The present invention is directed to kinase inhibitor compounds having the following structure: or a stereoisomer, pharmaceutically acceptable salt, oxide, or solvate thereof, where R1, R2, X, n, R3, Y, Z, R4, R5, R6, and = are as defined herein. The present invention also relates to compositions containing the kinase inhibitor compounds, methods of inhibiting activity of a kinase in a cell, methods of increasing cell proliferation in a population of pancreatic beta cells, methods of treating a subject for a condition associated with insufficient insulin secretion, and methods of treating a subject for a neurological disorder.

The Dual-Specificity Tyrosine-Regulated kinases ("DYRKs") belong to the CMCG family of eukaryotic protein kinases which include the CDK-like kinases (CLKs), Glycogen Synthase Kinase 3 (GSK3), Cyclin Dependent Kinases (CDKs), and Mitogen-Activated Protein Kinases (MAPKs). DYRK family proteins self-activate by autophosphorylation of the conserved tyrosine residue in the activation loop, then subsequently phosphorylate substrates only on serine and threonine residues (Lochhead et al., "Activation-Loop Autophosphorylation is Mediated by a Novel Transitional Intermediate Form of DYRKs," Cell 121(6):925-936 (2005); Walte et al., "Mechanism of Dual Specificity Kinase Activity of DYRK1A," FEBS J. 280(18):4495-4511 (2013); and Becker et al., "Activation, Regulation, and Inhibition of DYRK1A," FEBS J. 278(2):246-256 (2011)). The DYRK family consists of five subtypes, including 1A, 1B, 2, 3 and 4. Among them, DYRK1A is the most extensively studied subtype. It is ubiquitously expressed and has been shown to play an important role in brain development and function (Becker et al., "DYRK1A: A Potential Drug Target for Multiple Down Syndrome Neuropathologies," CNS Neurol. Disord.: Drug Targets 13(1):26-33 (2014)), neurodegenerative diseases (Wegiel et al., "The Role of DYRK1A in Neurodegenerative Diseases," FEBS J. 278(2):236-245 (2011) and Smith et al., "Recent Advances in the Design, Synthesis, and Biological Evaluation of Selective DYRK1A Inhibitors: A New Avenue for a Disease Modifying Treatment of Alzheimer's?," ACS Chem. Neurosci. 3(11):857-872 (2012)), tumorigenesis, apoptosis (Ionescu et al., "DYRK1A Kinase Inhibitors With Emphasis on Cancer," Mini-Rev. Med. Chem. 12(13):1315-1329 (2012) and Fernandez-Martinez et al., "DYRK1A: The Double-Edged Kinase as a Protagonist in Cell Growth and Tumorigenesis," Mol. Cell. Oncol. 2(1):e970048 (2015)), and human pancreatic β-cell proliferation (Wang et al., "A High-Throughput Chemical Screen Reveals That Harmine-Mediated Inhibition of DYRK1A Increases Human Pancreatic Beta Cell Replication," Nat. Med. 21(4):383-388 (2015); Shen et al., "Inhibition of DYRK1A and GSK3B Induces Human β-cell Proliferation," Nat. Commun. 6:8372 (2015); Rachdi et al., "Dyrk1A Induces Pancreatic β Cell Mass Expansion and Improves Glucose Tolerance," Cell Cycle 13(14):2221-2229 (2014); and Dirice et al., "Inhibition of DYRK1A Stimulates Human Beta-Cell Proliferation," Diabetes 65:(6):1660-1671 (2016)).
Regulated expression of DYRK1A during fetal, postnatal life, as well as in adults, is essential for normal neuronal development and brain function. DYRK1A is located in the Down Syndrome Critical region ("DSCR") on human chromosome 21, a genomic region that has an important role in pathogenesis of Down Syndrome ("DS"), one of the most common and frequent human genetic disorders (Becker et al., "Activation, Regulation, and Inhibition of DYRK1A," FEBS J. 278(2):246-256 (2011) and Becker et al., "Structural and Functional Characteristics of Dyrk, a Novel Subfamily of Protein Kinases With Dual Specificity," Prog. Nucleic Acid Res. Mol. Biol. 62:1-17 (1999)). Overexpression of DYRK1A in mouse and Drosophila models mimics the neurodevelopmental abnormalities associated with DS (Becker et al., "DYRK1A: A Potential Drug Target for Multiple Down Syndrome Neuropathologies," CNS Neurol. Disord.: Drug Targets 13(1):26-33 (2014); Wegiel et al., "The Role of DYRK1A in Neurodegenerative Diseases," FEBS J. 278(2):236-245 (2011); Park et al., "Function and Regulation of Dyrk1A: Towards Understanding Down Syndrome," Cell. Mol. Life Sci. 66(20):3235-3240 (2009); and Ogawa et al., "Development of a Novel Selective Inhibitor of the Down Syndrome-Related Kinase Dyrk1A," Nat. Commun. 1: Article Number 86 (2010)). Recent evidences has also implicated DYRK1A in the tau dysfunction and tau pathology of Alzheimer's disease ("AD"), dementia with Lewy bodies, and Parkinson's disease (Wegiel et al., "The Role of DYRK1A in Neurodegenerative Diseases," FEBS J. 278(2):236-245 (2011); Smith et al., "Recent Advances in the Design, Synthesis, and Biological Evaluation of Selective DYRK1A Inhibitors: A New Avenue for a Disease Modifying Treatment of Alzheimer's?," ACS Chem. Neurosci. 3(11):857-872 (2012); and Stotani et al., "DYRK1A Inhibition as Potential Treatment for Alzheimer's Disease," Future Med. Chem. 8(6):681-696 (2016)). It has been reported that DYRK1A is overexpressed in various tumors such as, ovarian cancer, colon cancer, lung cancer, and pancreatic cancer, signifying its role in tumorigenesis and uncontrolled cell proliferation (Ionescu et al., "DYRK1A Kinase Inhibitors With Emphasis on Cancer," Mini-Rev. Med. Chem. 12(13):1315-1329 (2012) and Fernandez-Martinez et al., "DYRK1A: The Double-Edged Kinase as a Protagonist in Cell Growth and Tumorigenesis," Mol. Cell. Oncol. 2(1):e970048 (2015)). Inhibition of DYRK1A leads to destabilized EGFR and reduced EGFR-dependent tumor growth in glioblastoma (Pozo et al., "Inhibition of DYRK1A Destabilizes EGFR and Reduces EGFR-Dependent Glioblastoma Growth," J. Clin. Invest. 123(6):2475-2487 (2013)). Also, DYRK1A inhibition induces activation of caspase-9 which leads to massive apoptosis in specific cancer cell types (Seifert et al., "DYRK1A Phosphorylates Caspase 9 at an Inhibitory Site and is Potently Inhibited in Human Cells by Harmine," FEBS J. 275(24):6268-6280 (2008)). Recently, DYRK1A has been shown to be involved in molecular pathways relevant to human β-cell proliferation, making it a potential therapeutic target for β-cell regeneration in Type 1 and Type 2 diabetes (Wang et al., "A High-throughput Chemical Screen Reveals That Harmine-Mediated Inhibition of DYRK1A Increases Human Pancreatic Beta Cell Replication," Nat. Med. 21(4):383-388 (2015); Shen et al., "Inhibition of DYRK1A and GSK3B Induces Human β-cell Proliferation," Nat. Commun. 6:8372 (2015); Rachdi et al., "Dyrk1A Induces Pancreatic β Cell Mass Expansion and Improves Glucose Tolerance," Cell Cycle 13(14):2221-2229 (2014); and Dirice et al., "Inhibition of DYRK1A Stimulates Human Beta-cell Proliferation," Diabetes 65:(6):1660-1671 (2016)). DYRK1A inhibition has been proposed to drive β-cell proliferation by inducing translocation of the nuclear factor of activated T cells ("NFAT") family of transcription factors to the nucleus, allowing access to the promoters of genes which subsequently activate human β-cell proliferation (Wang et al., "A High-throughput Chemical Screen Reveals That Harmine-Mediated Inhibition of DYRK1A Increases Human Pancreatic Beta Cell Replication," Nat. Med. 21(4):383-388 (2015) and Rachdi et al., "Dyrk1A Induces Pancreatic β Cell Mass Expansion and Improves Glucose Tolerance," Cell Cycle 13(14):2221-2229 (2014)).
Because of its involvement in neurodegenerative disease, cancer, and diabetes, DYRK1A has attracted increasing interest as a potential therapeutic target. A significant amount of work has been carried out to not only understand its underlying role in diseases, but also in identifying novel DYRK1A inhibitors (Becker et al., "Activation, Regulation, and Inhibition of DYRK1A," FEBS J. 278(2):246-256 (2011); Becker et al., "DYRK1A: A Potential Drug Target for Multiple Down Syndrome Neuropathologies," CNS Neurol. Disord.: Drug Targets 13(1):26-33 (2014); Wegiel et al., "The Role of DYRK1A in Neurodegenerative Diseases," FEBS J. 278(2):236-245 (2011); Smith et al., "Recent Advances in the Design, Synthesis, and Biological Evaluation of Selective DYRK1A Inhibitors: A New Avenue for a Disease Modifying Treatment of Alzheimer's?," ACS Chem. Neurosci. 3(11):857-872 (2012); Ionescu et al., "DYRK1A Kinase Inhibitors with Emphasis on Cancer," Mini-Rev. Med. Chem. 12(13):1315-1329 (2012); Fernandez-Martinez et al., "DYRK1A: The Double-Edged Kinase as a Protagonist in Cell Growth and Tumorigenesis," Mol. Cell. Oncol. 2(1):e970048 (2015); Wang et al., "A High-throughput Chemical Screen Reveals That Harmine-Mediated Inhibition of DYRK1A Increases Human Pancreatic Beta Cell Replication," Nat. Med. 21(4):383-388 (2015); Shen et al., "Inhibition of DYRK1A and GSK3B Induces Human β-cell Proliferation," Nat. Commun. 6:8372 (2015); and Dirice et al., "Inhibition of DYRK1A Stimulates Human Beta-cell Proliferation," Diabetes 65:(6):1660-1671 (2016)).
Several DYRK1A inhibitors from natural sources as well as small molecule drug discovery programs have been identified and characterized. Among all the DYRK1A inhibitors, harmine and its analogues (β-carbolines) are the most commonly studied and remain the most potent and orally bioavailable class of inhibitors covered to date (Becker et al., "Activation, Regulation, and Inhibition of DYRK1A," FEBS J. 278(2):246-256 (2011) and Smith et al., "Recent Advances in the Design, Synthesis, and Biological Evaluation of Selective DYRK1A Inhibitors: A New Avenue for a Disease Modifying Treatment of Alzheimer's?," ACS Chem. Neurosci. 3(11):857-872 (2012)).
Apart from harmine, EGCg and other flavan-3-ols (Guedj et al., "Green Tea Polyphenols Rescue of Brain Defects Induced by Overexpression of DYRK1A," PLoS One 4(2):e4606 (2009) and Bain et al., "The Specificities of Protein Kinase Inhibitors: An Update," Biochem. J. 371(1):199-204 (2003)), leucettines (Tahtouh et al., "Selectivity, Cocrystal Structures, and Neuroprotective Properties of Leucettines, a Family of Protein Kinase Inhibitors Derived from the Marine Sponge Alkaloid Leucettamine B," J. Med. Chem. 55(21):9312-9330 (2012) and Naert et al., "Leucettine L41, a DYRK1A-preferential DYRKs/CLKs Inhibitor, Prevents Memory Impairments and Neurotoxicity Induced by Oligomeric Aβ25-35 Peptide Administration in Mice," Eur. Neuropsychopharmacol. 25(11):2170-2182 (2015)), quinalizarin (Cozza et al., "Quinalizarin as a Potent, Selective and Cell-permeable Inhibitor of Protein Kinase CK2," Biochem. J 421(3):387-395 (2009)), peltogynoids Acanilol A and B (Ahmadu et al, "Two New Peltogynoids from Acacia nilotica Delile with Kinase Inhibitory Activity," Planta Med. 76(5):458-460 (2010)), benzocoumarins (dNBC) (Sarno et al., "Structural Features Underlying the Selectivity of the Kinase Inhibitors NBC and dNBC: Role of a Nitro Group that Discriminates Between CK2 and DYRK1A," Cell. Mol. Life Sci. 69(3):449-460 (2012)), and indolocarbazoles (Staurosporine, rebeccamycin and their analogues) (Sanchez et al., "Generation of Potent and Selective Kinase Inhibitors by Combinatorial Biosynthesis of Glycosylated Indolocarbazoles," Chem. Commun. 27:4118-4120 (2009), are other natural products that have been shown to inhibit DYRK1A and other kinases.
Among the other scaffolds identified from small molecule drug discovery attempts, INDY (Ogawa et al., "Development of a Novel Selective Inhibitor of the Down Syndrome-Related Kinase Dyrk1A," Nat. Commun. 1: Article Number 86 (2010)), DANDY (Gourdain et al., "Development of DANDYs, New 3,5-Diaryl-7-Azaindoles Demonstrating Potent DYRK1A Kinase Inhibitory Activity," J. Med. Chem. 56(23):9569-9585 (2013)), and FINDY (Kii et al., "Selective Inhibition of the Kinase DYRK1A by Targeting its Folding Process," Nat. Commun. 7:11391 (2016)), pyrazolidine-diones (Koo et al., "QSAR Analysis of Pyrazolidine-3,5-Diones Derivatives as Dyrk1A Inhibitors," Bioorg. Med. Chem. Lett. 19(8):2324-2328 (2009); Kim et al., "Putative Therapeutic Agents for the Learning and Memory Deficits of People with Down Syndrome," Bioorg. Med. Chem. Lett. 16(14):3772-3776 (2006)), amino-quinazolines (Rosenthal et al., "Potent and Selective Small Molecule Inhibitors of Specific Isoforms of Cdc2-Like Kinases (Clk) and Dual Specificity Tyrosine-Phosphorylation-Regulated Kinases (Dyrk)," Bioorg. Med. Chem. Lett. 21(10):3152-3158 (2011)), meriolins (Giraud et al., "Synthesis, Protein Kinase Inhibitory Potencies, and In Vitro Antiproliferative Activities of Meridianin Derivatives," J. Med. Chem. 54(13):4474-4489 (2011); Echalier et al., "Meriolins (3-(Pyrimidin-4-yl)-7-Azaindoles): Synthesis, Kinase Inhibitory Activity, Cellular Effects, and Structure of a CDK2/Cyclin A/Meriolin Complex," J. Med. Chem. 51(4):737-751 (2008); and Akue-Gedu et al., "Synthesis and Biological Activities of Aminopyrimidyl-Indoles Structurally Related to Meridianins," Bioorg. Med. Chem. 17(13):4420-4424 (2009)), pyridine and pyrazines (Kassis et al., "Synthesis and Biological Evaluation of New 3-(6-hydroxyindol-2-yl)-5-(Phenyl) Pyridine or Pyrazine V-Shaped Molecules as Kinase Inhibitors and Cytotoxic Agents," Eur. J Med. Chem. 46(11):5416-5434 (2011)), chromenoidoles (Neagoie et al., "Synthesis of Chromeno[3,4-b]indoles as Lamellarin D Analogues: A Novel DYRK1A Inhibitor Class," Eur. J Med. Chem. 49:379-396 (2012)), 11H-indolo[3,2-c]quinoline-6-carboxylic acids, 37 thiazolo[5,4-f]quinazolines (EHT 5372) (Foucourt et al., "Design and Synthesis of Thiazolo[5,4-f]quinazolines as DYRK1A Inhibitors, Part I," Molecules 19(10):15546-15571 (2014) and Coutadeur et al., "A Novel DYRK1A (Dual Specificity Tyrosine Phosphorylation-Regulated Kinase 1A) Inhibitor for the Treatment of Alzheimer's Disease: Effect on Tau and Amyloid Pathologies In Vitro," J Neurochem. 133(3):440-451 (2015)), and 5-iodotubercidin (Dirice et al., "Inhibition of DYRK1A Stimulates Human Beta-cell Proliferation," Diabetes 65:(6):1660-1671 (2016) and Annes et al., "Adenosine Kinase Inhibition Selectively Promotes Rodent and Porcine Islet β-cell Replication," Proc. Natl. Acad. Sci. 109(10):3915-3920 (2012)) showed potent DYRK1A activity with varying degrees of kinase selectivity.
Most of these compounds are non-selective inhibitors of DYRK1A and exhibit pharmacological side effects, such as CNS activity or apoptosis, thereby limiting their therapeutic utility and potential for pharmaceutical development. This non-selectivity may be attributed to the fact that all these DYRK1A inhibitors are Type I kinase inhibitors, which bind to a highly conserved ATP binding pocket.
The present invention is directed to overcoming deficiencies in the art.

Kinase inhibitor compounds and compositions and methods of use


The present disclosure provides for categorization of lists of words. The method comprises querying DBpedia to find the resources related to the given list of words. Once the resources are found, the corresponding media Wikipedia categories can be retrieved, as well as their ancestors, generating a graph of categories. A number of graph analysis algorithms can then be applied to the graph, each returning a selected category. For each algorithm a classifier is trained to decide whether the output of the algorithm is indeed the “best” category. An ensemble weighted majority voting can then be used to select the best category based on votes cast by each classifier. The disclosure demonstrates a more accurate selection of the best category and can include an ensemble majority rated voting algorithm comprising all voting members initially casting one vote; i.e., highest frequency, most frequently occurring word, least common ancestor and centrality measures.

Any application dealing with large amounts of structured data (such as databases and spreadsheets) that benefits from knowing an exact semantic category for the various fields of data can utilize the method to be described hereinafter.
Given a list of words of "arbitrary origin" that are assumed to have one or more categories in common, the problem becomes finding the category that best fits (based on human judgment or other methods) the list of words with enough accuracy to be used in automated data processing applications. In one illustrative example a list of numbers can include (2, 3, 5, 7, 11, 13). The question becomes what is the best category that all of, or most of, the aforementioned numbers belong. At least three categories can be listed: prime numbers; odd numbers; and, positive integers. It appears that the category of prime numbers would be the best category for these numbers. Another illustrative example includes (dog, cat, hamster, gold fish). Two categories that this list belongs to are: pets and animals. It would appear that the aforementioned list is best categorized as pets.
It is to be appreciated that categorizing a list of words of "arbitrary origin" requires a large comprehensive, multifaceted categorization system that reflects how a wide range of people would naturally categorize the words in the list. For example, the category of "Presidents of the United States" or "Assassinated Presidents of the United States" would depend on the particular list of Presidents. One present categorization system involves Wikipedia's crowd sourced "folksonomy" which is used to organize Wikipedia articles using a sense of classification and organization that is agreeable to the authors and other individuals that categorize articles. Wikipedia's classification system is effective for classifying a list of words when there is strong semantic similarity between the words in the list. For example, the classification system is good for categories like: countries, 'Presidents of the USA', and birds. Wikipedia's classification system is not as good for: 'objects found in the sky' or 'people born in January'. There are many applications where knowing what lists of words represent is useful. One such application is the conversion of tabular data into resource description framework (RDF) triples (linked data). An RDF file can parse down to a list of triples. A triple comprises a subject, a predicate, and an object.
Another application is combining two distinct databases into one database where both of the original databases contain records with the same type of information but have different syntactic schemas. The problem being resolved in the present disclosure is the automatic categorization of arbitrary fields in a spread sheet or database to make easier a class of problems like the two described above. Current approaches to this problem typically require a large amount of contextual information about the specific problem in order to create a one off solution that does not generalize well to the entire class of problems in this area.

System for categorizing lists of words of arbitrary origin


An improved power supply and platform for a military radio has been developed. The apparatus includes a base that is adapted and arranged for supporting a HARRIS 117 radio and a power amplifier adapted to amplify radio frequency output of the radio. The connectors include an electrical connector for the radio and a connector for the amplifier. A power supply is housed within the assembly. A power supply for the connector to the amplifier is also housed within the assembly. Also included is a wiring harness for a SINCGARS LS/671 device and a LED indicator to identify which radio is in operation for multiple radio configurations.

The U.S. Department of Defense employs a type of UHF, VHF-FM, and SATCOM combat net radio known as the "Harris 117 Radio". These radios have a military nomenclature of AN/PRC-117. The HARRIS 117 radios, are designed to provide the primary means of tactical communications and control for U.S. ground mounted and dismounted units, all in coordination with naval and air support. HARRIS 117 radios are designed on a modular basis for achieving maximum commonality among the various ground airborne system configurations of the armed forces. HARRIS 117 radios provide U.S. military commanders with a highly reliable, secure, and easily maintainable tactical radio net.
HARRIS 117 radios possess a nominal input power requirements of 24-32 volts direct current, which is supplied by rechargeable on-board batteries. Recharging the HARRIS 117 radio batteries is inconvenient and, in certain mission applications, unattainable. Currently, specialized and complex battery recharging systems are available for recharging HARRIS 117 radio batteries; however, these systems are not always operable in a given application.

This patent is subject to a terminal disclaimer.

Integrated power supply and platform for military radio


A self-centering cable includes a restoring and energy-dissipation unit and a cable reinforcement connected to the restoring and energy-dissipation unit by a connecting unit. The restoring and energy-dissipation unit includes an outer trough, an axial tube provided in an opening at the upper end of the outer trough, two inverted U-shaped mild steel members provided side by side and fixedly mounted in the outer trough, an axial pallet sandwiched between and fixedly connected to the two inverted U-shaped mild steel members, and a disc spring set provided in the outer trough and sleeved onto the axial tube. The cable reinforcement includes a tensile reinforcement penetrating into a reinforcement bottom connector and a reinforcement top connector. The reinforcement bottom connector is connected to the axial tube, the top end connector, connected to the reinforcement top connector, and a bottom end connector are connected to a structure to be reinforced.

To improve the lateral stiffness of a structure and reduce damage to the structure caused by an earthquake, braces are often provided in the structure to increase the lateral stiffness of the structure and dissipate the seismic input energy. Existing ordinary braces may produce irreparable residual deformation under a strong earthquake and exert some adverse impacts on the structure. To avoid irreparable damage to the structure under a strong earthquake, self-restoring energy-dissipative braces come into being. At present, most existing self-restoring energy-dissipative braces are bidirectional load-carrying braces. To avoid compressive buckling and achieve resetting effect, the self-restoring energy-dissipative braces are often complex in configuration and expensive to build.
At present, main sources of restoring forces in restorable functional braces are disc springs, steel strands, fiber reinforced polymer (FRP) reinforcements, memory alloys, and the like. However, the steel strands and the FRP reinforcements have strict requirements for anchoring and may produce relatively large prestress losses during use, and memory alloy materials are expensive currently.
At present, energy-dissipative braces mostly use plastic deformation energy dissipation of metal, friction energy dissipation, and flow energy dissipation of viscous material. The plastic deformation energy dissipation of metal has stable performance and high reliability. The friction energy dissipation has the problems of easy aging of friction materials and a large difference between a maximum static friction force and a sliding friction force. The flow energy dissipation of viscous materials has disadvantages such as temperature sensitivity and leakage of viscous material. At present, the restorable functional braces have widespread problems such as a complex structure, a large self-weight, high costs, an unstable energy dissipation effect, and a low material strength utilization rate.

Self-centering cable with metal-based energy-dissipation


Systems and methods for performing hybrid symbolic execution to detect exploitable bugs in binary code are described. In some example embodiments, the systems and methods determine that resources associated with an execution client performing symbolic execution of a target program are below, at, or above a threshold performance level, generate checkpoints for active executing paths of the online symbolic execution, and cause the execution client to perform symbolic execution in response to the determination that the resources are at or above the threshold performance level.

An exploit, such as a control flow exploit, may allow an attacker to perform harm to a computer. Typically, an attacker will manually review the code of a software program, identify a vulnerability, or bug, and attempt to exploit that vulnerability. If the vulnerability is exploitable, the attacker may seize control of the software, and any computing device running the software, until the exploit is discovered and removed, and the vulnerability is fixed. Alternatively, the attacker's exploit may steal sensitive information, or launch unauthorized commands, or cause other malice.
Manual, or somewhat automated, techniques can be suitable for attackers when seeking vulnerabilities, as they only need to find one exploitable bug to be successful in compromising a computing system. However, computer security professionals cannot rely on a manual review of software alone, as they would ideally like to identify and fix any and all exploitable bugs in software before certifying that software as secure. Otherwise, that software could be compromised.
Symbolic execution (or, symbolic evaluation), refers to analyzing programs by tracking symbolic values. A computer security professional may utilize and/or perform symbolic execution on a program in order to detect vulnerabilities in the program, because the symbolic execution is capable of reasoning about all inputs that take the same paths through a program, which may identify the vulnerabilities in the program, among other things. Existing symbolic execution frameworks include Bouncer, BitFuzz, BitTurner, FuzzBall, McVeto, SAGE, and S2E, CUTE, BitBlaze, KLEE, and others.

Detecting exploitable bugs in binary code


A floor molding forming a transition at a corner between a floor and a wall disposed at a right angle to the floor. The floor and wall are both tiled with each tile having a bottom surface, side edges and a top surface. A wall bracket is secured between the wall and the wall tiles, including a leg disposed adjacent to the side edge of the wall tile facing the corner. A floor bracket is secured between the floor and the floor tiles at a distance from the wall bracket forming a gap therebetween. The floor bracket has an L-shaped member including a leg disposed adjacent to the side edge of the floor tile facing the corner. The L-shaped member also includes an arm connected to the leg disposed adjacent to the top surface of the floor tile. An elastic plastic bridge is coupled between the wall bracket leg and the floor bracket L-shaped member across the gap. The elastic plastic bridge permits relative movement between said wall bracket and said floor bracket while maintaining the transition between the wall and the floor.

1. Field of the Invention
The present invention relates to a floor molding forming a transition bridge at a corner between a floor and a wall. More specifically, the invention relates to a floor molding for use with a tiled floor and a tiled wall.
2. The Prior Art
The German Patent DE-OS 35 03 396 discloses two separate plastic angle sections which form a sliding connection. This sliding connection may compensate for movement between surfaces due to changes in the floor structure and thermal expansion or contraction. These connections are particularly useful if the floor is to be arranged on a heat insulating layer, for example, polystyrene foam sold under the trademark STYROPOR. Heat and sound insulation boards become compressed over time which can lower the height of the floor.
The angle sections are provided with relatively thin fastening legs which contain perforations and are attached to the floor or wall by being placed into the mortar or adhesive layer between the wall or floor and the tile. The angle section connected to the wall is provided with an elastically-linked connecting leg which slidingly engages a pocket formed on the floor mounted angle section. As the floor and its angle section sink, the connecting leg is exposed as it slides out of the pocket.
With the known device, it is difficult to form the joint between the floor tiles and the angle section which is secured to the floor. Due to the irregular angles formed between the floor and wall surfaces, the edges of the perimeter tiles have to be cut. The irregularities of the joint, as a rule, are filled with joint mortar. The transition zone between the angle section secured on the wall and the angle section secured on the floor remains visible with the prior art device, as does the top side of the angle section secured on the floor. Therefore, the angle sections cannot be made from recycled material which tends to show variations in color.
With adjacent tiled surfaces where only minor movement or settling is expected, the use of a device having two assembled sections is relatively costly. Another drawback exists in the fact that when the sections are slid together, an open joint remains between the pocket and the inserted leg. This joint cannot be sealed because of the required relative movement between the two sections. There is a risk that bacteria or other contaminants may enter the joint which poses a particular problem in large institutional kitchens.


A power supply includes at least one current source for providing current and a reference voltage generator for providing a first reference voltage and a second reference voltage. A control circuit selectively couples the current to the power supply output as a function of a monitored voltage, the first reference voltage, and the second reference voltage.

A wide variety of electric power supplies have been developed for use with integrated circuit and other devices. Some common examples include DC/DC converters and VRMs. In many applications, including those utilizing low voltage digital circuitry, such as microprocessors, the power supply must provide a fast dynamic response to changes or variations in the load or load requirements.
A typical DC/DC converter converts a DC voltage supplied from one or more power sources to a desired voltage. This can be accomplished using switching devices that selectively couple one or more current sources to the power supply output. By dynamically controlling the on/off timing of each switching device, the number of current sources supplying current to the output, and thus the amount of output current supplied to the load, can be dynamically controlled. This is particularly useful when, for example, a constant voltage across a variable load is desired.
As recognized by the inventor hereof, one disadvantage of many known power supplies is the effect of parasitics on circuit performance, including increased output noise levels, undesirable voltage ripple, and switching losses.


A compression seal for a coaxial cable connector has a main body with an upward facing surface or flange on the outer surface thereof, the upward facing surface or flange facing away from the main body. The outer surface of the main body also has at least one first portion having a first diameter and at least one second portion having a second diameter, the first diameter being smaller than the second diameter. The compression seal may also have an outer body that receives the main body and also engages a connector at both ends.

1. Field of the Invention
The present invention relates generally to compression seals for coaxial cable connectors, and particularly to seals for sealing gaps at interfaces between coaxial cable connectors and terminals.
2. Technical Background
Coaxial cable connectors such as F-connectors are used to attach a coaxial cable to another object such as an appliance or junction having a terminal adapted to engage the coaxial cable connector. When used outdoors in weather-exposed areas it is desirable to prevent moisture from entering the terminal/connector/cable system. Various connectors are commercially available for outdoor applications and generally prevent moisture from entering the connector/cable junction. Such connectors must be attached to a coaxial cable using various cable preparation techniques and installation tools. Cable preparation typically requires removal of portion of the cable jacket, braid, outer conductor and core to expose the cable center conductor. Another portion of the cable jacket is removed to expose the cable braid. Cable preparation is often completed by folding of the cable braid structure back against the remaining cable jacket. The cable is then inserted into the connector, after which the connector is activated to secure the connector to the coaxial cable. For outdoor applications the connector is generally sealed to the cable either by the internal workings of the connector or by the use of an external sealant, heat shrinkable tubing, rubber cement, fusing tape or rubberized boot.
In order to maintain the integrity of the coaxial system, moisture must be prevented from entering the connector/appliance junction as well. In the past, others have attempted to provide a connector/appliance seal by using a rubber type material in the form of a tight fitting ring with an inner bore and an outer diameter or shape. For various reasons, the foregoing attempts have yielded less than satisfactory results. For example, attempts at encapsulating the connectors with tapes, shrink % wrappings and plastic or rubber cements are too prone to installation errors, resulting in exposed seams and/or internal voids where moisture can collect and eventually penetrate to the cable junction. Moreover, shrink wrappings require the use of heat or chemicals which further complicate installation procedures. Cements require time to set up and cure, thus also prolonging and complicating installation procedures. The use of sealing components such as externally applied flexible boots and/or grommets again results in internal voids where moisture can collect. Installation of tight fitting seal rings is difficult and therefore many times is avoided. Subsequent removal of tight fitting seal rings after a lengthy period of service can be even more difficult than installation and oftentimes requires the use of a knife or similar instrument to cut the seal ring off of the appliance junction. This can likely result in damage to the junction threads and is not desirable. Additionally, existing seal rings are limited in use by the length of terminal port on which they are installed. A specific length seal ring must be matched with and installed on a terminal port of compatible length, thereby requiring the technician to recognize various port lengths and have a correct assortment of seal rings on hand. One example of a known seal ring is illustrated in FIG. 1. As illustrated, a seal ring 10 typically has a smooth outer surface 12 and a first internal bore 14 that is slightly smaller than the diameter of the threaded section 16 of terminal 18. Terminal 18 projects out from a wall surface, for example the exterior surface of an electrical or electronic device. This seal ring 10 also has a second internal bore 20 that has a diameter slightly smaller than the coupling nut 22 associated with coaxial cable connector 24. In this manner, a tight seal may be achieved by the tight fit between the seal ring 10 and, at each end, the coupling nut 22 and the threaded section 16 of terminal 18.
However, this and many of the known seal rings cover substantially most of the threads on the appliance port and require that at least a portion of the corresponding cable connector coupler engage the seal ring while engaging the port threads. This engagement of the seal ring can cause difficulty in turning the connector coupler, making the connector hard to install.
It would be desirable therefore to provide a terminal/connector junction sealing device that is easily installed, reliable, economical, easily removable, cover a range of terminal port lengths and allow easier turning of the connector coupler during installation.

Compression seal for coaxial cable connector and terminal


An apparatus for dismantling filter inserts, especially disposable oil filters which comprise a filter paper element and an internal metal supporting tube, as well as metal end plates. The apparatus has two support rails 15 and 16 with upper edges formed as cutting edges. The support rails are mounted in a frame 11 for displacement transversely toward or away from each other to vary the spacing between them. Vertically above and perpendicular to the direction of displacement of the two support rails is a platen 26 driven by a compressed-air cylinder 24 or the like to move along the perpendicular such that the platen will compress a filter insert 19 placed upon the two support rails and sever the end plates 21 and 22 from the filter paper element 20.

This invention relates to an apparatus for dismantling filter inserts.
The use of disposable oil filters for filtering motor oil in motor vehicles is generally known. These disposable oil filters consist of a casing which is permanently joined to the bottom by means of a cover. The inlet and outlet openings for the oil to be filtered are provided in this bottom. In the casing there is a filter insert which usually comprises a tube of pleated paper. The casing may also contain a bypass valve or a shut-off valve which prevents the filter from draining empty when the motor is shut off.
After a certain period of use, such a filter must be removed and replaced with a new one. The disposal of such disposable oil filters whole, which generally still contain a certain amount of old oil in their interior, is problematical. Problem-free disposal is therefore possible only if this disposable oil filter is broken down to its individual components, so that they can be reused or disposed of safely.
Published German Patent Application No. DE 3,705,391 discloses an apparatus for the disposal, elimination and processing of used oil filters. In this apparatus individual oil filters are transported by a conveyor system into a defined final position, then delivered to a cutting station, and in a separating apparatus that follows, the filter paper is freed from the holder. This apparatus is said to make it possible to disassemble a relatively large number of oil filters in a short time.
A disadvantage of this apparatus is that it is very costly, and therefore its use appears to be practical only when there is a large number of used oil filters to be disposed of. Due to the use of handling apparatus to correctly position the oil filters, there is also the disadvantage that filters which have been damaged or crushed during removal from the motor vehicle, which is the case with most disposable oil filters, interfere with the progress of the operation and thus cause the apparatus to be shut down.
Another disadvantage of this apparatus is that, although the casing is separated from the filter insert, the filter insert itself is not completely broken down into its individual components. This filter insert consists of a filter paper element, a so-called "paper star," which is sealed at its ends by two end plates and has a metal center tube. To dispose of this filter insert as a whole as "hazardous waste" is uneconomical.

Apparatus for dismantling filter inserts


A method for manufacturing a group III nitride semiconductor substrate includes a sapphire substrate preparation step S10 for preparing a sapphire substrate having, as a main surface, a {10-10} plane or a plane obtained by inclining the {10-10} plane at a predetermined angle in a predetermined direction; a heat treatment step S20 for performing a heat treatment over the sapphire substrate while performing a nitriding treatment or without performing the nitriding treatment; a buffer layer forming step S30 for forming a buffer layer over the main surface of the sapphire substrate after the heat treatment; and a growth step S40 for forming a group III nitride semiconductor layer, in which a growth surface has a predetermined plane orientation, over the buffer layer, in which at least one of a plane orientation of the main surface of the sapphire substrate, presence or absence of the nitriding treatment during the heat treatment, and a growth temperature in the buffer layer forming step is adjusted such that the growth surface of the group III nitride semiconductor layer has the predetermined plane orientation.

Related techniques are disclosed in Patent Document 1. As disclosed in Patent Document 1, in a case where a device (for example, an optical device, an electronic device, or the like) is formed on the c-plane of a group III nitride semiconductor crystal, the internal quantum efficiency is reduced due to a piezoelectric field. Therefore, attempts are being made to form devices on so-called semipolar planes (planes different from polar planes and non-polar planes).

Group III nitride semiconductor substrate and method for manufacturing group III nitride semiconductor substrate


A sterile to sterile connection device comprising a connector and one or more coupling devices. The connector has body portion which has two openings sealed from the environment so as to form a sterile environment within the connector. At least one of the openings being sealed from the environment by a sterile barrier plug. The connector also has a port capable movement within the body of the connector to at least an open and a closed position. The coupling device is formed of a body having two openings and a stem having a bore through at least a portion of the stem. The stem is contained within the body and capable of moving at least linearly through the body between a first and second stem position. One of the openings of the stem is sealed from the environment by a sterile barrier plug and the other is sealed to a presterilized component. The coupling device opening containing the sterile barrier plug is attached to either the inlet or outlet of the connector.

In the pharmaceutical, biotechnology and even food, beverage and cosmetics industries, it is often desired to provide a processing system that is capable of handling fluids in a sterile manner. This is designed to prevent unwanted, often dangerous organisms, such as bacteria as well as environmental contaminants, such as dust, dirt and the like from entering into the process stream and/or end product. It would be desirable to have a completely sealed system but this is not always possible with the processes that take place in production.
There is a need for the introduction or removal of materials from the process stream in order to add components of the product, such as media or buffers to a bioreactor; withdraw samples from the process stream to check for microbial contamination, quality control, process control, etc; and to fill the product into its final container such as vials, syringes, sealed boxes, bottles and the like.
Typically, the systems have been made of stainless steel and the system is exposed to live steam before use and then cleaned with chemicals such as caustic solutions after use to ensure that all contaminants are removed.
Steaming is the most effective means of sterilization. The use of steam in a set system is known as steaming in place or SIP. Saturated steam carries 200 times the BTU heat transfer capacity of heated air because of the latent heat released by the steam as it changes from vapor to liquid.
Several disadvantages exist with the use of steam. Any connections to or openings of the system made after the system has been SIP'd is an aseptic (but not sterile) connection or opening. This increases the risk of contamination of the entire system. One typically uses alcohol wipes or an open flame to clean the components to be connected, (e.g. connecting a sample collection bag to a system after SIP has occurred) and thus minimize the risk of contamination.
Also the high temperatures and pressure differentials of the steam make the selection of materials and components very difficult and limited and even then an accidental pressure differential at high temperatures can cause a non-steel component to fail.
Additionally, such systems that are reused need to undergo rigorous testing and validation to prove to the necessary authorities that the system is sterile before each use. The expense of validation as well as the cleaning regiment required is very high and very time consuming (typically taking 1 to 2 years for approval). In addition, some components are very difficult to adequately clean after use.
As an alternative to requiring a sterilization step with steam, some systems have advocated the use of alcohol wipes and other bactericides on the adjoining parts before assembly. While this may significantly reduce the presence of organisms, it does not eliminate them and at best this provides an aseptic connection.
U.S. Pat. No. 6,341,802 teaches the use of peelable membranes formed on the outer surfaces of two mating components. The membranes are exposed to the environment. Layers beneath of two outer membranes are sterile. The membranes are mated and the two devices attached and the membranes are then pulled out of the union between the two components. A piercable probe extends through the sterile barriers that face each other to form an environmentally tight seal. This approach is cumbersome and there is still some risk of contamination in the removal of the outer membranes. Also the use of piercing device creates the generation of particles that are unacceptable as well as the potential for tearing the seals between the two components that might add more contaminants to the system or clog the openings. Lastly, the device is limited in size making its use at large volumes or flows impracticable.
In a further improvement, a connector or valve can be formed that has a nonsterile closed face and a presterilized (typically with gamma radiation) downstream component(s) (such as a tubing and bag assembly). The face of the device is then attached to the desired equipment such as a port of a bioreactor or storage tank, or attached to a pipe fitting by a Tri-Clover® or Ladish fitting. The face along with the rest of the system upstream of the face is then steam sterilized in place (SIP). When the face is open after steaming, a sterile connection is achieved.
What is still desired is a simple, reliable sterile connection device that allows for a sterile to sterile connection without the need for steam or other cumbersome procedures.


A drive device for a vehicle includes a first motor, a first case, a second motor, a second case, a right-and-left communication passage, and a sensor. The first case houses the first motor and has a left reservoir to store liquid fluid. The second case houses the second motor and has a right reservoir to store liquid fluid. The right-and-left communication passage communicates with the left reservoir and the right reservoir. The sensor is configured to detect a property of the liquid fluid and disposed in the right-and-left communication passage.

1. Field
The present disclosure relates a drive device for a vehicle.
2. Description of the Related Art
The electric vehicle described in Japanese Unexamined Patent Application Publication No. 2010-249220 includes as a conventional drive device for a vehicle: a pair of electric motors on the right and left; first and second oil temperature sensors which each output a signal corresponding to the temperatures of oil stored in an oil pan of corresponding one of the electric motors; and first and second oil level sensors which each output a signal corresponding to an oil level in an oil pan of corresponding one of the electric motors (see FIG. 7 in Japanese Unexamined Patent Application Publication No. 2010-249220).


The present invention relates to a flow control valve to be connected to a pipe. The valve includes: a plurality of fluid transport tubes having a geometrically variable cross-section and placed in parallel with each other; and a means for connecting to the pipe and located at one end of the fluid transport tubes.

A flow control valve is a mechanical device used to control the flow of the fluid which passes in a duct. It can thus be used to decrease or to increase the flow of the fluid.
A flow control valve makes it possible to regulate the flow of fluid by creating the loss of load. This loss of load is variable according to the opening of the valve. When a polymer solution passes through a flow control valve, a substantial decrease in the viscosity is observed. Reference is then made to mechanical degradation of the polymer solution.
Within the context of EOR (Enhanced Oil Recovery) the requirement is to develop a new flow control valve model in order to limit the mechanical degradation of the viscous polymer solutions (polyacrylamide, HPAM etc.).
This invention applies to all projects comprising injection of a polymer which is sensitive to mechanical degradation (polymer and surfactant flooding), and to flow control valves at well heads. This is the case in particular for fields developed offshore, or wherein the fluid is transported over long distances. In fact, this type of development comprises an injection line which supplies a plurality of wells, each comprising a flow control valve at the well head.
By way of example, a petroleum field may comprise a plurality of complexes. In general, a single injection line makes it possible to distribute the water to be injected to each of the wells of a complex. Since the head pressure and the hydrodynamic resistance of each of the wells is variable, it is necessary to use a flow control valve at the head of each well, in order to control the flow injected.
In fact, since the head pressure is equal to the pressure at the start of the injection line, less the losses of load between the start of the injection line and the well head, the head pressure of each of the wells is all the greater, the closer the well is to the start of the injection line. The hydrodynamic resistance depends on many factors such as the length of the injection drain, the permeability of the formation, the porosity and the saturation with oil. For example, a well A which injects into an area with low permeability will have injectivity which is far less good than another well B on the same line which injects into a permeable area. In other words, for an identical head pressure, the flow injected into the well A will be lower than that injected into the well B. If it is wished to increase the ratio of flow between the wells A and B, it is necessary to decrease the head pressure of the well B. For this purpose, a valve will be placed at the head of the well B which will create the loss of load required.
For a given flow Q (in m3/h) and a given opening of the valve Op (as a %), the valve will create a loss of load ΔP (in bars). If flow increases, or if the opening of the valve decreases, the loss of load increases. For each opening of the valve, the valve manufacturer provides a coefficient of flow Cv defined as follows:
  Cv  =            f                    (        Op        )                        Q                        Δ                                                                          P            /            G                              where G is the gravitational constant (in m/s2).
Thus, when two variables are set, the third is known. The curve Cv is determined experimentally by the manufacturer. It depends on the geometry of the valve.
Within the context of Enhanced Oil Recovery, a polymer solution is used in order to accelerate the recuperation of the oil, and to increase this recuperation when the production is stopped. In fact dissolving the polymer in the water injected improves control of the mobility, i.e. by increasing the viscosity of the water, the mobility of the water is decreased, which is favorable to improved recuperation of the oil. Thus, the main objective is to maintain the viscosity of the polymer solution injected. However, this polymer solution is very sensitive to shearing. In fact, when it passes into the valve, the polymer chains can break, which gives rise to a decrease in the viscosity of the polymer solution.
The rheological behavior of a polymer solution in a porous medium differs from the behavior in terms of volume (viscosity measured in the rheometer). FIG. 1 illustrates this behavior. With a low level of shearing, the apparent viscosity of the polymer in a porous medium (represented by the curve A) is lower than the viscosity in terms of volume (represented by the curve B). With a low gradient, there is a Newtonian platform, then a rheofluidifying area (decrease of the viscosity with the shearing). Starting from a critical shearing point {dot over (γ)}T there is observation of rheothickening behavior (increase in the viscosity with the shearing) which will pass through a maximum point, then regain the viscosity of the water at a very high gradient. The rheothickening is associated with the resilient nature of the polymer chains.
The physics of diluted polymer solutions has been quite extensively described. For a level of critical elongation {dot over (ε)}T such as {dot over (ε)}Tτ>1 where τ is the relaxation time of the polymer chain, the polymer chains undergo transition from a "ball" state to a "drawn" state, which takes the form of the appearance of elongational viscosity which is far greater than the viscosity in terms of volume measured in simple shearing. The hydrodynamic force exerted by the solvent on the polymer chain in a "drawn" state is expressed by F∝ηS{dot over (ε)}L2. When this force is greater than the force of the carbon-carbon bond of the chain, the polymer chain breaks, preferentially at its center. A decrease in the molecular mass of the chains leads to a decrease in the viscosity of the solution. This is what is known as the mechanical degradation (represented by the curve D), which takes place at a critical elongation level {dot over (ε)}D. A shearing field therefore exists in the porous medium [{dot over (γ)}T−{dot over (γ)}D] corresponding to the elongational shearing field [{dot over (ε)}T−{dot over (ε)}D] for which the polymer develops elongational viscosity, without however undergoing significant degradation.
The present control valves s generally consist of a cage pierced with holes with a variable diameter (FIG. 2). The fluid input (E) takes place through the holes in the cage, and the output (P), which is perpendicular, is at the center of the cage. The accessible surface, and thus the number of holes through which the fluid passes, is adjusted by the height of a mobile piston with movement parallel to the axis of the cage. For a given flow, the loss of load increases when the accessible surface at the fluid input decreases.
The origin of the mechanical degradation of the polymer solutions during their passage into a flow control valve is partially known. The polymer chains in solution are flexible balls which are elongated when they are subjected to elongational shearing. When the hydrodynamic forces associated with this field of elongational speeds are great, the polymer chains break.
The present control valves s generate a loss of load by passage of the fluid into holes. This type of geometry creates a high level of elongational shearing as a result of the high contraction ratio between the input of the flow control valve and the holes, thus generating a strong decrease in the viscosity of the polymer solution. Reference is then made to degradation of the polymer solution. Since the viscosity of the polymer solution is a key parameter of the EOR, it is therefore necessary to limit the degradation of the polymer solution injected during its passage through the flow control valve.
Different solutions for flow control valves have been described in order to limit the degradation of the polymer solution.
For example, U.S. Pat. No. 4,276,904 describes a flow control valve which makes it possible to modify a flow of fluid by making the fluid pass into a limited number of pipes with lengths between 3,048 m (10 ft) and 60.96 m (200 ft) and with different diameters between 0.635 cm (0.25″) and 2.540 cm (1″). This flow control valve is difficult to implement (in particular it comprises a large number of shutters, which have to be activated independently at the output of each of the pipes, and it is voluminous).
WO 2012/001671 A2 also describes a flow control valve consisting of a capillary system with a constant diameter of between 0.125 mm and 11 mm, which in particular is designed for implementation of a method for injection of a fluid into an underground formation. In this type of flow, the polymer particle is animated by a rapid rotation movement (ω=γc/2) which subjects the particle to successive elongations and compressions which do not give the particle time to become elongated. On the other hand, in an elongational flow such as in a duct which involves strong contraction, the particle can have the time to become significantly elongated, and consequently be subjected to significant elongation (proportional to the viscosity of the suspension fluid, the gradient of speed of elongation γE and the square of the length reached L:Fe1˜μ γE L2). If this force becomes greater than its internal resistance, the particle breaks and loses its properties. In this case, reference is made to mechanical degradation. However, this valve does not make it possible to reduce the degradation of the polymer solution to percentages lower than 10%, whilst having a size suitable for use in the petroleum industry, in particular on a platform or in a petroleum deposit on land. It is thus desirable to develop a flow control valve which limits the degradation of the polymer solution, and which is compact and easy to implement.

Flow control valve including a plurality of tubes having a geometrically variable cross-section


A hinge with a hinge cup can be inserted into a boring in a furniture part. A damper housing is fixed onto the hinge cup, and the damper housing can be fastened onto or removably secured to the hinge cup. The damper housing is disposed at least partially outside the boring when the hinge cup is inserted into the boring in the furniture part.

The invention concerns a hinge with a hinge cup which can be inserted into a boring in a furniture part, with a damper housing fixed onto the hinge cup.
Hinges fitted with a damper which brakes furniture doors during closing are known in the art from EP 1 199 433 A2, from the Austrian utility model AT 005 477 U1 and the German utility models DE 201 15 250 U and DE 202 05 905 U. The problem addressed by the present invention is to create a hinge with a damper such that the damper can be used universally.


With a plasma being generated between a cathode electrode to which a high-frequency power is applied and an electrically conductive substrate opposed to the electrode in a reaction vessel the pressure of which can be reduced, a photoconductive layer having the matrix of silicon atoms is deposited on a substrate to be processed, a surface layer comprised of non-monocrystal carbon containing hydrogen is provided on the photoconductive layer, a surface of the surface layer is etched to fluorinate the surface, the surface roughness Rz by etching is controlled below 1000 .ANG., the fluorine contained in the surface layer is made present within 50 .ANG. from the surface, and the concentration of fluorine to carbon in that region is 20% or more, thereby providing a photosensitive member for electrophotography that can obtain high-quality images free of image faintness and image smearing without using a heating means for the photosensitive member, that has high durability, that shows less change in potential characteristics, that can obtain high-quality images on a stable basis, and that is free of the ghost phenomenon and providing a fabrication process of the photosensitive member.

1. Field of the Invention
The present invention relates to a photosensitive member for electrophotography and a fabrication process thereof and, more particularly, to a photosensitive member for electrophotography that can obtain high-quality images free of image faintness and image smearing with no heating means for photosensitive member, that has high durability enough to maintain the characteristics, that exhibits less variation in potential characteristics, that can obtain high-quality images on a stable basis, that experiences no ghost phenomenon, and to a fabrication process thereof for achieving the performance thereof with good repeatability.
2. Related Background Art
Proposed for a light receiving layer used in the photosensitive member for electrophotography are a variety of materials including selenium, cadmium sulfide, zinc oxide, phthalocyanine, amorphous silicon (hereinafter referred to as a-Si), and so on. Among others, non-monocrystalline deposited films containing silicon atoms as a main ingredient typified by a-Si, for example, amorphous deposited films of a-Si or the like compensated by hydrogen and/or halogen (for example, fluorine, chlorine, or the like), are proposed as high-performance, high-durability, and nonpolluting photosensitive members, some of which are used practically. U.S. Pat. No. 4,265,991 discloses the technology of the electrophotographic, photosensitive member the photoconductive layer of which is formed mainly of a-Si.
The a-Si photosensitive members have high surface hardness, demonstrate high sensitivity also to long-wavelength light of semiconductor lasers (770 nm to 800 nm) and the like, and exhibit little deterioration after repetitive use, and they are widely used, particularly, as photosensitive members for electrophotography in high-speed copiers, LBPs (laser beam printers), and the like.
As methods for forming such deposited films there are many conventional methods known, including the sputtering process, the method for decomposing source gas by heat (the thermal CVD process), the method for decomposing the source gas by light (the photo-CVD process), the method for decomposing the source gas by plasma (the plasma enhanced CVD process), and so on.
Among them, the plasma CVD process, which is a method for decomposing the source gas by glow discharge or the like induced by direct current, high-frequency (RF or VHF) wave, or microwave and for forming a deposited film of thin film on a substrate of glass, quartz, heat-resistive, synthetic resin film, stainless steel, aluminum, or the like, is now under very quick development into practical use as a method for forming the a-Si deposited films for electrophotography. A variety of proposals were also made on apparatus for the process.
Further, demands are becoming stronger for improvements in quality of film and in throughput and many ideas are under research.
Especially, the plasma process using high-frequency power is used because of its various advantages including high stability of discharge, applicability to formation of insulating materials such as oxide film, nitride film, and so on.
A process recently reported is the plasma enhanced CVD process with high-frequency power supply of 50 MHz or higher by use of a parallel plate plasma enhanced CVD system (Plasma Chemistry and Plasma Processing, Vol. 7, No. 3 (1987), pp. 267-273), which shows a possibility that the rate of deposition can be increased without degrading the performance of a deposited film by using the frequency of discharge higher than 13.56 MHz conventionally used and which is drawing attention. There are also reports of increasing the frequency of discharge in sputtering etc. and wide research is under way in recent years.
In applications of the a-Si photosensitive members fabricated by these methods to the electrophotographic apparatus, charging and decharging (charge-eliminating) means of photosensitive members used in the most cases are corona chargers (Corotron, Scorotron) composed of main components of a wire electrode (a metal wire such as a tungsten wire with gold plating in 50 to 100 .mu.m.phi.) and a shield plate. Specifically, charging or decharging (elimination of charge) of the surface of the photosensitive member is effected by applying a high voltage (approximately 4 to 8 kV) to the wire electrode of the corona charger and causing corona electric current generated with the application of the voltage to act on the surface of the photosensitive member. The corona chargers are excellent in uniform charging and decharging.
However, ozone (O.sub.3) is generated with corona discharge to oxidize nitrogen in the air to generate nitrogen oxides (NO.sub.x) etc. In addition, the nitrogen oxides etc. thus generated react with water in the air to generate nitric acid etc. Then the products by the corona discharge, including nitrogen oxides, nitric acid, etc., adhere to and are deposited on the photosensitive member and peripheral devices, thus polluting surfaces thereof.
Since the corona discharge products are highly hygroscopic, the surface of photosensitive member adsorbing them decreases its resistance because of absorption of moisture by the corona discharge products thus deposited, so as to substantially degrade the charge holding ability totally or partly, which is a cause to induce defects of image as called image faintness and image smearing (a pattern of electrostatic latent image is destroyed or is not formed because of leakage of charge on the surface of photosensitive member in directions along the surface).
The corona discharge products, depositing on the internal surface of shield plate in the corona charger, are volatilized and liberated not only during operation of electrophotographic apparatus, but also during rest of apparatus, for example, during the night and then adhere to the surface of photosensitive member in the region corresponding to the discharge opening of the charger. Such corona discharge products further absorb moisture to decrease the resistance of the surface of photosensitive member. Therefore, with the first copy or several copies outputted initially at restart of apparatus after rest of apparatus, the image faintness and the image smearing tend to take place in the aforementioned region corresponding to the charge opening in the rest of apparatus. This phenomenon sometimes appears prominent, especially, when the corona charger is an AC corona charger.
Particularly, when the photosensitive member is an a-Si photosensitive member, the problems of image faintness and image smearing due to the above corona discharge products become more serious. Specifically, since the a-Si photosensitive member has lower efficiency of charging and decharging than the other photosensitive members (it requires more electric current of corona charging for obtaining a predetermined charging or decharging potential), the charging current amount is increased greatly by applying a higher voltage to the charger than in the case of the other photosensitive members, in the charging and decharging processes by corona discharge to the a-Si photosensitive member.
Since an amount of ozone generated is in proportional relation with the current amount of corona charging, in the case of the arrangement wherein the photosensitive member is the a-Si photosensitive member and wherein it is charged or decharged by corona charging, the amount of ozone generated particularly becomes large, which could make the problems of image faintness and image smearing due to generation of the aforementioned corona discharge products particularly serious in some cases. In addition, in the case of the a-Si photosensitive member, the surface hardness thereof is extremely higher than those of the other photosensitive members, and the extremely high surface hardness inversely acts to keep the corona discharge products on the surface of photosensitive member, remaining indefinitely.
The following two methods are considered to be methods for preventing the phenomena of image faintness and image smearing.
(1) The first method is a method for decreasing relative humidity by heating the surface of the photosensitive member (up to 30 to 50.degree. C.) by a heater for heating the photosensitive member built in the photosensitive member or by hot air supplied from a hot wind supplying device to the photosensitive member. This method is a process for preventing the substantial decrease in resistance of the surface of photosensitive member by volatilizing the corona discharge products and water adhering to the surface of photosensitive member and this method is in practical use.
(2) The second method is a method for increasing the water repellency of the surface so as to make the corona discharge products hard to adhere to the surface from the beginning, thereby preventing the image smearing. For example, the bulletin of Japanese Patent Application Laid-Open No. 61-289354 discloses an a-C surface layer a surface of which is plasma-processed with a gas containing fluorine. Further, the bulletin of Japanese Patent Application Laid-Open No. 64-84257 discloses an electrophotographic, photosensitive member wherein the surface of a surface layer comprised of amorphous carbon containing fluorine has unevenness 0.1 to 0.5 .mu.m deep and 0.1 to 1 .mu.m wide, and a fabrication process thereof. It is described that this method can further increase water repellency by increasing the surface area.
While the problem of image smearing was solved by the heating device of a drum in the above-stated method of (1), new problems described below arose with recent growing demands for copiers. Namely, circumstances have been changing so that use of the heating means by drum heater should be preferably avoided from the viewpoints of energy saving and ecology.
Another problem arises when the a-Si drum assuring high quality of image is mounted in a full-color copier. The problem is to increase a possibility of fusing and sticking low-melting-point toner of color toner or the like onto the surface of drum. Still another problem is that image densities change partly depending upon cycles of rotation of a rotary, cylindrical developer-carrying member.
The reason is that during rest of the apparatus the heat of the photosensitive member expands the rotary, cylindrical developer-carrying member to decrease the distance to the portion of photosensitive member opposed thereto, whereby the developer becomes easier to transfer than in the normal condition. These problems raised demands for a photosensitive member free from occurrence of image faintness and image smearing without heating.
On the other hand, as to the technology for increasing water repellency as disclosed in the aforementioned bulletins in the above-stated method of (2), the bulletins describe the increase in water repellency by exposure to ozone, but they describe nothing about whether durability tests were conducted or not by carrying out a large number of copying operations in actual.
Then the inventors conducted follow-up tests according to the method disclosed in the bulletin of Japanese Patent Application Laid-Open No. 61-289354 to carry out durability tests of performing continuous copying operations without use of heating means. The durability tests verified that durability was insufficient, though the image smearing characteristics at an initial stage were improved in fact. It was found that a property of being capable of maintaining necessary and sufficient water repellency even after sheet-pass durability tests of many sheets was more preferable in consideration of the high durability as one of merits of the a-Si photosensitive member.
The inventors also conducted follow-up tests of the method disclosed in the bulletin of Japanese Patent Application Laid-Open No. 64-84257. In this case, it was confirmed that increasing the surface area by providing the surface with unevenness was effective in increasing water repellency, but it was also found that the effect of water repellency decreased with progress of sheet-pass durability test. A reason of this is possibly that amorphous carbon containing fluorine is soft and thus is shaved gradually by slip abrasion with members around the photosensitive member, paper, or the like.
Under these circumstances, the desire has been growing for a photosensitive member that has a surface layer with high water repellency so as not to cause the image faintness or the image smearing without use of heating means and that exhibits no degradation of the high water repellency even after copying operations of many sheets for a long period.
With recent increase in the requirements for copy images, in addition to the problem of image smearing, there is earnest desire for the technology for supplying high-quality images on a stable basis. Since uses of copier have been changing from copy originals mainly containing letters to images of photographs or the like to increase copy originals frequently using halftones, a severer standard than before is required for stability of density. When potentials of charging vary with time against the desire to keep charging equal as described above, the change of potential is called a potential shift, and the smaller the potential shift, the higher the stability.
With photographic originals, the requirement becomes severer as to the ghost phenomenon as well as the stability of density. This is because halftone portions are likely to be affected especially by ghost. The "ghost" herein is a phenomenon that an image in previous copying operation is visualized as a light image. A difference between a potential in a portion where the ghost appears upon application of a halftone potential and the halftone potential is called as a ghost potential, and the smaller the ghost potential, the less the ghost appears.
A reason why these occur is possibly that the charge is trapped in the film for some reason in the process of carrying out charging or decharging. Attempts have been made to decrease the potential shift and ghost potential by various methods, but the technology capable of achieving a further improvement is desired earnestly.

Photosensitive member for electrophotography and fabrication process thereof


A boiler includes a combustion chamber, a heat exchange section, and an outer housing. Coupling holes are formed in the outer housing, a circulation chamber is formed at a lower portion of the outer housing, and a burner is provided at an upper portion of the combustion chamber so as to generate heat in a downward direction thereof. The combustion chamber is vertically installed in one of the coupling holes, and a lower portion of the combustion chamber is communicated with the circulation chamber. The heat exchange section includes first and second heat exchangers and is vertically installed in the outer housing adjacent to the combustion chamber. An upper portion of the heat exchange section is coupled to one of the coupling holes and a lower portion of the heat exchange section is communicated with the circulation chamber.

Boilers are appliances for feeding hot water to separate rooms in homes and offices after heating water using combustion heat, which is generated when burning fuel in the boilers. The boilers have come into wide use for the purpose of heating houses or feeding hot water in the houses. The boilers are classified into various types according to the sort of heat sources for heating water or fuel used in the boilers. For instance, the boilers are classified into gas boilers using LPG or LNG and oil boilers using burning-oil according to fuel used in the boilers.
In addition, the boilers are classified into normal type boilers and condensing type boilers. The condensing type boiler has been developed so as to reuse energy, which may be wasted in the normal type boiler. The condensing type boiler operates as follows:
Fuel of the boiler includes hydrogen (H2), which reacts with oxygen (O2) when the fuel is burned so that water (H2O) is created while generating heat. Such water is converted into water vapor due to heat contained in water and the water vapor is exhausted to an exterior in the form of an exhaust gas. Accordingly, if the temperature of the water vapor is lowered below 100° C., the water vapor is again converted into water.
When a phase of a material is shifted, latent heat is emitted or absorbed from/into the material. Therefore, latent heat is generated when the water vapor contained in the exhaust gas is liquefied into water. The condensing type boiler includes a latent heat exchanger so as to heat water by using the latent heat. According to the condensing type boiler, sensible heat contained in the exhaust gas and latent heat contained in the water vapor are simultaneously retrieved, thereby improving the thermal efficiency of the boiler up to 95 to 105%. Therefore, it is preferred to widely spread the high-efficiency condensing type boilers in order to reduce energy consumption.
However, in order to apply the condensing scheme to the oil boiler, a latent heat exchanger for retrieving the latent heat from the exhaust gas must be installed in the boiler separately from a main heat exchanger capable of absorbing combustion sensible heat. Differently from the gas boiler, the oil boiler may generate strong acidic condensing water due to sulfuric components contained in oil fuel, so the latent heat generator must be fabricated by using a material having superior endurance against the strong acidic condensing water. For this reason, the condensing type oil boiler must be provided with the main heater exchanger and the latent heat exchanger, which are fabricated by using mutually different materials.
FIG. 1 is a schematic sectional view of a conventional condensing type oil boiler. The conventional condensing type oil boiler includes a main heat exchanger 12 for absorbing sensible heat generated when fuel is burned in the boiler and a latent heat exchanger 16 aligned in parallel to the main heat exchanger 12 while forming a predetermined space therebetween so as to absorb remaining heat and latent heat from an exhaust gas fed to the main heat exchanger 12. The main heat exchanger 12 is provided at a lower portion thereof with a combustion chamber 11, in which fuel is burned by means of a burner 10. In addition, a plurality of funnels 14 are provided in the main heat exchanger 12. The funnels 14 are connected with an upper portion of the combustion chamber 11 so as to convey an exhaust gas generated from the combustion chamber 11. Water reservoirs 13 are provided between an outer peripheral portion of the combustion chamber 11 and the funnels 14 in order to circulate hot water. Sensible heat of the exhaust gas, which is generated when the fuel is burned in the boiler, is applied to hot water being circulated through the water reservoirs 13.
Arrows shown in FIG. 1 represent a flowing direction of the exhaust gas. As shown in FIG. 1, the exhaust gas flowing upwards from the combustion chamber 11 of the main heat exchanger 12 along the funnels 14 is transferred to a noise-absorbing container 15, which connects an upper portion of the main heat exchanger 12 with an upper portion of the latent heat exchanger 16, so that the exhaust gas is introduced into the latent heat exchanger 16. The latent heat exchanger 16 has a cylindrical structure and the upper portion of the latent heat exchanger 16 is communicated with the noise-absorbing container 15. The latent heat exchanger 16 is provided at an inner portion thereof with a plurality of funnels 18, which are communicated with a funnel support 19 provided at a lower portion of the latent heat exchanger 16. In addition, water reservoirs 17 are provided between the funnels 18 so as to store hot water therein. Latent heat of the exhaust gas passing through the latent heat exchanger 16 is transferred to hot water stored in the water reservoirs 17.
Generally, since condensing water, which is generated because water vapor contained in the exhaust gas is liquefied while passing through the latent heat exchanger 16, represents a strong acidic property, the condensing water may cause environmental contamination. For this reason, the funnel support 19 for collecting the condensing water and a neutralization unit 21 for neutralizing the condensing water collected in the funnel support 19 are provided at a lower portion of the funnels 18. One end of the funnel support 19 is communicated with the funnels 18 of the latent heat exchanger 16 and the other end of the funnel support 19 is coupled with a funnel 20 so that the exhaust gas passing through the funnels 18 may be discharged to an exterior through the funnel 20.
However, the conventional condensing type oil boiler having the above structure presents a problem in that the latent heat exchanger for retrieving latent heat from the exhaust gas is installed separately from the main heat exchanger, so separate manufacturing equipment and jigs must be provided for the conventional condensing type oil boiler. That is, in order to manufacture the conventional condensing type oil boiler, a separate assembling line must be provided and additional labor force is supported. In addition, since parts for the condensing type oil boiler cannot be used for the normal type oil boiler, the manufacturing cost may be increased while reducing the productivity.
Furthermore, the conventional condensing type boiler having the above structure presents another problem in that a volume and a weight of the conventional condensing type boiler may increase as compared with those of the normal type oil boiler, which can absorb only sensible heat from the exhaust gas. For this reason, a relatively large space is required for installing the conventional condensing type boiler, while complicating the manufacturing processes for the conventional condensing type boiler.

Mutually convertible boiler between normal type and condensing type


This invention provides methods for manufacturing compound-material wafers and methods for recycling donor substrates that results from manufacturing compound-material wafers. The provided methods includes at least one further thermal treatment step configured to at least partially reduce oxygen precipitates and/or nuclei. Reduction of oxygen precipitates and/or nuclei, improves the recycling rate of the donor substrate.

Use of compound-material wafers, in particular, silicon on insulator (SOI) type wafers, as starting materials in the semiconductor device manufacturing process is becoming more and more important. One way to fabricate such wafers with good crystalline quality at reasonable cost is by transferring a layer from a donor substrate also of good crystalline quality onto a handle substrate. Specifically, donor and handle substrates are bonded, and then the donor substrate is detached at a predetermined splitting area previously formed in the donor substrate. In the SMART-CUT® process, the splitting area is formed by implanting atomic species, in particular hydrogen ions or rare gas ions, into the donor substrate. The advantage of this process is that the remainder of the donor substrate, which remains after the transfer of the layer onto the handle substrate, can be re-used as a donor substrate in a subsequent component material wafer fabrication process. Thus, one donor substrate can serve for several compound-material wafers, like SOI type wafers.
It appeared, however, that the donor substrate could only be re-used three to four times, because from run to run, the crystalline quality of the donor substrate deteriorated. As a consequence, the crystalline quality of the final SOI substrate also deteriorated.
Efforts have been made to allow the recycling of the used donor substrates. Japanese patent application JP19980114176 (Japanese publication JP11297583), for example, proposes to first polish the donor substrate to remove the surface step at the edge of the wafer, which is present after the transfer of a layer onto the handle substrate, and then to carry out a second finishing polishing step before re-using the remainder of the donor substrate as a new donor substrate. U.S. Pat. No. 6,211,041, although not being directed to recycling processes, discloses a different approach, which consists in providing, right from the beginning, a silicon substrate with an appropriate oxygen content. An appropriate oxygen content is claimed to prevent the creation of crystal defects, which according to the authors, are related to the presence of oxygen precipitates generated in the SOI device layer during the heat treatments that the wafers undergo during the SOI fabrication process.
Despite this disclosure, however, the number of possible re-uses of donors substrate is still not satisfactory. In particular, it appears that controlling the initial oxygen content does not prevent crystal defects from appearing in the final SOI layer after multiple reuse. Thus, improvements in this area are needed and these are now provided by the present invention.

Methods for manufacturing compound-material wafers and for recycling used donor substrates

S.O.I.Tec Silicon on Insulator Technologies


A device for acquiring first and subsequent images of a suspect area on a patient and methods for monitoring or detecting changes of the suspect area over time and providing notification when the changes exceed a threshold. The device may be an imaging device, such as a digital camera, possibly augmented with physical or optical devices for arranging the orientation and/or distance of the imaging device with respect to the suspect area. In addition, methods for identifying, relocating, acquiring a first and/or subsequent image of the suspect area, and performing a comparative analysis of respective images are also described. Results of the comparative analysis can be used to notify and/or assist a medical professional in treating or counseling patient.

1. Field of the Invention
This disclosure relates to devices and methods, which can be used alone or in combination, to identify and monitor changes of a suspect area on a patient, for example dermatological changes.
2. Description of the Related Art
There are many reasons why a medical professional, patient, or both would want to monitor changes on an exterior or internal surface of a patient. For a suspect area, especially one that may indicate some form of skin cancer, it is important to detect and treat the area in its early stages. One type of skin cancer is known as melanoma, which is a malignant cancer of the pigment cells (melanocytes). Other forms of skin cancer also exist and are known as basal and squamous cell cancers, which are tumors of unpigmented cells (keratinocytes) of the skin.
Melanocytes occur at various depths within the epidermal (upper) and dermal (lower) layers of skin. Melanocytes are normally distributed in the layers of the skin and produce pigment in response to being subjected to ultraviolet light (e.g., sunlight). Aggregated melanocytes are termed naevus cells and can be indicative of a melanoma. Because a melanoma may appear as a mole, medical professionals typically attempt to ascertain whether the suspicious area is changing over time. Identifying changes early typically results in a rapid diagnosis, which in turn often leads to rapid and highly effective treatments that can greatly increase the patient's survival rate and in most cases, complete recovery.
Historically, the standard of care for screening or monitoring melanoma is a visual inspection or visual comparison of photographs by a medical professional. These visual inspections or comparisons are subjective and do not enable the medical professional to detect small or subtle changes in a suspect area. Changes in the perimeter, depth, shape, and even color of a melanoma can be subtle for a time and then progress rapidly. Moreover, changes in the color or perimeter, for example, of a melanoma are not easily discernable to the human eye so these changes may go unnoticed for a long period of time.
In U.S. Pat. No. 6,427,022, issued to Craine et al., a skin lesion is monitored by obtaining a series of digital baseline images over time and comparing these images. The method of comparison taught in Craine et al. is that the baseline image is compared visually by the viewer with a subsequently obtained image by alternately displaying the respective images, in a blinking fashion. The blinking action is created by quickly alternating the images with respect to one another on a display monitor to enable the viewer to detect changes in the skin lesion.
Even though the standards of care discussed above may involve images, each standard of care suffers from the subjectivity and uncertainty associated with the medical professional trying to ascertain changes in a suspicious area by visual comparison. The visual comparison methods are subjective and less accurate for a number of reasons. For instance, the medical professional may be inexperienced, may have been distracted during the examination, or may have selected the wrong location on the patient's body during a follow-up examination.
Therefore, a more effective, less subjective, and low-cost approach for at least monitoring changes in a suspect area is desirable.

Devices and methods for identifying and monitoring changes of a suspect area of a patient


A washing method characterized in that washing is carried out under conditions that a pH of a washing liquid starts increasing after a water hardness of the washing liquid starts decreasing; a detergent composition characterized by containing particles capable of delayed-exerting an alkalizing effect of a washing liquid, wherein a pH of a washing liquid starts increasing after a water hardness of the washing liquid starts decreasing; and a detergent composition comprising an alkalizing agent coated with an organic material, or organic and inorganic materials, the alkalizing agent occupying an amount of 70% by weight or more of the entire alkalizing agents in the detergent composition. In the washing method and the detergent composition of the present invention, since washing is carried out under conditions that a pH of a washing liquid starts increasing after a water hardness of the washing liquid starts decreasing, excellent detergency can be achieved even at a low surfactant concentration in a washing liquid.

Generally, it is known that the addition of metal ion capturing agents, such as zeolites, to detergents reduces the effects of calcium ions and magnesium ions in tap water on surfactants, thereby removing dirt stains adhered to clothes, while the detergents inhibiting redeposition owing to freed dirt stains by making the washing liquid alkaline to increase dispersion of the dirt stains.
Therefore, in general, conventional detergent granules include alkalizing agents and metal ion capturing agents. The detergent granules are generally produced by the following method.
Specifically, a slurry comprising aqueous dispersion of surfactants, mainly comprising anionic surfactants and nonionic surfactant; alkalizing agents, such as sodium carbonate and sodium silicates; calcium ion capturing agents (metal ion capturing agents), such as zeolites and sodium tripolyphosphates; fillers, such as sodium sulfate; and other components (those which are stable against heat) is prepared. Thereafter, the resulting slurry is dried to be powdered. Subsequently, materials which are unstable against heat including perfumes, and in certain cases, bleaching agents and bleaching activators are post-blended, to give desired detergent granules.
Incidentally, phosphorus-based metal ion capturing agents typically exemplified by tripolyphosphates have been formulated in dry granules, the tripolyphosphates being generally employed as calcium ion capturing agents before the use of zeolites. This is due to the fact that the phosphorus-based metal ion capturing agents have a function of alkalizing agents besides the calcium ion capturing capacity and also have the most suitable properties for improvement in powder properties, such as flowability, of the dry granules.
In the detergent granules mentioned above, since the alkalizing agents, such as alkali metal carbonates and alkali metal silicates, also have the characteristics of improving flowability by mechanically strengthening the granules themselves, the alkalizing agents act to form into granules with surfactants having plasticity and zeolite fine particles, so that the alkalizing agents are generally included in the same granules as the surfactants and the zeolites.
As mentioned above, since the metal ion capturing agents and the alkalizing agents are formulated in the same granule in the conventional detergents, the dissolution of these components may simultaneously show alkalizing ability and metal ion capturing capacity in the washing liquid. In certain cases, the alkalizing ability is shown earlier than the metal ion capturing capacity because the rate of reaction of the metal ion capturing agents with calcium ions and magnesium ions in water is delayed more than the rate of reaction of an alkalizing agent and water. The same can be said for liquid detergents, and since the metal ion capturing agents and the alkalizing agents are mixed in the same liquid, the alkalizing ability and the metal ion capturing capacity may be simultaneously shown, or the alkalizing ability is shown earlier than the metal ion capturing capacity.
Aside from the above, most man-derived sebum dirt stains contain fatty acids. In the process of washing, calcium and magnesium together with fatty acids form a scum, thereby lowering solubility and inhibiting the dispersion of the dirt stains in water. In particular, the present inventors have found that the scum-formation rate becomes faster as the alkalization degree (pH) becomes higher, and that washing performance cannot be exhibited to its optimum in conventional washing methods.
On the other hand, besides ones mentioned above, several methods comprising dry-blending alkalizing agents as separate granules from detergent granules have been conventionally known.
For instance, (1) Japanese Examined Patent Publication No. 3-52798 discloses a method for producing detergent builders having a small bulk density comprising adding organic compounds, such as polyethylene glycols, to alkali metal carbonates and/or alkali metal sulfates; and granulating the resulting mixture. In this publication, however, the purpose is to improve the granular strength and the solubility, not to increase the detergency effects by making the dissolution of the alkalizing agents delayed more than that of the metal ion capturing agents. Therefore, the alkalizing agent particles shown in Examples contain a small amount of a binder, and the polyethylene glycol has a low molecular weight, never teaching a delayed exertion of the alkalizing ability.
(2) Japanese Patent Laid-Open No. 55-52396 discloses a method of dry-blending particular alkali metal silicate granules to detergent granules containing surfactants and chelating agents, such as zeolites. In this publication, however, the purpose is to prevent the formation of water-insoluble materials owing to mutual interactions between silicates and zeolites and to maintain anti-corrosive effects on the washing machines, but not to increase the detergency effects by making the dissolution of the alkalizing agents delay more than that of the chelating agents. Therefore, the silicate granules shown in Examples have a large particle size, but they are not intended to delay the alkalizing ability by changing the particle sizes.
(3) Japanese Patent Laid-Open No. 62-167399 discloses a method for producing detergent granules having a high bulk density by limiting the amount of water-soluble, crystalline inorganic salts in the detergent base materials and dry-blending alkalizing agents with detergent granules in order to prevent the decrease in solubility of the detergent granules by increasing bulk densities thereof. However, for the same reasons set forth in (2) above, this publication does not suggest the increase in the detergency effects by making the dissolution of the alkalizing agents delay more than that of the metal ion capturing agent.
(4) Japanese Patent Laid-Open No. 58-213099 discloses a method for producing clothes detergents comprising dry-blending sodium carbonate with spray-dried powdery detergent base materials, the sodium carbonate having a particular density, particle size, and particle size distribution. The purposes of this publication, however, are to improve caking resistance and to prevent classification of sodium carbonate, and not to increase the detergency effects by making the dissolution of the alkalizing agents delay more than that of the metal ion capturing agents. Therefore, even in Examples, sodium silicate is included in the detergent base materials in relatively large amounts, the sodium silicates being incorporated in the same granules as zeolites, which are metal ion capturing agents.
Accordingly, there are no prior art references having the purpose of exhibiting an alkalizing ability to be delayed more than that of the metal ion capturing capacity. In the methods of post-blending alkalizing agents as described above, the alkalizing agents are blended simply for the following purposes: Since the zeolites are water-insoluble, the alkalizing agents are added for preventing the zeolites to remain on fibers caused by the action of the silicates to suppress the dispersion of the zeolite in cases where the zeolites are blended with silicates in the form of fine particles. Also, the alkalizing agents are added to improve caking resistance and solubility of the detergents. Moreover, in the conventional detergents mentioned above, since the alkalizing agents directly contact the washing liquid, the initiation of the alkalizing effect is faster than the case where the metal ion capturing agent and the surfactants are formulated in the same granules.

Washing method and detergent compositions