasculature, a high percentage of patients undergoing major surgery in the lower extremities or the abdominal area suffer from thrombus formation in the venous vasculature which can result in reduced blood flow to the affected extremity and a predisposition to pulmonary embolism. Disseminated intravascular coagulopathy commonly occurs within both vascular systems during septic shock, certain viral infections and cancer and is characterized by the rapid consumption of coagulation factors and systemic coagulation which results in the formation of life-threatening thrombi occurring throughout the vasculature leading to widespread organ failure.
Pathogenic thrombosis in the arterial vasculature is a major clinical concern in today's medicine. It is the leading cause of acute myocardial infarction which is one of the leading causes of death in the western world. Recurrent arterial thrombosis also remains one of the leading causes of failure following enzymatic or mechanical recanalization of occluded coronary vessels using thrombolytic agents or percutaneous transluminal coronary angioplasty (PTCA), respectively. Ross, A. M., Thrombosis in Cardiovascular Disorder, p. 327, W. B. Saunders Co. (Fuster, V. and Verstraete, M. edit. 1991); Califf, R. M. and Willerson, J. T., Id. at p 389. In contrast to thrombotic events in the venous vasculature, arterial thrombosis is the result of a complex interaction between fibrin formation resulting from the blood coagulation cascade and cellular components, particularly platelets, which make up a large percentage of arterial thrombi. Heparin, the most widely used clinical anticoagulant administered i.v., has not been shown to be universally effective in the treatment or prevention of acute arterial thrombosis or rethrombosis. Prins, M. H. and Hirsh, J., J. Am. Coll. Cardiol., 67: 3A (1991).
Besides the unpredictable, recurrent thrombotic reocclusion which commonly occurs following PTCA, a profound restenosis of the recanalized vessel occurs in 30 to 40% of patients 1 to 6 months following this procedure. Califf, R. M. et al., J. Am. Coll. Cardiol., 17: 2B (1991). These patients require further treatment with either a repeat PTCA or coronary artery bypass surgery to relieve the newly formed stenosis. Restenosis of a mechanically damaged vessel is not a thrombotic process but instead is the result of a hyperproliferative response in the surrounding smooth muscle cells which over time results in a decreased luminal diameter of the affected vessel due to increased muscle mass. Id. As for arterial thrombosis, there is currently no effective pharmacologic treatment for the prevention of vascular restenosis following mechanical recanalization.
The need for safe and effective therapeutic anticoagulants has in one aspect focused on the role of the serine protease thrombin in blood coagulation.
Most preferred natural substrates for thrombin are reported to contain an uncharged amino acid in the P3 recognition subsite. For example, the thrombin cleavage site on the A.alpha. chain of fibrinogen, which is the primary physiological substrate for thrombin, is reported to contain a glycine residue in this position while the cleavage site on the B.beta. chain contains a serine, as shown below:
P4 P3 P2 P1 P1' PA1 Gly-Gly-Val-Arg/Gly Fibrinogen A.alpha. Chain PA1 Phe-Ser-Ala-Arg/Gly Fibrinogen B.beta. Chain PA1 (1) alkyl of 1 to about 12 carbon atoms, PA1 (2) alkyl of 1 to about 3 carbon atoms substituted with cyclic alkyl of about 3 to about 8 carbon atoms, which optionally is substituted in the ring carbons with hydroxyl, amino, guanidino, amidino, or alkoxyl or alkyl each of 1 to about 3 carbons, PA1 (3) cyclic alkyl of 3 to about 15 carbon atoms, which optionally is substituted in the ring carbons with hydroxyl, amino, guanidino, amidino, or alkoxyl or alkyl each of 1 to about 3 carbons, PA1 (4) heterocycloalkyl of 4 to about 10 ring atoms with the ring atoms selected from carbon and heteroatoms, wherein the heteroatoms are selected from the group consisting of oxygen, nitrogen, and S(O)i, wherein i is 0, 1 or 2, and which is optionally substituted on the ring carbons with hydroxyl, alkoxyl or alkyl each of 1 to about 3 carbons, amino, guanidino, or amidino, PA1 (5) heterocyclo of 4 to about 10 ring atoms with the ring atoms selected from carbon and heteroatoms, wherein the heteroatoms are selected from the group consisting of oxygen, nitrogen, and S(O).sub.i, wherein i is 0, 1 or 2, including the group ##STR2## is a 5 to 7 member heterocycle of 3 to 6 ring carbon atoms, where V is --CH.sub.2 --, --O--, --S(.dbd.O)--, --S(O).sub.2 -- or --S--, and which is optionally substituted on the ring carbons with hydroxyl, alkoxyl or alkyl each of 1 to about 3 carbons, amino, guanidino, or amidino, PA1 (6) alkenyl of 2 to about 6 carbon atoms which is optionally substituted with cyclic alkyl of about 3 to about 8 carbon atoms, which optionally is substituted in the ring carbons with hydroxyl, amino, guanidino, amidino, or alkoxyl or alkyl of 1 to about 3 carbons, PA1 (7) aryl of about 6 to about 14 carbon atoms which is optionally mono-, di- or tri-substituted with Y.sub.1, Y.sub.2, and/or Y.sub.3, PA1 (8) heteroaryl of 5 to 14 atoms with the ring atoms selected from carbon and heteroatoms, wherein the heteroatoms are selected from oxygen, nitrogen, and S(O).sub.i, wherein i is 0, 1 or 2, and which is optionally mono-, di- or tri-substituted with Y.sub.1, Y.sub.2, and/or Y.sub.3, PA1 (9) aralkyl of about 7 to about 15 carbon atoms which is optionally substituted on the alkyl chain with hydroxy or halogen and optionally mono-, di-, or tri-substituted on the aryl ring with Y.sub.1, Y.sub.2, and/or Y.sub.3, PA1 (10) heteroaralkyl of 6 to 11 atoms with the ring atoms selected from carbon and heteroatoms, wherein the heteroatoms are selected from oxygen, nitrogen, and S(O).sub.i, wherein i is 0, 1 or 2, and which is optionally substituted on the alkyl chain with hydroxy or halogen and optionally mono-, di- or tri-substituted on the ring with Y.sub.1, Y.sub.2, and/or Y.sub.3, PA1 (11) aralkenyl of about 8 to about 15 carbon atoms which is optionally mono-, di-, or tri-substituted on the aryl ring with Y.sub.1, Y.sub.2, and/or Y.sub.3, respectively, PA1 (12) heteroaralkenyl of 7 to 12 atoms with the ring atoms selected from carbon and heteroatoms, wherein the heteroatoms are selected from oxygen, nitrogen, and S(O).sub.i, wherein i is 0, 1 or 2, and which is optionally mono-, di- or tri-substituted on the ring with Y.sub.1, Y.sub.2, and/or Y.sub.3, ##STR3## (17) difluoromethyl and perfluoroalkyl of 1 to about 12 carbon atoms, (18) perfluoroaryl of about 6 to about 14 carbon atoms, PA1 (19) perfluoroaralkyl of about 7 to about 15 carbon atoms, and PA1 (20) hydrogen, PA1 (2) R.sub.5 is selected from the group consisting of PA1 (3) R.sub.6 is selected from the group consisting of PA1 (4) R.sub.7 is independently selected from the R.sub.5 group of substituents, provided that R.sub.7 is not halogen; and pharmaceutically acceptable salts thereof.
Peptidyl derivatives having an uncharged residue in the P3 position are said to bind to the active site of thrombin and thereby inhibit the conversion of fibrinogen to fibrin and inhibit cellular activation. These derivatives have either an aldehyde, chloromethyl ketone or boronic acid functionality associated with the P1 amino acid. For example, substrate-like peptidyl derivatives such as D-phenylalanyl-prolyl-argininal (D-Phe-Pro-Arg-a1), D-phenylalanyl-prolyl-arginine-chloromethyl ketone (P-PACK) and acetyl-D-phenylalanyl-prolyl-boroarginine (Ac-(D-Phe)-Pro-boroArg) have been reported to inhibit thrombin by directly binding to the active site of the enzyme. Bajusz, S., Symposia Biologica Hungarica, 25: 277 (1984), Bajusz, S. et al, J. Med. Chem., 33: 1729 (1990) and Bajusz, S. et al., Int. J. Peptide Protein Res. 12: 217 (1970); Kettner, C. and Shaw, E., Methods Enzymol., 80: 826 (1987), Kettner, C. et al., EP 293,881 (published Dec. 7, 1988), Kettner, C., et al., J. Biol. Chem., 265: 18209 (1990). These molecules have been reported to be potent anticoagulants in the prevention of platelet-rich arterial thrombosis. Kelly, A. B. et al., Thromb. Haemostas., 65: 736 at abstract 257 (1991). Other peptidyl aldehydes have been proposed or reported as inhibitors of thrombin. Bey, P. et al., EP 363,284 (published Apr. 11, 1990) and Balasubramanian, N. et al., EP 526,877 (published Feb. 10, 1993).
Peptidyl compounds which are said to be active site inhibitors of thrombin but which differ in structure from those containing a uncharged amino acid in the P3 recognition subsite have been reported.
The compound, Argatroban (also called 2R,4R-4-methyl-1-[N-2-(3-methyl-1,2,3,4-tetrahydro-8-quinolinesulfonyl)-L- argininal]-2-piperdinecarboxylic acid), is also reported to bind directly to the active site of thrombin and has been thought to be the most potent and selective compound in the class of non-peptidyl inhibitors of this enzyme. Okamoto, S. et al., Biochem. Biophys. Res. Commun., 101: 440 (1981). Argatroban has been reported to be a potent antithrombotic agent in several experimental models of acute arterial thrombosis. Jang, I. K. et al., in both Circulation, 81: 219 (1990) and Circ. Res., 67: 1552 (1990).
Peptidyl compounds which are said to be inhibitors of thrombin and whose mode of action is thought to be by binding to both the active site and another site on the enzyme have been reported. Hirudin and certain peptidyl derivatives of hirudin have been reported to inhibit both conversion of fibrinogen to fibrin and platelet activation by binding to either both the active site and exo site, or the exo site only, of thrombin. Markwardt, F., Thromb. Haemostas., 66: 141 (1991). Hirudin is reported to be a 65 amino acid polypeptide originally isolated from leech salivary gland extracts. It is said to be one of the most potent inhibitors of thrombin known. Marki, W. E. and Wallis, R. B., Thromb. Haemostas., 64: 344 (1990). It has been reported to inhibit thrombin by binding to both its anion-binding exo-site and to its catalytic active site which are distinct and physically distant from each other. Rydel, T. J. et al., Science, 249:277 (1990). Hirudin has been reported to be a potent antithrombotic agent in vivo. Markwardt, F. et al., Pharmazie, 43: 202 (1988); Kelly, A. B. et al., Blood, 77: 1 (1991). In addition to its antithrombotic effects, hirudin has been reported to also effectively inhibit smooth muscle proliferation and the associated restenosis following mechanical damage to a atherosclerotic rabbit femoral artery. Sarembock, I. J. et al., Circulation, 84: 232 (1991).
Hirugen has been reported to be a peptide derived from the anionic carboxy-terminus of hirudin. It is reported to bind only to the anion binding exo-site of thrombin and thereby inhibit the formation of fibrin but not the catalytic turnover of small synthetic substrates which have access to the unblocked active site of the enzyme. Maraganore, J. M. et al., J. Biol. Chem., 264: 8692 (1989); Naski, M. C. et al., J. Biol. Chem., 265: 13484 (1990). Based on x-ray crystallographic analysis, it has been reported that the region of hirudin represented by hirugen binds directly to the exo site of thrombin. Skrzypczak-Jankun, E. et al., Thromb. Haemostas., 65: 830 at abstract 507 (1991). Moreover, the binding of hirugen has also been reported to enhance the catalytic turnover of certain small synthetic substrates by thrombin, indicating that a conformational change in the enzyme active site may accompany occupancy of the exo-site. Liu, L. W. et al., J. Biol. Chem, 266:16977 (1991). Hirugen also is reported to block thrombin-mediated platelet aggregation. Jakubowski, J. A. and Maraganore, J. M., Blood, 75: 399 (1990).
A group of synthetic chimeric molecules comprised of a hirugen-like sequence linked by a glycine-spacer region to the peptide, D-phenylalanyl-prolyl-arginine, which is based on a preferred substrate recognition site for thrombin, has been termed to be hirulog. Maraganore et al., U.S. Pat. No. 5,196,404 (Mar. 23, 1993). The hirugen-like sequence is said to be linked to this peptide through the C-terminal end of the peptide. Maraganone, J. M. et al., Biochemistry, 29: 7095 (1990). The hirulogs have been reported to be an effective antithrombotic agents in preventing both fibrin-rich and platelet-rich thrombosis. Maraganone, J. M. et al., Thromb. Haemostas., 65: 651 at abstract 17 (1991).
Certain benzamidines have been reported to inhibit thrombin though non-selectively. 4-amidinophenylpyruvic acid (APPA) has been reported to be a thrombin inhibitor with low toxicity and favorable pharmacokinetics. However, this compound was reported to be non-selective, inhibiting trypsin, plasmin and kallikrein. Markwardt et al., Thromb. Res., 1:243-52 (1972). Other benzamidine-derived structures which have been reported to inhibit thrombin include the cylic amides of Na-substituted 4-amidinophenylalanine and 2-amino-5-(4-amidinophenyl)-1-valeric acid. The inhibitory constant displayed by these compounds was reported to be in the micromolar range. Markwardt et al., Thromb. Res., 17:425-31 (1980). Moreover, derivatives of 4-amidinophenylalanine whose a-amino group is linked to the arylsulfonyl residue via an w-aminoalkylcarboxylic acid as spacer have also been assessed for their inhibitory effect. Among these N.sup.a -(2-naphthylsulphonylglycyl)-4-amidino-phenylalanine piperidide (a-NAPAP) has been reported to possess an affinity for thrombin (K.sub.i =633 10.sup.-9 M). Banner et al., J. Biol. Chem., 266:20085 (1991) and Sturzebecher et al., Thromb. Res., 29:635-42 (1983).
Certain bis-benzamidines have been reported to inhibit thrombin. The antithrombin activity of bis-benzamidines was reported to increase with the length and bulkiness of the central chain. However, these compounds were reported to be generally toxic in the micromolar range where they are also inhibitory. Geratz et al., Thromb. Diath. Haemorrh., 29:154-67 (1973); Geratz et al., J. Med. Chem., 16:970-5 (1973); Geratz et al., J. Med. Chem., 19:634-9 (1976); Walsmann et al., Acta Biol. Med. Germ., 35:K1-8 (1976); and Hauptmann et al., Acta Biol. Med. Germ., 35:635-44 (1976).
Certain amidino-bearing aromatic ring structures such as beta-naphthamidines have been reported to possess modest antithrombin and anticoagulant activity. This class of compounds include the non-selective 6-amidino-2-naphthyl-4-guanidinobenzoate dimethanesulfonate (FUT 175). Fuji et al., Biochim. Biophys. Acta, 661:342-5 (1981); and Hitomi et al., Haemostasis, 15:164-8 (1985).
Certain phenylguanidines have been reported to inhibit thrombin. Derivatives of 4-guanidinophenylalanine with inhibitory constants in the micromolar range have been reported to inhibit thrombin. This class includes the N.sup.a -tosylated and dansylated 4-guanidino phenylalanine piperidides. Claeson et al., Thromb. Haemostas., 50:53 (1983). Another compound, [ethyl p-(6-guanidinohexanoyloxy) benzoate] methane sulfonate (FOY) was reported to be a non-selective competitive inhibitor of thrombin. Ohno et al., Thromb. Res., 19:579-588 (1980).

Aromatic hetherocyclic derivatives as enzyme inhibitors


A method of preparing an aqueous electroless deposition composition for electrolessly depositing Co or a Co alloy onto a substrate in manufacture of microelectronic devices by treating water or an aqueous electroless deposition composition with a deoxygenating treatment to reduce the oxygen concentration.

Electroless deposition of Co is performed in a variety of applications in the manufacture of microelectronic devices. For example, Co is used in capping of damascene Cu metallization employed to form electrical interconnects in integrated circuit substrates. Copper can diffuse rapidly into a Si substrate and dielectric films such as, for example, SiO2 or low k dielectrics. Copper can also diffuse into a device layer built on top of a substrate in multilayer device applications. Such diffusion can be detrimental to the device because it can cause electrical leakage in substrates, or form an unintended electrical connection between two interconnects resulting in an electrical short. Moreover, Cu diffusion out of an interconnect feature can disrupt electrical flow. Copper also has a tendency to migrate from one location to another when electrical current passes through interconnect features in service, creating voids and hillocks. This migration can damage an adjacent interconnect line and disrupt electrical flow in the feature where the metal migrates.
Accordingly, among the challenges facing integrated circuit device manufacturers is to minimize diffusion and electromigration of metal in metal-filled interconnect features. This challenge becomes more acute as the devices further miniaturize, and as the features further miniaturize and densify. Cobalt capping is employed to inhibit this Cu diffusion and migration.
Another challenge in the context of metal interconnect features is to protect them from corrosion. Certain interconnect metals, especially Cu, are more susceptible to corrosion. Copper is a fairly reactive metal which readily oxidizes under ambient conditions. This reactivity can undermine adhesion to dielectrics and thin films, resulting in voids and delamination. Another challenge is therefore to combat oxidation and enhance adhesion between the cap and the Cu, and between structure layers.
The industry has deposited Co-based caps over Cu and other metal interconnect features in response to these challenges, as discussed in, for example, U.S. Pat. Pub. Nos. 2003/0207560 and 2005/0275100.
A particular Co-based metal capping layer employed to reduce Cu migration, provide corrosion protection, and enhance adhesion between the dielectric and Cu is a ternary alloy including Co, W, and P. Another refractory metal may replace or be used in addition to W, and B is often substituted for or used in addition to P. Each component of the ternary alloy imparts advantages to the protective layer.
A particular problem for the integration of this technology to current ULSI fabrication lines is capping layer defectivity. In recent years, the defectivity has been an object in inventions relating to plating baths and tools. See Katakabe et al. (U.S. Pat. Pub. No. 2004/0245214), Kolics et al. (U.S. Pat. Pub. No. 2004/0134375), Dubin et al. (U.S. Pat. Pub. No. 2005/0008786), Cheng et al. (U.S. Pat. Pub. No. 2004/0253814), Weidman et al. (U.S. Pat. Pub. No. 2005/0084615), Pancham et al. (U.S. Pat. Pub. No. 2005/0072525), and Saijo et al. (U.S. Pat. Pub. No. 2005/0009340). Defectivity reduction remains a challenge in ULSI fabrication lines.
Typical defects in electroless plated cobalt alloys for use as caps on interconnect features may be summarized as follows.
Nodulation: localized preferential growth or particle formation on the Cu deposit, at Cu/dielectric and Cu/barrier interfaces, and on dielectric surfaces. This problem may be partially caused by a lack of stability of the working bath, metal impurities in the solutions, etc. The existence of Co3+ due to the oxidation of Co2+ by dissolved oxygen are thought to corrode the copper surface prior to initiation by oxidizing copper to Cu2+. The Cu2+ ions can be easily reduced by DMAB or other reducing agents present in the bath and form Cu particles which are available as nuclei for growth of cobalt particles.
"Grain decoration": uneven morphology of electroless Co film along the Cu line that replicates Cu erosion before plating and/or unevenly grown Co film due to initiation delay at Cu grain interfaces. Such growth can contribute to overall deposit roughness. The existence of dissolved oxygen and Co3+ ions can cause initiation delay of electroless cobalt plating, resulting in the excessive copper corrosion on small crystalline and grain boundaries prior to deposition, thus changing the surface topography.
Granularity: irregularly sized nanocrystallites and clusters of amorphous electroless deposits of Co and its alloys with large grains and well-defined grain interfaces. This type of morphology can contribute to surface roughness.
Non-uniform growth: varying deposit thickness along the Cu substrate due to different initiation time and/or plating rate of electroless Co on different size features, features located in different areas, dense and isolated, and/or features with different surface areas. The presence of trace levels of dissolved oxygen and Co3+ ions in the plating bath affect the initiation and plating rate differently on different features due to diffusion limitation effects, resulting in non-uniform growth of cobalt alloy deposits.
Pitting: the formation of pits or pinholes due to localized incomplete Cu surface coverage or extensive hydrogen bubble formation during the deposition process of the electroless film.
Those defects decrease diffusion barrier effectiveness, lower the capability of the capping layer to suppress electromigration, cause electromigration failure, affect the signal propagation across the circuitry, increase current leakage, result in electrical shorts, and are the major limitation for this technology to be adopted in the 45 nm node or beyong.
Therefore, a need continues to exist for substantially defect free, uniform, and smooth electrolessly deposited capping layers over Cu interconnects.

Manufacture of electroless cobalt deposition compositions for microelectronics applications


The spark plug for an internal combustion engine has a cylindrical housing, a center electrode held inside the housing, a ground electrode connected to the housing and forming a spark discharge gap between itself and the center electrode, and, an end projection projected from the end portion of the housing toward the head end side of the spark plug. The center electrode and ground electrode are arranged so that most of the spark discharge gap is disposed over the open areas and the electrode area in which the end projection is arranged.

1. Technical Field of the Invention
The present invention relates to a spark plug for an internal combustion engine, which is used such as for an automotive engine.
2. Related Art
A spark plug is used as an igniting means in an internal combustion engine, such as an automotive engine. For example, in such a spark plug, a center electrode and a ground electrode are arranged opposed to each other in the axial direction of the spark plug to form a spark discharge gap therebetween. In such a spark plug, discharge is permitted to occur in the spark discharge gap so that the discharge can ignite air-fuel mixture in the combustion chamber.
In the combustion chamber, a flow of air-fuel mixture, such as a swirl flow or a tumble flow is formed. The flow is also moderately led to the spark discharge gap to ensure ignitability.
A spark plug is mounted in a posture to an internal combustion engine. Depending on the posture of the spark plug with respect to the internal combustion engine (hereinafter referred to as a "mounted posture"), a part of the ground electrode connected to an end portion of a housing may be located upstream of the spark discharge gap within the flow of air-fuel mixture. With this location, the flow of air-fuel mixture in the combustion chamber is blocked by the ground electrode and accordingly, the flow in the vicinity of the spark discharge gap is likely to stagnate.
As a result, ignitability of the spark plug may be deteriorated. Specifically, depending on the mounted posture of the spark plug with respect to the internal combustion engine, ignitability of the spark plug may be problematically varied. In recent years, in particular, there is a growing trend of using a lean-burn internal combustion engine. In such an internal combustion engine, combustion stability is likely to be deteriorated depending on the mounted posture of the spark plug.
In addition, it is difficult to control the mounted posture of the spark plug with respect to the internal combustion engine, i.e. to control the location of the ground electrode in the circumferential direction of the spark plug (i.e. mounting angle). The mounted posture is varied depending such as on the mounting state (for example, mounting angle) of the screws used for mounting the spark plug in a housing, or the degree of tightening the screws in the work of mounting the spark plug to the internal combustion engine.
A patent document JP-A-H05-315049 discloses a spark plug in which a spark discharge gap is formed being distanced from the body of the spark plug as much as possible, so that the spark discharge gap is exposed to a larger amount of air-fuel mixture and that fresh air-fuel mixture can easily flow into the spark discharge gap.
However, it is also difficult for the spark plug disclosed in JP-A-H05-315049 to avoid the problem set forth above. That is, the problem that ignitability of the spark plug is varied depending on the mounted posture of the spark plug with respect to the internal combustion engine, i.e. the location of the ground electrode in the circumferential direction of the spark plug. In the configuration disclosed in JP-A-H05-315049 as well, the ground electrode or the center electrode is located upstream of the spark discharge gap, depending on the mounted posture of the spark plug, causing the flow of air-fuel mixture to stagnate in the spark discharge gap. In this way, ignitability of the spark plug is likely to be varied depending on the mounted posture of the spark plug.

Spark plug for internal combustion engine


A device, system and process for accessing electronic mail from remotely located user-interface devices is disclosed. The users at the user-interface devices enter the electronic mail address and password, if any, for retrieval of electronic mail from the user's mailbox. The device locates one host computer from a plurality of host computers which contains the mailbox corresponding to the electronic mail address. The device then retrieves the electronic mail and transmits the electronic mail to the user-interface device. For large electronic mail messages, the device commences transmission of the electronic mail to the user-interface device while still receiving the electronic mail from the host computer. The device comprises a memory unit which stores domain names and the corresponding host computers which contain the mailbox for those domain names. Domain names not located in the memory unit can be searched through name servers to locate the host computer containing the mailbox.

Computer mail systems, also known as electronic mail systems, allow one user to send messages by electronic transmission to mailboxes of other users. In general, the electronic mail is stored in an electronic virtual mailbox, contained on a host computer. The virtual mailbox can be a memory location or a disk storage area on a host computer.
The host computer can be operated by electronic mail providers, such as America-On-Line (AOL), Prodigy or CompuServe. Each electronic mail provider generally uses different proprietary systems to receive, store and retrieve electronic mail. In addition, the host computer can also be a private computer of a particular company for use by the employees of that company. The private computer of each particular company could use different electronic mail systems.
Most users access their electronic mail from their personal computer, whether it is located at their office, for corporate users, or at their residence, for personal users. In this case, the personal computer of the user will be configured and have the appropriate format to allow transfer of data, namely receiving and transmitting information including electronic mail to and from the host computer which contains the user's mailbox.
However, when the user is away from their personal computer, it is difficult, if not impossible, to retrieve electronic mail from their mailbox. One solution would be for the user to have a lap-top or a portable computer with them at all times to facilitate accessing electronic mail when away from their personal computers. However, it is not practical for many people to have a lap-top or personal computer with them at all times solely for retrieving their electronic mail.
Another solution would be for electronic mail providers to have remotely located user-interface devices, such as kiosks. In this way, users that subscribe to a particular electronic mail provider can access electronic mail from these remotely located user-interface devices.
A disadvantage of these user-interface devices is that they are source dependent in that a user-interface device which has been configured and has the formatting and protocol information for accessing electronic mail from AOL cannot access electronic mail from host computers of other electronic mail providers, such as Prodigy. It is not cost-effective to configure and provide formatting, protocol and configuration information at each user-interface device for accessing mailboxes contained on two or more host computers. This problem is compounded when the large number of private organizations having internal electronic mail systems for their employees is considered.
Furthermore, there is limited space at the user-interface devices on which to store formatting, protocol and configuration information to access mailboxes contained on each of the different host computers. In addition, there are potential incapability problems between the various mail systems which could prevent one user-interface device having the ability to access electronic mail from a plurality of host computers.
In addition, some user-interface devices, such as telephones having electronic mail capability, simply do not have the storage space to store the information necessary to receive electronic mail stored in mailboxes contained on a plurality of host computers.

Device and system to facilitate accessing electronic mail from remote user-interface devices


A magnetostriction type torque sensor has a magnetostrictive film formed on an outer peripheral surface of a rotary shaft, a coil having a coil centerline extending in a radial direction of the rotary shaft, and a signal processor responsive to coil impedance. Since the coil includes a coil centerline extending in a radial direction of the rotary shaft, magnetic fluxes are formed mainly in a radial direction of the rotary shaft. Accordingly, the magnetic fluxes intruding deep into the rotary shaft are decreased, and the rate of the magnetic fluxes passing through the magnetostrictive film is increased. As a result, the magnetostriction type torque sensor comes to have high sensitivity even when the rotary shaft has high magnetic permeability or high electric conductivity.

1. Field of the Invention
The present invention relates to a magnetostriction type torque sensor.
2. Description of the Prior Art
FIG. 11 illustrates an example of prior art magnetostriction type torque sensors. The magnetostriction type torque sensor comprises magnetostrictive films 91 and 92 formed on outer peripheral surfaces of a rotary shaft 9, excitation coils 93 and 93 disposed around the rotary shaft 9 away from the magnetostriction films 91 and 92 by a predetermined distance in a radial direction, and detection coils 94 and 94 disposed on the excitation coils 93 and 93.
Configurational magnetic anisotropies are given to the configurations of the magnetostrictive films 91 and 92 so that the magnetostrictive films 91 and 92 are subjected to stresses acting in direction being opposite to each other. In a magnetic film having positive magnetostriction, for instance, in the magnetostrictive film 91 subjected to a tensile stress, the magnetic permeability of the magnetostrictive film 91 increases because of the inverse magnetostrictive effect. 0n the other hand, for instance, in the magnetostrictive film 92 subjected to a compression stress, the magnetic permeability of the magnetostrictive film 92 decreases because of the inverse magnetostrictive effect. Hence, the mutual inductances between the excitation coils 93 and the detection coils 94 vary in directions being opposite to each other when an alternating current is applied in the excitation coils 93 and 93, and accordingly the torques of the rotary shaft 9 can be detected from the output voltage differences between the detection coils 94 and 94.
However, when detecting the torques of a rotary shaft 9 made of iron, steel or the like having high magnetic permeability with the prior art magnetostriction type torque sensor, most of the mutual inductances between the excitation coils 93 and the detection coils 94 are generated by the rotary shaft 9 itself, and small mutual inductance components result from magnetic fluxes passing through the magnetostrictive films 91 and 92, namely most of the magnetic fluxes have passed through the rotary shaft 9. Hence, the variation rate of the mutual inductance resulting from the magnetic permeability variation of the magnetostrictive film 92 has been small. As a result, the prior art magnetostriction type torque sensor has been suffering from a problem of low detection sensitivity or S/N ratio (i.e., signal-to-noise ratio).
Likewise, when detecting the torques of a rotary shaft 9 made of iron, steel, aluminum alloy, titanium or the like having high electric conductivity with the prior art magnetostriction type torque sensor, the impedances of the excitation coils 93 decrease because of the eddy current loss resulting from alternating magnetic fluxes penetrating through the rotary shaft 9. Hence, the prior art magnetostriction type torque sensor has again exhibited deteriorated detection sensitivity or S/N ratio.

Kabushiki Kaisha Toyoda Jidoshokki Seisakusho


The invention relates to a crosslinker composition comprising a reaction product of a cyclic urea U and a multifunctional aliphatic aldehyde A, and at least one crosslinker selected from the group consisting of reaction products of an aminotriazine and at least one aldehyde selected from the group consisting of aliphatic monoaldehydes and multifunctional aliphatic aldehydes having the structure Y(CHO)n, where Y is an n-functional aliphatic residue, and n is greater than 1; reaction products of urea and/or cyclic ureas and formaldehyde; alkoxycarbonyl-aminotriazines; multifunctional isocyanates which may be partially or completely blocked; reaction products of phenols and aliphatic monoaldehydes; multifunctional epoxides; multifunctional aziridines; and multifunctional carbodiimides, wherein any of the crosslinkers which have hydroxyl groups may be etherified with one or more linear, branched, or cyclic aliphatic alcohols.

Crosslinking agents based on amino resins and coating compositions made with these are well known in the art and have been used for more than half a century in diverse applications including general industrial coatings, automotive coatings, coil coatings, powder coatings, baking enamels, and wood finishes. These crosslinking agents are based on reaction products of formaldehyde with amine or amide compounds such as melamine, guanamines, urea, and substituted ureas. Among the major drawbacks of these amino resin based coatings are formaldehyde emissions during cure.
Various crosslinking compositions have been developed that are based on combinations of aminoplast formers and aldehydes other than formaldehyde. Many of these are either less efficient or more expensive than the known formaldehyde-based systems, or are otherwise objectionable from a safety and health view. Despite the numerous efforts made, none of the crosslinker resins proposed has found wide market acceptance.
It is therefore an object of this invention to provide crosslinking compositions that have no formaldehyde emission, or a low formaldehyde emission that can be tolerated from a safety and health viewpoint, and that have application properties that are either on par with the known formaldehyde based systems, or at least provide a favourable match to these known systems.


Video data with both ultra-high definition (UHD) resolution and high or enhanced dynamic range (EDR) data are coded in a backward-compatible layered stream which allows legacy decoders to extract an HD standard dynamic range (SDR) signal. In response to a base layer HD SDR signal, a predicted signal is generated using separate luma and chroma prediction models. In the luma predictor, luma pixel values of the predicted signal are computed based only on luma pixel values of the base layer, while in the chroma predictor, chroma pixel values of the predicted signal are computed based on both the luma and the chroma pixel values of the base layer. A residual signal is computed based on the input UHD EDR signal and the predicted signal. The base layer and the residual signal are coded separately to form a coded bitstream. A compatible dual-layer decoder is also presented.

Audio and video compression is a key component in the development, storage, distribution, and consumption of multimedia content. The choice of a compression method involves tradeoffs among coding efficiency, coding complexity, and delay. As the ratio of processing power over computing cost increases, it allows for the development of more complex compression techniques that allow for more efficient compression. As an example, in video compression, the Motion Pictures Expert Group (MPEG) from the International Standards Organization (ISO) has continued improving upon the original MPEG-1 video standard by releasing the MPEG-2, MPEG-4 (part 2), and H.264/AVC (or MPEG-4, part 10) coding standards.
Despite the compression efficiency and success of H.264, a new generation of video compression technology, known as High Efficiency Video Coding (HEVC), in now under development. HEVC, for which a draft is available in "High efficiency video coding (HEVC) text specification draft 8," ITU-T/ISO/IEC Joint Collaborative Team on Video Coding (JCT-VC) document JCTVC-J1003, July 2012, by B. Bross, W.-J. Han, G. J. Sullivan, J.-R. Ohm, and T. Wiegand, which is incorporated herein by reference in its entirety, is expected to provide improved compression capability over the existing H.264 (also known as AVC) standard, published as, "Advanced Video Coding for generic audio-visual services," ITU T Rec. H.264 and ISO/IEC 14496-10, which is incorporated herein in its entirety.
Video signals may be characterized by multiple parameters, such as bit-depth, color space, color gamut, and resolution. Modern televisions and video playback devices (e.g., Blu-ray players) support a variety of resolutions, including standard-definition (e.g., 720×480i) and high-definition (HD) (e.g., 1920×1080p). Ultra high-definition (UHD) is a next generation resolution format with at least a 3,840×2,160 resolution (referred to as 4K UHD) and options to go as high as 7680×4320 (referred to as 8K UHD). Ultra high-definition may also be referred to as Ultra HD, UHDTV, or super high-vision. As used herein, UHD denotes any resolution higher than HD resolution.
Another aspect of a video signal's characteristic is it dynamic range. Dynamic range (DR) is a range of intensity (e.g., luminance, luma) in an image, e.g., from darkest darks to brightest brights. As used herein, the term 'dynamic range' (DR) may relate to a capability of the human psychovisual system (HVS) to perceive a range of intensity (e.g., luminance, luma) in an image, e.g., from darkest darks to brightest brights. In this sense, DR relates to a 'scene-referred' intensity. DR may also relate to the ability of a display device to adequately or approximately render an intensity range of a particular breadth. In this sense, DR relates to a 'display-referred' intensity. Unless a particular sense is explicitly specified to have particular significance at any point in the description herein, it should be inferred that the term may be used in either sense, e.g. interchangeably.
As used herein, the term high dynamic range (HDR) relates to a DR breadth that spans the some 14-15 orders of magnitude of the human visual system (HVS). For example, well adapted humans with essentially normal (e.g., in one or more of a statistical, biometric or ophthalmological sense) have an intensity range that spans about 15 orders of magnitude. Adapted humans may perceive dim light sources of as few as a mere handful of photons. Yet, these same humans may perceive the near painfully brilliant intensity of the noonday sun in desert, sea or snow (or even glance into the sun, however briefly to prevent damage). This span though is available to 'adapted' humans, e.g., those whose HVS has a time period in which to reset and adjust.
In contrast, the DR over which a human may simultaneously perceive an extensive breadth in intensity range may be somewhat truncated, in relation to HDR. As used herein, the terms 'enhanced dynamic range' (EDR), 'visual dynamic range,' or 'variable dynamic range' (VDR) may individually or interchangeably relate to the DR that is simultaneously perceivable by a HVS. As used herein, EDR may relate to a DR that spans 5-6 orders of magnitude. Thus while perhaps somewhat narrower in relation to true scene referred HDR, EDR nonetheless represents a wide DR breadth. As used herein, the term 'simultaneous dynamic range' may relate to EDR.
To support backwards compatibility with legacy playback devices as well as new HDR or UHD display technologies, multiple layers may be used to deliver UHD and HDR (or EDR) video data from an upstream device to downstream devices. Given such a multi-layer stream, legacy decoders may use the base layer to reconstruct an HD SDR version of the content. Advanced decoders may use both the base layer and the enhancement layers to reconstruct an UHD EDR version of the content to render it on more capable displays. As appreciated by the inventors here, improved techniques for the coding of UHD EDR video are desirable.
The approaches described in this section are approaches that could be pursued, but not necessarily approaches that have been previously conceived or pursued. Therefore, unless otherwise indicated, it should not be assumed that any of the approaches described in this section qualify as prior art merely by virtue of their inclusion in this section. Similarly, issues identified with respect to one or more approaches should not assume to have been recognized in any prior art on the basis of this section, unless otherwise indicated.

Backward-compatible coding for ultra high definition video signals with enhanced dynamic range

Dolby Laboratories Licensing Corporation


A system and method for flexible and efficient routing of communications transmissions is disclosed. Service providers submit information comprising cost and service parameter data to a centralized server node. The server node evaluates the information and generates a rate-table database comprising efficient routing paths for connecting transmissions between any two locations in a communications switching network. The server may substantially optimize its rate-table database with respect to one or more parameters, such as price, network utilization, return traffic volumes, and others. Service requesters submit service requests to the centralized server node. The server node identifies efficient routes which meet the requesters' requirements and brokers sales of communication (or connect) time from the service providers to the service requesters. The telecommunications node may be programmed to dynamically monitor current volume and sell or buy communication bandwidth on the basis of the actual and predicted requirements for connect time. When a carrier wishes to establish communication via a route purchased through the global network, it passes supervision to a local telecommunications node which establishes transmission via a routing path for which the carrier has purchased connect time. When necessary, the system employs particular data messages to inform a switch in the routing path that an incoming communication transaction is in transit to a different location, and is not for termination at the location of the switch. This allows a switch to distinguish terminating traffic from transit traffic and set rates for transit traffic without invoking settlement agreement accounting rates.

The cost of a long distance telephone call is usually paid by the calling party rather than by the called party. Payment for the call is typically collected from the calling party by the carrier that originated the service, either directly or through the agency of the caller's local telephone service provider. Consequently, when a call is placed from a first location served by an originating carrier to a second location served by a different terminating carrier, provision must be made to share with the terminating carrier some of the revenue collected by the originating carrier from the calling party.
For international telephone calls, this revenue sharing has traditionally been accomplished through the use of settlement agreements. Settlement agreements typically establish an accounting rate related to the cost of connecting the call between the countries, and specify how the accounting rate will be split between the two carriers. This split is typically 50-50.
For example, assume that a United States carrier and an overseas carrier negotiate a settlement agreement with a one dollar per minute accounting rate and a 50-50 revenue split. In accordance with the agreement, the U.S. carrier must pay 50 cents for every minute of connect time to called locations serviced by the overseas carrier. Conversely, the overseas carrier must pay 50 cents for every minute of connect time on calls terminated by the U.S. carrier.
As has been recognized, however, the negotiated accounting rate is frequently significantly higher than the actual cost of completing the international call. See, e.g., Frieden, Accounting Rates: The Business of International Telecommunications and the Incentive to Cheat, 43 Federal Communications Law Journal 111, 117, which is hereby incorporated by reference. For this reason, and because outbound calling volumes from the United States are significantly greater than inbound calling volumes from many foreign countries, U.S. carriers make large outbound payments to overseas carriers. In large measure, these charges are ultimately passed on to rate payers.
This payment imbalance is exacerbated when overseas carriers route inbound U.S. traffic under their control via private telephone lines into the United States. In this way, the overseas carriers are able to avoid paying high accounting rate settlements for calls to the United States from their countries, while receiving high accounting rate settlements from U.S. carriers who are forced to route outbound U.S. traffic through the overseas carrier because the overseas carrier is a monopolist in its home country. Moreover, overseas carriers often employ these alternative less-expensive routings for inbound U.S. traffic despite express contractual provisions in settlement agreements prohibiting such behavior.
To date, U.S. carriers have been forced to suffer such payment imbalances and have no immediate way to respond to breaches of contract by overseas carriers because of the significant time and expense required to reconfigure the global network to reroute calling traffic. The cumbersome reconfiguration process gives foreign carriers the opportunity to route inbound U.S. traffic via private lines, and otherwise run up settlement balances, without fear of retaliation from U.S. carriers.
More generally, this inflexible routing structure precludes telephone service providers from taking advantage of fluctuations in world-wide telephone rates. It would be desirable to provide a way for dynamic routing in response to rate changes so as to pass the savings on to the consumer. There is also a need to provide telephone companies with means to dynamically purchase and sell blocks of telephone connection bandwidth.
The need for flexible allocation of connection routes and for an ability to trade connection bandwidth accordingly exists not only in the international arena but in any internal market allowing competition in the field of communications.

Method and system for global communications network management


This invention provides bainite steel materials having a less scattering of properties in a thickness direction or between steel materials by using a chemical composition of C: not less than 0.001 wt % but less than 0.030 wt %, Si: not more than 0.60 wt %, Mn: 1.00-3.00 wt %, Nb: 0.005-0.20 wt %, B: 0.0003-0.0050 wt % and Al: not more than 0.100 wt % and rendering not less than 90% of the material into a bainite texture in steel materials such as thick steel plates, steel sheets, section steels, rod steels and the like.

As mentioned above, thick steel materials represented by thick plates are used in various fields for improving properties such as high strength, high toughness and the like. Recently, it is demanded that these properties are uniform in the thickness direction of the steel material and the scattering of these properties between the steel materials is less.
For example, it is reported in pages 11 to 21 of "Tetsu-to-Hagane", Vol. 74(1988), No. 6 that the destruction of high-rise buildings is designed to be controlled by absorbing vibration energy through the deformation of the building against big earthquake with the heightening of the building. Concretely, the framework of the building is fallen down at a given form in the occurrence of earthquake and hence the deconstruction of the building is controlled by the plasticization of the framework. That is, assuming that the framework of the building indicates a behavior aimed by the designer in the occurrence of earthquake, it is required that the proof ratio of the steel material used in pillar, beam and the like of the building is completely grasped by the designer. Therefore, it is inevitable that the steel materials such as plates, H-sections and the like for use in the pillar, beam and the like are homogeneous, and also the scattering of strength in the steel material becomes a great problem.
Since the steel materials used in the buildings and shipbuildings are required to have high tension and toughness, these materials are usually produced by controlled rolling and controlled cooling process or so-called TMCP process. However, if thick steel materials are produced by the TMCP process, the cooling rate differs in the thickness direction or between the steel materials to change the texture, and hence the scattering of properties is caused in the thickness direction of the resulting steel material or between the steel materials. The scattering of properties appears in the thickness direction of the thick steel plate, between web and flange of H-section steel because of non-uniform cooling between the web and the flange, between the lots of the steel material or the like.
In JP-A-4-224623, it is proposed that the texture in the thickness direction can be changed into a mixed texture of ferrite and bainite by adding Nb and making the cooling rate after the rolling not less than 3.degree. C./s and setting an upper limit of the cooling stop temperature at 500.degree. C., whereby the strength of a center portion in the thickness direction is increased to decrease the difference of hardness in the thickness direction. In this case, however, the cooling rate should strictly be controlled to not less than 3.degree. C./s even in the center portion, because if a cooling rate distribution is formed in the thickness direction, a scattering of properties is immediately caused. As a result, it is required to strictly control production, so that the above proposal is unsuitable for the production in industrial scale.
In JP-A-62-130215, it is proposed to improve low-temperature toughness by ensuring strength through precipitation strengthening of Cu and by cooling to 300-700.degree. C. at a cooling rate of not less than 0.5.degree. C./s after the hot rolling and holding at a temperature zone of 500-650.degree. C. for a constant time and then cooling to room temperature. However, this technique aims at the improvement of low-temperature toughness, so that it is difficult to satisfy the uniformity of the properties required in recent structural steels or the like by controlling the scattering of properties at various forms as mentioned above.

Bainitic steel materials having a less scattering of properties and method of producing the same


A split ring pliant ligature for the mouthpiece of a reed instrument displays a pair of longitudinally spaced straps including lateral arms attached to a medial bottom span. A thumbscrew mechanism attached to the joined ends of the arms draws the straps compressively about the mouthpiece and a reed shank. Transversly spaced members bridge the bottom spans and carry pads which project radially inwardly therefrom to contact the mouthpiece on both sides of the reed's shank. The pliant bottom spans provide the sole compressive contact between the ligature and the reed shank. The configuration of the ligature and its resilience causes the tensile force generated by the thumbscrew to be distributed generally evenly between the two bottom spans bearing upon the reed shank.

This invention generally relates to an improved ligature for securing a reed to the mouthpiece of a single reed woodwind instrument.
The field of endeavor of this invention is old and well developed. Numerous reed instruments have been devised throughout history and their modern counterparts have changed little in essential structural and operational characteristics. Likewise, the below-listed criteria of instrument builders and musicians regarding ligature means have not changed significantly:
1. The ligature must be mechanically competent to position and retain the reed in proper juxtaposition to the mouthpiece; PA1 2. The ligature should facilitate easy attachment and careful adjustment of the reed relative to the mouthpiece; PA1 3. The ligature must embrace the reed and mouthpiece with sufficient radial compression to perform its reed-retention function while, at the same time, permitting the development of those vibratory characteristics of the reed-mouthpiece-ligature assembly most productive of the fuller, richer, mellower sounds highly desired by instrumentalists; PA1 4. The compressive forces imparted to the reed and mouthpiece when operatively embraced by the ligature should be distributed in a manner that does not inhibit the beneficial vibrational coaction of the reed-mouthpiece-ligature assembly; and PA1 5. The degree of surface engagement between the ligature and the reed should not cause excessive damping of the sound emanating from the reed and mouthpiece.
Early ligatures, as the word suggests, comprised a length of stout string wrapped continuously about the reed and mouthpiece. Such string ligatures provided satisfactory mechanical means for retaining the reed in its mounted position upon the mouthpiece. Many modern musicians believe that the yieldability and resilience of such string ligatures facilitated the production of superior tone, timbre and responsiveness which established the standards in these catagories. Indeed, this ancient method of reed retention is employed yet today with respect to certain double reed instruments. Despite the fact that string ligatures do satisfy most of the five criteria listed hereinabove, they have fallen into general disuse with respect to single reed instruments due to the considerable time required to handwind the string properly about the reed and mouthpiece and because such ligatures do not allow quick and easy adjustment and replacement of reeds. Moreover, the wrapping technic required for successful use of string ligatures cannot be readily mastered by beginning, usually youthful, instrumentalists.
For the reasons just stated, split ring ligatures made of thin, light metal have generally replaced string ligatures, at least with respect to single reed instruments such as clarinets and saxophones. This well-known ligature device typically includes one or more thumbscrews penetrating threaded bores through the opposed ends of metallic rings or bands for drawing these ends together whereby the rings unyieldably embrace the reed and mouthpiece to secure the same in assembled relation with considerable compressive force. Contrary to the difficulties encountered with string ligatures in assembling and accurately adjusting the reed to the mouthpiece, the split ring-thumbscrew construction greatly simplifies these tasks for both professional musicians and inexperienced players.
Even though the split ring ligature has become very popular, many instrumentalists detect a noticeable reduction in tone quality compared to the mellowness and fullness produced with a string wound ligature. Most investigators of this problem have concluded that unyielding metallic split ring ligatures produce clamping forces which act upon both the mouthpiece and the reed in a deleterious manner. Some posit that compressive forces produced by this ligature inherently diminish the free vibration of the reed and mouthpiece. Others believe that poorly situated, localized points of contact between the ring ligature and the reed and mouthpiece contribute to the tinny and unsteady tone produced. Some reason that the ligature ring or rings stress the reed shank unequally or non-homogeneously whereby excessive unit pressures acting only upon certain segments of the reed degrade instrument performance.
The proposed remedies for the recognized loss of tone quality encountered by split ring ligature users have been at least as plentiful and varied as the aforerecited theories regarding the causes of this problem; and, numerous remedial ligature constructions have been described in a substantial body of prior art. For example, prior United States patents disclose various resilent materials mechanically retained between a split ring ligature and a reed embraced thereby to cushion and/or equalize the reed vibration damping pressure exerted by the ligature. U.S. Pat. Nos. 1,575,621 (rubber); 1,801,421 (cork, felt, rubber); 2,292,584 (felt strips); 2,648,246 (resilient metal); 4,428,271 (mechanical spring, elastomeric or plastomeric material); 4,941,385 (sound vibration insulation such as foam rubber and pliable plastic).
Many prior art split ring devices have been structrually modified to minimize ligature contact with the reed and/or to provide ligature-to-reed contact only at certain selected locations in the belief that the reed was thereby rendered more free to vibrate whereby better tone and/or quicker response were provided. U.S. Pat. Nos. 2,791,929 (essentially line contact between two longitudinally extending, raised bars spaced near the longitudinal centerline of the reed); 2,837,003 (point contact only intermediate the ends of the reed away from its lateral edges); 3,410,170 (ligature has raised longitudinally extending bars each bar having spaced lands for contacting the reed); 4,080,866 (ligature has transverse bars extending across the reed and contacting the same only at its longitudinal centerline); 4,745,838 (longitudinally extending shoulders are raised on the interior ligature wall and provide line contact with the reed along the longitudinal edges thereof); 4,941,385 (the ligature carries a plate having raised longitudinally extending rails in line contact with the convex reed surface); 5,000,073 (a pair of longitudinally spaced, circumferential ribs project radially inwardly from the ligature wall to provide the sole clamping contact with the reed).
After metallic split ring ligatures were introduced, attempts were made to modify this basic ligature construction so that it could yieldably retain the reed upon the mouthpiece more in the manner of a string ligature. An early U.S. Pat. No. 555,561 to Cadwallader shows an alternative ligature which suggests split metal brackets between which a length of stout cord is interwoven. Thumbscrews draw the brackets together to cause the cords to embrace the reed and mouthpiece in a yieldable fashion. A similar version of the Cadwallader ligature is disclosed in U.S. Pat. No. 4,258,604. In U.S. Pat. No. 2,483,327 the stout cord suggested by Cadwallader is replaced by a piece of flexible fabric which is gripped by rigid brackets movable by thumbscrews in the usual manner to draw the fabric compressively inwardly against the reed. Another attempt to approximate string ligature tone quality in a thumbscrew tightenable device is disclosed in U.S. Pat. No. 4,056,997 where a unitary plastic strip overlies most of the reed shank and compressivly surrounds a major portion of the outer circumferential surface of the mouthpiece.
None of the just described thumbscrew-actuated ligatures which are intended to embrace the reed and mouthpiece yieldably and to promote maximum vibration leading to the classic tonal qualities of a string ligature have been broadly accepted by reed instrumentalists. This is because these prior art ligatures place all or at least a major portion of the reed shank and mouthpiece surface in direct contact with some pliable material such as cord, nylon string, woven or knitted fabric, or plastic thereby damping or totally eliminating desirable vibrations and resonances with might otherwise be produced by a reed-mouthpiece-ligature assembly. Many players rate this class of yieldable ligature as unacceptable due to the production of overly dark, even dull tones throughout the entire range of the instrument.
Prior art split ring ligatures structurally similar to those typically fabricated of thin metal, but which are instead made of pliant plastic, would appear to combine advantageously the resilient reed clamping effect of a string ligature and the handiness of a thumbscrew clamping mechanism. Flexible and somewhat elastic strap portions of known plastic ligatures transversly overlie one or more segments of the reed shank and generally conform to the surface configuration of the shank when drawn into engagement therewith by the tightening action of one or more thumbscrews. Windows or cutout portions in the prior art plastic ligatures generally conform in area and shape to those of metallic split ring ligatures and serve to avoid the overly dark tones attributable to the yieldable ligatures of Cadwallader and others of that type discussed hereinabove.
Any of these prior art plastic ligatures might finally have brought together a flexible ligature and a thumbscrew tightener to provide superior tone quality as well as ease of operation; nevertheless, each has failed to do so to any substantial degree. Thus, U.S. Pat Nos. 3,205,753 to Luyben; 3,618,440 to Ratterree; and 4,275,636 to Van Doren disclose plastic strap-thumbscrew ligatures which have purposely incorporated structural features which largely eliminate the string ligature effect otherwise made available by the flexibility and resilence of their plastic straps. While each of these ligatures could have resiliently embraced the reed shank without the high compressive forces of its metallic counterpart, each appears to have deliberately added specific structure which creates deleterious unit pressure levels when the ligature is tightened. In this regard, the Luyben ligature displays four small projecting nodules providing the sole contact points with the reed. Ratterree's plastic ligature strap has two projecting bars which hold the reed in place with a minimum of surface contact; and, Van Doren shows two spaced plastic split rings formed with projecting ribs intended to limit the contact area between the ligature and the reed. Thus each of these plastic ligatures, displays some bort of protrusion in compressive engagement with the reed which produces highly localized stress in the reed leading to an undesirably bright, reedy tone throughout an instrument's entire range.
From the foregoing discussion, it appears that those pliant, split ring ligature constructions found in the prior art pertinent to this invention have failed to emulate the venerable string ligature because, in some cases, too much of the reed surface is overlain and constrained by the ligature body resulting in dull, overly damped tone characteristics, or because, in other cases, exaggerated efforts to reduce aggregate ligature-to-reed contact area produce bright, reedy tone characteristics.


The present invention provides a statistical modeling approach to automatic linguistic indexing of photographic images. The invention uses categorized images to train a dictionary of hundreds of statistical models each representing a concept. Images of any given concept are regarded as instances of a stochastic process that characterizes the concept. To measure the extent of association between an image and a textual description associated with a predefined concept, the likelihood of the occurrence of the image based on the characterizing stochastic process is computed. A high likelihood indicates a strong association between the textual description and the image. The invention utilizes two-dimensional multi-resolution hidden Markov models that demonstrate accuracy and high potential in linguistic indexing of photographic images.

A picture is worth a thousand words. As human beings, we are able to tell a story from a picture based on what we have seen and what we have been taught. A 3-year old child is capable of building models of a substantial number of concepts and recognizing them using the learned models stored in his or her brain. Hence, from a technological stance, it is appreciated that a computer program may be adapted to learn a large collection of semantic concepts from 2-D or 3-D images, build models about these concepts, and recognize these concepts based on these models.
Automatic linguistic indexing of pictures is essentially important to content-based image retrieval and computer object recognition. It can potentially be applied to many areas including biomedicine, commerce, the military, education, digital libraries, and Web searching. Decades of research have shown that designing a generic computer algorithm that can learn concepts from images and automatically translate the content of images to linguistic terms is highly difficult. Much success has been achieved in recognizing a relatively small set of objects or concepts within specific domains.
Many content-based image retrieval (CBIR) systems have been developed. Most of the CBIR projects were aimed at general-purpose image indexing and retrieval systems that focused on searching images visually similar to the query image or a query sketch. These systems were not adapted to have the capability of assigning comprehensive textual descriptions automatically to pictures, i.e., linguistic indexing, because of the great difficulty in recognizing a large number of objects. However, this function is essential for linking images to text and consequently broadening the possible usages of an image database.
Many researchers have attempted to use machine learning techniques for image indexing and retrieval. One such system included a learning component wherein the system internally generated many segmentations or groupings of each image's regions based on different combinations of features, then learned which combinations best represented the semantic categories provided as examples by the user. The system required the supervised training of various parts of the image.
A growing trend in the field of image retrieval is to automate linguistic indexing of images by statistical classification methods to group images into rough semantic classes or categories, such as textured-nontextured, graph-photograph. Potentially, the categorization enhances retrieval by permitting semantically-adaptive searching methods and by narrowing down the searching range in a database. The approach is limited because these classification methods are problem specific and do not extend straightforwardly.
Prior art methods for associating images explicitly with words have one major limitation in that the algorithm used with these methods relies on semantically meaningful segmentation, which is generally unavailable to image databases. Thus there is a need for a system and method of automatic linguistic indexing of images that overcomes the above disadvantage relative to segmentation and wherein the system provides scalability that allows for a large number of categories to be trained at once.

System and method for automatic linguistic indexing of images by a statistical modeling approach


A computer-implemented method for automating service provider status and reporting during a service visit includes the initial steps of creating a service provider transaction, initiating the transaction, and calculating an estimated completion time of the transaction. The estimated completion time is based on at least one service condition, which may include the availability of servicing tools and components, the availability of service provider employees, the priority status, if any, of the service provider transaction, and the level of difficulty of service provider transaction, among others. Preferably, the service conditions include constant or variable associated values. The completion time is calculated based upon a sum of these values. If an unexpected service need or service delay arises, the service provider transaction status is updated, which includes recalculating the estimated time of completion based on a new service condition that arose from the unexpected need or delay. When the service provider transaction is complete, the customer reviews the transaction, confirms that the service provider transaction is complete, and schedules a service completion event.

The present disclosure relates generally to automobile service visits, and more particularly to real-time tracking and reporting of the status of automobile service visits.
Automobile service visits have been around for as long as automobiles have been available for purchase. The typical service visit involves scheduling an appointment with a service provider, being given an approximate time frame for when the services will be complete, and then waiting to hear from the service provider regarding the status of the service. The wait period may include hours, days, or sometimes even weeks to receive a service update from a service provider.
Some service providers may focus on customer service and, in turn, have developed communication processes for informing a customer of the timeline and advances of a particular service visit. These communications typically involve phone calls, emails or similar updates. Though such processes are beneficial, there is a need for a streamlined process of internal and external communications related to automobile service visits.

Method and application for automating automobile service provider tracking and communications


A nozzle for mixing of two reacting fluids wherein the first reactant, flowing across the nozzle, exhibits a variation in reactivity towards the second fluid, introduced through the nozzle and mixing and reacting with the first fluid within the nozzle, and wherein the nozzle is configured to permit this second fluid to be introduced in a way as to compensate for the variation in reactivity and to produce uniform reactant mixture from the two fluids.

1. Field of the Invention
This invention relates to nozzles for providing a uniform reagent flow after one of the reactants has traveled variable distances to a chamber, and more particularly to providing a uniformly dissociated iodine flow in a high energy state to a laser cavity where the singlet delta oxygen reactant travels to the iodine injector over a variable distance from the oxygen generator.
2. Description of the Related Art
Chemical oxygen iodine lasers typically perform at optimum efficiency when the dissociation fraction of iodine in the laser cavity is approximately 85%. Either higher or lower dissociation levels result in degraded performance. The oxygen generator produces singlet delta oxygen, O.sub.2 (.sup.1 .DELTA.), which is mixed with iodine prior to entering into the laser cavity. Between the iodine mixing point and the laser cavity reactions occur between the O.sub.2 (.sup.1 .DELTA.) and the iodine which produce dissociated iodine in a high energy state. The distance provided is selected to achieve the desired level of dissociation at the concentrations and conditions of the mixed streams. For relatively low power chemical oxygen iodine lasers the oxygen generators are relatively small, leading to correspondingly small variations in the concentration and conditions of the O.sub.2 (.sup.1 .DELTA.) at the point at which iodine is mixed. For larger devices using larger oxygen generators these variations can be substantial and can impact laser performance.

Nozzle for providing uniform extraction from a non-uniform flow


The invention provides an electro-optical device having a light-shielding layer for preventing light from entering semiconductor elements. In particular, a liquid crystal display device of the present invention includes an electro-optical material between an element substrate having pixel electrodes and an opposing substrate facing the element substrate. The element substrate includes semiconductor elements for driving the pixel electrodes, insulation films covering the semiconductor element, and a reflective plate disposed on the insulation films, the reflective plate having openings. The semiconductor elements adjacent to the element substrate includes a light-shielding layer for shielding the semiconductor element from incident light, the light-shielding layer having openings in substantially the same regions as the openings in the reflective plate.

1. Field of Invention
The present invention relates to electro-optical devices and electronic apparatuses including such electro-optical devices. In particular, the present invention relates to a semi-transmissive reflective electro-optical device including a substrate provided with a reflective plate on the inner surface of the substrate.
2. Description of Related Art
An active matrix display device is known as an electro-optical device, such as a liquid crystal display device, that includes an electro-optical material, such as liquid crystal, disposed between a pair of substrates. In such an active matrix display device, a matrix of pixel electrodes is formed on one of the substrates and is energized through thin film transistor (TFT) elements for switching the display. In such a display device using TFT elements, when light is incident on a channel region of a TFT element, light leakage is caused. This leads to a display having defects, for example, low contrast and flicker. Japanese Unexamined Patent Application Publication No. 2000-298290, for example, discloses a technique that prevents light from entering the channel regions of the TFT elements by forming, for example, light-shielding films on the light incident surfaces of the TFT elements.
Another known active matrix display device is a semi-transmissive reflective display device in which a reflective plate having openings is formed on an element substrate having TFT elements thereon. The reflective plate reflects light incident on an opposing substrate to allow reflective display. The semi-transmissive reflective display device also allows transmissive display by transmitting through the openings light emitted from a light source disposed adjacent to the outer surface of the element substrate. Since the incident light on the channel regions of the TFT elements generates light leakage that deteriorates the display quality, the semi-transmissive reflective display device is also provided with a light-shielding film adjacent to the light incident surfaces of the TFT elements.
In the above-mentioned technique, having the light-shielding film on the element substrate for preventing the light leakage in the TFT elements, the light-shielding film shields the TFT elements from light. To efficiently utilize this light-shielding film to the fullest extent, it is desirable for the film to have other functions. As disclosed in Japanese Unexamined Patent Application Publication No. 09-127497, when the light-shielding film is formed only in the TFT regions, the surface of the element substrate between the TFT regions and non-TFT regions becomes irregular. The distance between the two substrates thus becomes uneven over these regions and leads to uneven retardation values. The structure in Japanese Unexamined Patent Application Publication No. 2000-298290, in which a light-shielding film is provided on the top surface of the TFT element substrate adjacent to the liquid crystal, is not applicable to a semi-transmissive reflective display panel. The structure in Japanese Unexamined Patent Application Publication No. 07-128658, in which a light-shielding film is provided on a source line, is also not applicable to the semi-transmissive reflective display panel.

Electro-optical device and electronic apparatus


A desaturation circuit for an IGBT is disclosed. In one embodiment, flooding of the component with charge carriers is reduced before the IGBT is turned off.

The invention relates to a desaturation circuit for an IGBT and to a method for desaturating an IGBT.
Insulated-gate bipolar transistors (IGBTs) combine the principle of a bipolar transistor with a wattless driving of a MOS (metal oxide semiconductor) field effect transistor. An electron current is conducted via a lateral or vertical MOS channel for driving the IGBT. This electron current leads to the injection of holes from a pn junction formed at a rear of the IGBT and polarized in the forward direction. As a result, the low conductivity of a voltage-accepting layer can be increased by several orders of magnitude in the turned-on state of the IGBT by injecting an electron hole plasma. When the IGBT is turned off, however, this conductive plasma must be removed from the active zone which is bound to lead to turn-off losses since, during a voltage rise between emitter and collector of the IGBT, a depletion current or part-current for removing the electron hole plasma continues to flow.
In known NPT (non-punch through) IGBTs with planar cell geometry such as IGBT2 by Infineon Technologies, the variation of gate voltage and collector voltage when the IGBT is turned off is determined by the impedance of the gate circuit, by a gate resistance within the driver, series resistances in modules and on the chip and by parasitic capacitances of the IGBT. A reduction in this impedance leads to a quicker discharge of the gate to a Miller plateau; the Miller plateau becomes shorter and the voltage at the collector rises more quickly. This behavior can be influenced within wide ranges by changing the impedance or a magnitude of the gate current in order to produce a corresponding reaction of the IGBT.
IGBTs of the latest IGBT generations with trench cells and field stop, such as e.g., IGBT3 by Infineon Technologies, however, illustrate a behavior which differs from the above behavior. Such IGBTs are characterized by very low on-state values with increased current densities which is achieved by improvements in the charge carrier distributions of electrons and holes. Lower on-state values are achieved by increased flooding of the component with electrons and holes in the conducting state. At the same time, however, the drive characteristics and the controllability of current and voltage variations change particularly when turning off under inductive loads such as in motor drives. The switching behavior is no longer determined by the parasitic capacitances and driver impedances alone. Instead, a voltage rise at the collector when turning off the IGBT can no longer follow the discharge of the gate capacitance when the impedances become smaller which is why the gate is discharged below the Miller plateau, i.e. the gate voltage when load current is flowing. Since the load current continues to flow during this time, it is fed by charge carriers stored in the IGBT. This also determines an increase in the collector voltage by the removal of the charge carriers stored in the IGBT and cannot be accelerated by greater discharge of the gate with lower gate impedance. However, such behavior impedes a delayless feedback of a temporal change in the collector current or overvoltages at the collector since the gate must firstly be charged up to the Miller plateau again until this novel IGBT reacts. In addition, a voltage rise in the IGBT cannot be accelerated which was possible in IGBTs of known prior generations by reducing the gate impedance. However, such acceleration in the voltage rise is desirable for fast switching applications.
To solve the above problems, it is known to increase impedances in the gate circuit of an IGBT to such an extent that it turns off with a slow current drop. Lowering the gate voltage below the Miller plateau was compensated for in this case by means of special gate control circuits in order to provide for a delayless feedback. Current units were limited to low di/dt by suitable adjustments of the IGBT.
EP 0 898 811 B1 describes a method for changing the turn-off behavior of a known IGBT of a generation such as IGBT2. For this purpose, the Miller capacitance is reduced by increasing the collector voltage before the turning off in order to be able to control a subsequent change in time of the collector voltage dV/dt. This is achieved by first reaching the Miller plateau because the delay time to the steeper voltage rise is thus shortened. The collector voltages are set to high voltages such as, for example, 200 V for reducing the Miller capacitance.
DE 102 06 392 A1 proposes a stepped turn-off of the IGBT.
For these and other reasons, there is a need for the present invention.


A new cultivar of Hosta named ‘Atlantis’, a sport of Hosta ‘Abba Dabba Do’, that is characterized by its unique variegated foliage with green centers and wide yellow-green margins comprising about on third of the leaf area. ‘Atlantis’ is a large Hosta with an upright, mounded habit, a vigorous growth rate, and lavender flowers held on upright scapes in mid summer.

The present invention, Hosta 'Atlantis', relates to a new and distinct cultivar of Hosta, botanically known as a Hosta hybrid, hereinafter referred to as 'Atlantis'.
The inventors discovered the new cultivar, 'Atlantis', in summer of 1998 in a cultivated growing area in Waseca, Minn. 'Atlantis' originated as a naturally occurring chimeral mutation of Hosta 'Abba Dabba Do' (unpatented). The parent plant, Hosta, 'Abba Dabba Do', is a variegated mutation of the gold foliaged cultivar, Hosta 'Sun Power' (unpatented). 'Atlantis' is unique in having wide yellow-green margins surrounding green centers. The variegation pattern is similar to the parent plant 'Abba Dabba Do', however the margins of 'Atlantis' are significantly wider. 'Atlantis' has a similar leaf variegation pattern to 'Satisfaction' (unpatented) and H. montana 'Aureo Marginata'. In comparison to 'Atlantis', the leaves of 'Satisfaction' are broader, more heart-shaped, and lack the terminal twist at the leaf apex. 'Aureo Marginata' differs from 'Atlantis' in having a more mounded, less upright plant habit, leaf blades that curve more downward and leaf blades that lack the twist at the apex.
Asexual reproduction of the new cultivar was first accomplished by the inventors utilizing in vitro propagation in Waseca, Minn. in fall of 2002. Asexual reproduction of the new cultivar by division and tissue culture has shown that the unique features of 'Atlantis' are stable and reproduced true to type in successive generations.


Styrene derivatives of the formula ##STR1## and an electrophotographic photoconductor comprising an electroconductive support material and a photosensitive layer comprising at least one styrene derivatives of the same formula are disclosed, in which Ar represents an unsubstituted of substituted phenyl group or an unsubstituted or substituted styryl group, R represents hydrogen, a lower alkyl group or an unsubstituted or substituted phenyl group, and A is selected from the group consisting of ##STR2## wherein R.sup.1 represents a lower alkyl group or a lower alkoxy group, R.sup.2 and R.sup.3 each represent a lower alkyl group, an aralkyl group, or an unsubstituted or substituted phenyl group.

The present invention relates to styrene derivatives and an electrophotographic photoconductor comprising a photosensitive layer containing at least one of the styrene derivatives overlayed on an electroconductive support material.
Conventionally, a variety of inorganic and organic electrophotographic photoconductors are known. As inorganic photoconductors for use in electrophotography, there are known types, in which the photoconductive material is, for instance, selenium, cadmium-sulfide and zinc oxide. In an electrophotographic process, a photoconductor is first exposed to corona charges in the dark, so that the surface of the photoconductor is electrically charged uniformly. The thus uniformly charged photoconductor is then exposed to original light images and the portions exposed to the original light images selectively become electroconductive so that electric charges dissipate from the exposed portions of the photoconductor, whereby latent electrostatic images corresponding to the original light images are formed on the surface of the photoconductor. The latent electrostatic images are then developed by the so-called toner which comprises a colorant, such as a dye or a pigment, and a binder agent made, for instance, of a polymeric material; thus, visible developed images can be obtained on the photoconductor. It is necessary that photoconductors for use in electrophotography have at least the following fundamental properties: (1) chargeability to a predetermined potential in the dark; (2) minimum electric charge dissipation in the dark; and (3) quick dissipation of electric charges upon exposure to light.
While the above-mentioned inorganic electrophotographic photoconductors have many advantages over other conventional electrophotographic photoconductors, at the same time they have several shortcomings from the viewpoint of practical use.
For instance, a selenium photoconductor, which is widely used at present, has the shortcoming that its production is difficult and, accordingly, its production cost is high. Further, it is difficult to work it into the form of a belt due to its poor flexibility, and it is so vulnerable to heat and mechanical shocks that it must be handled with the utmost care.
Cadmium sulfide photoconductors and zinc oxide photoconductors are prepared by dispersing cadmium sulfide or zinc oxide in a binder resin. They can be produced inexpensively compared with selenium photoconductors and are also used commonly in practice. However, the cadmium sulfide and zinc oxide photoconductors are poor in surface smoothness, hardness, tensile strength and wear resistance. Therefore, they are not suitable as photoconductors for use in plain paper copiers in which the photoconductors are used in quick repetition.
Recently, organic electrophotographic photoconductors, which are said not to have such shortcomings of the inorganic electrophotographic photoconductors, have been proposed, and some of them are in fact employed for practical use. Representative examples of such organic electrophotographic photoconductors are an electrophotographic photoconductor comprising poly-N-vinylcarbazole and 2,4,7-trinitro-fluorene-9-one (U.S. Pat. No. 3,484,237); a photoconductor in which poly-N-vinylcarbazole is sensitized by a pyrylium salt type dyestuff (Japanese Patent Publication No. 48-25658); a photoconductor containing as the main component an organic pigment (Japanese Laid-Open Patent Application No. 47-37543); and a photoconductor containing as the main component an eutectic crystaline complex (Japanese Laid-Open Patent Application No. 47-10735).
Although the above-mentioned organic electrophotographic photoconductors have many advantages over other conventional electrophotographic photoconductors, they still have several shortcomings from the viewpoint of practical use, in particular, in terms of cost, production, durability and electrophotographic sensitivity.


Stabilizing mixtures for a plastic material are disclosed. The mixture is comprised of (a) about one part by weight of a tocopherol compound; and (b) from about 1.4 to about 5.0 parts by weight of a secondary antioxidant.

1. Field of the Invention
This invention relates to stabilizers for plastic materials, and more specifically, to stabilizing mixtures to improve the color and the processing of plastic materials.
2. Background
Reducing oxidation and stabilizing the color of polymers during processing is important to the plastics industry. Polymers, during processing into articles, are subjected to high temperatures and pressures which can have an adverse affect on the molecular weight and physical properties of the polymer and appearance of the finished articles made from these polymers. The need exists, therefore, for antioxidant and color stabilizing materials which minimize oxidization and color instability.
U.S. Pat. No. 4,806,580 discloses a stabilizer mixture for stabilizing plastic material in processing. The disclosed stabilizer mixture contains (a) a chroman derivative and (b) an organic phosphite or phosphonite in a ratio (a:b) of 1:5 to 1:14.
Japanese Patent Publication No. JP62-86036 discloses a composition containing per 100 parts by weight of a polyolefin, 0.005 to 0.5 parts by weight of a compound selected from the vitamin E group, and 0.01 to 0.5 parts by weight of a phosphite.
Japanese Patent Publication No. JP 54-55043 discloses a composition containing polyolefin and a compound from the vitamin E group and various phosphites. In Examples 1-6 thereof the ratios of vitamin E:phosphite evaluated in polypropylene were 1:1.6 and 1:3.3.
It is an object of the present invention to provide a stabilizer mixture for plastic materials which contain polyethylene to improve the processing stability and color.

Stabilizers for thermo plastic materials