Boron-substituted graphite, which contains N-bonded boron atoms in a small proportion relative to whole substituted boron atoms, is produced by heating a feed fine particulate mixture of an infusibilized carbonaceous material and a boron compound such that the carbonaceous material is carbonized into a carbon structure, raising a temperature of the resulting heated fine particulate mixture promptly to a graphitization treatment temperature in an inert atmosphere unreactive with boron, retaining the graphitization treatment temperature for a time sufficient to allow graphitization of the carbon structure to proceed to a desired extent, and then quickly cooling the resulting graphitized mixture. The boron-substituted graphite is useful as a negative electrode in a lithium-ion secondary battery.

a) Field of the Invention
This invention relates to processes for the production of carbonaceous materials having high performance as negative-electrode materials, and especially to processes for the production of boron-substituted graphite, silicon-containing boron-substituted graphite and silicon-containing carbonaceous materials for lithium-ion secondary (rechargeable) batteries. This invention is also concerned with the boron-substituted graphite, silicon-containing boron-substituted graphite and silicon-containing carbonaceous materials obtained by the processes. This invention also pertains to lithium-ion secondary batteries making use of the boron-substituted graphite, silicon-containing boron-substituted graphite and silicon-containing carbonaceous materials as materials of negative electrodes.
b) Description of the Related Art
Recent years have seen rapid advancements in the size and weight reductions of electronic equipments and communication equipments, resulting in a strong demand for reductions in size and weight of secondary batteries used as drive power sources for them. Keeping in step with this, lithium-ion secondary batteries with high energy density and high voltage have been proposed. A lithium-ion secondary battery uses, for example, lithium cobaltate as a positive electrode and a carbonaceous material, such as graphite, as a negative electrode. Upon charging, lithium ions are caused to be occluded in the negative electrode, and upon discharging, these lithium ions are emitted from the negative electrode.
Employed as such negative-electrode materials are those available from carbonization or graphitization of carbonaceous raw materials or resins, such as MCMB (meso carbon microbeads) and fine particles of mesophase pitch, derived from petroleum pitch or coal tar pitch. However, dis-charge capacities available from these negative-electrode materials are not sufficiently high as batteries and moreover, initial efficiencies are not very high, either.
With a view to overcoming these problems, a variety of investigations have been made about boron-added carbonaceous materials. In 1992, J. R. Dahn et al. studied, as a host material for lithium intercalate, boron-substituted graphite which was obtained by adding, to artificial graphite, boron oxide in a proportion of about 8 wt. % in terms of boron and then conducting graphitization in a nitrogen gas atmosphere [Phys. Rev. B. 45(7), 3773 (1992)]. In this publication, however, properties or characteristics as an actual battery, such as dis-charge capacity and initial efficiency, are not disclosed.
The teaching of JP 5-266,880 A is only to conduct graphitization by simply adding boron to an organic substance as a raw material for graphite instead of the addition of boron oxide to artificial graphite as disclosed in the technical bulletin referred to in the above. The teaching of this patent publication is therefore not different at all from that of the technical bulletin.
In JP 8-31422 A and JP 9-63584 A, for example, the raw material for graphite to be produced is limited to pitch, or the graphitization temperature is limited to prevent an increase in the particle size of graphite. With these conditions alone, it is impossible to obtain a carbonaceous material optimal as a negative-electrode material for lithium-ion batteries. Further, JP 8-31422 A indicates that, when the thus-obtained carbonaceous material is used as a negative material in a battery, boron carbide remaining in the carbonaceous material leads to a reduction in the charge capacity of the battery. As a measure for dis-problem, this patent publication discloses merely to control the amount of a boron compound to be added. The carbonaceous material is likewise not considered to be optimal as a negative-electrode material for lithium-ion batteries.
Concerning industrial production of such boron-substituted graphite, JP 10-162829 A discloses that, after graphitization of a carbonaceous material is conducted in a nitrogen gas atmosphere, boron nitride formed in a surface layer is decreased by treating the graphitized carbonaceous material at 2,000xc2x0 C. or higher under reduced pressure or subjecting it to halogen treatment.
From the standpoint of industrial production of a negative-electrode material, however, the inclusion of such treatment requires more complex production facilities and higher cost. To cope with this problem, JP 10-255799 A discloses to disperse a boron compound in softened or molten pitch so that the boron compound can be prevented from coming into contact with the nitrogen gas atmosphere. It is however very difficult to completely encapsulate the boron compound with the pitch. Effects of this proposal are therefore suspicious. Except for the above patent publications, there is no technical bulletin or patent publication that makes mention about an atmosphere gas to be employed upon graphitization of a carbonaceous material. Even in most of the above patent publications referred to in the above, nothing is disclosed beyond graphitization of a carbonaceous material xe2x80x9cin an inert atmospherexe2x80x9d.
Carbonaceous materials, which can be obtained by either substituting boron for or adding boron to these boron-substituted graphites, are disclosed in JP 3-245458 A. As this patent publication discloses only treatments up to carbonization, the carbonaceous materials disclosed there are totally different from the previously-mentioned boron-substituted graphites in which portions of graphite carbons were replaced by boron.
Further, JP 7-73898 A discloses as a carbonaceous material graphite or amorphous graphite in which boron has substituted for a portion of carbon atoms. This carbonaceous material is however considerably different from the previously-mentioned boron-substituted graphite in which boron has substituted for a portion of carbon in the graphite, because its graphite layer spacing (d002) as determined by X-ray diffraction is 0.337 nm or greater and in addition, its use as a negative-electrode material in a battery provides a charge-discharge curve different from that available from a battery making use of a carbonaceous material.
As is disclosed inter alia in JP 7-73898 A and JP 6-333601, these boron-substituted or boron-added carbonaceous materials are synthesized by CVD processes each of which makes use of a mixed gas of a boron source gas and a carbon source gas. When industrial production is intended, these processes have no practical utility in cost.
In addition to boron-added carbonaceous materials, a variety of investigations have also been made about silicon-added carbonaceous materials. Silicon is known to be alloyed with lithium atoms, and as a specific capacity, approximately 4,017 mAh/g is achieved. However, these silicon-lithium alloys have large irreversible capacity, and due to expansion in volume resulting from the alloying, they involve a problem in stability.
To resolve this problem, JP 7-315822 A is proposing a material with atoms of an element capable of forming an alloy, such as silicon, incorporated in graphitized carbon as a host material without modification to the structure of an intact region in the host material. To product such a material, however, a costly synthetic process such as CVD is needed. Further, due to the insertion of silicon in carbon on the order of atoms, no improvements have been made yet as to the problem of large irreversible capacity in batteries.
Carbonaceous materials with boron and silicon mixed therein are disclosed, for example, in PCT International Publication WO 98/24134 and JP 11-40158 A. These carbonaceous materials are obtained by adding boron and silicon to the carbonaceous materials and then graphitizing the resulting mixture, and are not improved substantially in dis-charge capacity.
An object of the present invention is therefore to industrially provide boron-substituted graphite and a silicon-containing carbonaceous material which, when used in lithium-ion secondary batteries, can produce constant discharge potential while assuring higher energy density and higher service capacity than the conventional carbonaceous materials.
To achieve the above-described object, the present invention provides a process for the production of boron-substituted graphite for lithium-ion secondary batteries, said boron-substituted graphite containing N-bonded boron atoms in a small proportion relative to whole substituted boron atoms, which comprises heating a feed fine particulate mixture of an infusibilized carbonaceous material and a boron compound such that the carbonaceous material is carbonized into a carbon structure, raising a temperature of the resulting heated fine particulate mixture promptly to a graphitization treatment temperature in an inert atmosphere unreactive with boron, retaining the graphitization treatment temperature for a time sufficient to allow graphitization of the carbon structure to proceed to a desired extent, and quickly cooling the resulting graphitized mixture; boron-substituted graphite produced by the above process; and a lithium-ion secondary battery comprising a negative electrode made of the boron-substituted graphite.
The present invention also provides a process for the production of a silicon-containing carbonaceous material for lithium-ion secondary batteries, which comprises adding, to highly-crystalline graphite selected from a graphitized material of a carbonaceous material or natural graphite, silicon or a silicon compound such that said silicon or silicon compound amounts to 0.1 to 30 wt. % of the whole resulting mixture in terms of silicon, and subjecting said resulting mixture to heat treatment as 350 to 1,500xc2x0 C.; a silicon-containing carbonaceous material produced by the above process; and a lithium-ion secondary battery comprising a negative electrode made of the boron-substituted graphite.
Use of the boron-substituted graphite or silicon-containing carbonaceous material, which is available from the present invention, as a negative-electrode material in a lithium-ion secondary battery makes it possible to provide the lithium-ion secondary battery with a constant discharge level characteristic, excellent cycling characteristic, and higher energy density and higher service capacity than the conventional carbonaceous materials.
Firstly, the present invention will be discussed from a theoretical standpoint. It should however be borne in mind that the present invention is by no means limited by or to the following theoretical discussion.
As a process commonly usable for obtaining boron-substituted graphite, it is most convenient to graphitize a carbonaceous material in the presence of a boron compound as proposed y C. E. Lowell in Journal of The American Ceramic Society, 50(3), 142 (1967). Upon practicing this process, mixing of the boron compound and the carbonaceous material into a homogeneous mixture is important for evenly substituting boron for a portion of the carbon atoms in the carbonaceous material. To achieve this, some methods can be contemplated, including making smaller the particle size of a boron compound to be mixed or adding and mixing a boron compound in a liquid form. About specific methods for evenly mixing a boron compound in a carbonaceous material, a detained description will be made subsequently herein.
The boron material to be added to the carbonaceous material can be in any chemical form, including boron element, inorganic boron compounds such as boric acid, boron oxide and boron carbide, and organic boron compounds. Preferred as the carbonaceous material, however, is one having good wetting property for the boron compound to be added, permitting easy formation of boron carbide, and also having high graphitizability. As a rationale for the requirement of such a carbonaceous material, the substitution of boron for carbon and the conversion of carbon into a solid solution with boron is believed to proceed as will be described hereinafter.
As a mixture of a carbonaceous material and a boron compound is heated and raised in temperature in an atmosphere unreactive with boron, they first act each other and form boron carbide irrespective of the form of the boron compound so added. At this time, the reaction velocity of the formation of boron carbide considerably varies depending on the nature of the carbonations material employed as a raw material. The carbonaceous material to be used, therefore, may preferably be one having good wetting property to the boron compound and permitting easy formation of the carbide of boron. At each interface of boron carbide so formed, there is a region where a solid solution of carbon and boron, said solid solution being represented by B4C1xe2x88x92x (0 less than x less than 0.65), is formed. From this region, boron spreads into a carbon structure while forming a solid solution. Owing to this spreading in the form of the solid solution, resulting graphite crystals are rendered free of distortion and as a consequence, boron-substituted graphite with a well-developed graphite structure is formed.
For the above-described development of the graphite structure, the carbonaceous material employed as a raw material is required to be a readily-graphitizable material. The present inventors conducted an extensive investigation with a view to finding a starting carbonaceous material which has a high reaction velocity for the formation of boron carbide and also has high graphitizability. As a result, high softening-point pitch with optically isotropic portions contained therein was found to be most suitable.
To allow the above-described graphitization to proceed by the substitution of boron for carbon and the formation of carbon into a solid solution with boron and hence to produce homogeneous boron-substituted graphite, the atmosphere gas upon conducting graphitization is of first importance. In this regards, it is proposed in JP 10-162829 A to conduct graphitization in a nitrogen gas atmosphere from the viewpoint of cost. This patent publication however discloses to the effect that as a result, the boron compound and nitrogen in the atmosphere react and form boron nitride and further that the existence of this boron nitride becomes a sole cause for deteriorated battery properties or characteristics when the resultant graphite is used as a negative-electrode material in a battery.
However, the present inventors have found that the existence of boron nitride so formed is not a sole problem but that the reaction for the formation of boron nitride in the course of graphitization interferes with the above-mentioned spreading of boron into a carbon structure while forming a solid solution and thus renders the above-described reaction for the formation of boron nitride fail to form a homogeneous boron-substituted graphite. This has led to a further finding that there is a need to set the graphitization temperature at 2,200xc2x0 C. or higher upon graphitization of a carbonaceous material and also to use, as an atmosphere gas upon conducting the graphitization, an inert atmosphere which does not undergo a reaction with boron during the graphitizing reaction as will be described subsequently herein.
The ramp-up time to a temperature at which a carbonaceous material is graphitized, the graphitization temperature and its retention time, and the cooling time after the graphitization vary depending on the type of the apparatus, the amount of a boron compound added, etc. In general, however, the carbonaceous material may be heated to a graphitization temperature in 100 hours, and the graphitization temperature and its retention time may be set at 2,200xc2x0 C. or higher and in a range of from 0.1 to 48 hours. Subsequent cooling from the graphitization temperature to 100xc2x0 C. in 100 hours can bring about desired results. Incidentally, a temperature of 2,400xc2x0 C. or higher causes melting of the boron compound (e.g., boron carbide), which is added first in this graphitization, or of the resulting boron carbide, leading to graphite with an increased particle size. To avoid this problem, it is preferred to add highly-crystalline graphite which has such effectiveness as somewhat lowering the bulk density upon graphitization.
The above-described cooling rate is very important from the standpoint that boron spread as a solid solution in such a carbon structure is allowed to reprecipitate in a minimized amount as B4C on the surfaces of the resulting fine graphite particles and moreover, the reprecipitatation of such B4C takes place with as small a particle size as possible, because, when graphite is used as a negative-electrode material in a lithium-ion secondary battery, B4C in the graphite does not contribute to the reversible occlusion of lithium ions and on the contrary, increases an irreversible capacity and reduces the conductivity of the graphite.
The amount of B4C precipitated on the surfaces of the fine graphite particles can be determined by XPS. As a negative-electrode material for lithium-ion secondary batteries, a boron 1s spectrum is required to include around 186 eV a B 1s peak ascribed to substituted solid-solution boron and moreover, a percentage of boron determined from an intensity ratio of a B 1s peak appearing around 188 eV and ascribed to boron of B4C is needed to account for 5 atom % or less of surface layer elements as detected by XPS. These conditions can be met by controlling the cooling rate as described above.
On the other hand, the silicon-containing carbonaceous material is produced by adding silicon or a silicon compound to highly-crystalline graphite, which is selected from a graphitized product of a carbonaceous material and/or natural graphite, or boron-substituted graphite according to this invention and then subjecting the resulting mixture to heat treatment at 350 to 1,500xc2x0 C. in an inert atmosphere, reducing atmosphere or slightly-oxidizing atmosphere. By this heat treatment, compounds of carbon, silicon, boron and oxygen are formed, and the resulting silicon-containing carbonaceous material therefore shows low irreversible capacity and large service capacity, both of which are so good that they would not be expectable if only single crystals were used. No specific reason, however, has been elucidated yet for this unexpected result.
Preferred embodiments of the process according to the present invention for the production of boron-substituted graphite will next be described in the order of its steps. A description will also be made about the production process of a silicon-containing carbonaceous material.
1. Production Process of Boron-substituted Graphite
a. Step in Which a Boron Compound is Added to and Mixed with a Carbonaceous Material and the Resulting Mixture is Subjected to Heat Treatment
After the boron compound is added to and dispersed in feed pitch, the resulting mixture was subjected to heat treatment such that the feed pitch is converted into high softening-point pitch. This high-softening-point pitch contains 5 to 98 vol. %, preferably 10 to 95 vol. % of optically isotropic portions having strong reducing power to the boron compound, and has a softening point of 250xc2x0 C. or higher. The boron compound, which is to be dispersed in the feed pitch, may be either in a liquid form or in a solid form. When it is in a solid form, one having a smaller particle size is preferred because it disperses evenly in the pitch. For example, use of fine particles the average particle size of which is 50 xcexcm or smaller is preferred.
Concerning the amount of the boron compound to be added to the feed pitch, the boron compound can be added in an amount such that the proportion of the boron compound ranges from 0.1 to 7 wt. %, preferably from 1 to 5 wt. % in terms of boron based on the high softening-point pitch to be formed subsequent to the heat treatment. If the proportion of the boron compound so added is lower than 0.1 wt. % in terms of boron, the added boron compound is caused to evaporate in the subsequent graphitization treatment step so that boron-substituted graphite is not formed sufficiently. If the proportion of the boron compound so added is higher than 7 wt. % in terms of boron, on the other hand, B4C which does not spread as a solid solution into the resulting graphite is formed excessively, and due to the inclusion of this B4C, the resulting graphite is lower in battery properties or characteristics. Amounts of the boron compound outside the above range are therefore not appropriate.
The feed pitch employed as described above is a fraction which is left after coal tar, from which light fractions have been eliminated by atmospheric distillation, is subjected further to vacuum distillation. One having a softening point of from 110 to 115xc2x0 C. is preferred. Pitch the softening point of which is lower than 100xc2x0 C. contains lots of substances which undergo thermal decomposition when the pitch is subjected to heat treatment subsequent to the addition of the boron compound, thereby developing inconvenience such that a longer time is required for the heat treatment. On the other hand, a feed pitch having a softening point higher than 115xc2x0 C. is not preferred, because in an initial stage of the heat treatment subsequent to the addition of the boron compound, its viscosity is high and the dispersion of the boron compound so added cannot be fully achieved within the heat treatment time.
The pitch with the boron compound contained therein is subjected to the heat treatment at 420xc2x0 C. or lower, preferably 380 to 400xc2x0 C. During this heat treatment, the molten pitch is agitated mechanically or bubbling nitrogen gas from a bottom part of a reactor through plural nozzles. This makes it possible to keep uniform the temperature of the molten pitch, to prevent the pitch component from concentrating on any particular part, and also to assure dispersion of the boron compound.
It is preferred to conduct the above-mentioned heat treatment by setting conditions, such as heating temperature, heating time and pressure, such that the softening point of the heat-treated product becomes 250xc2x0 C. or higher, preferably falls in a range of from 330 to 370  C. If the softening point of the heat-treated product is lower than 250xc2x0 C., the fine particles soften and fuse and cannot retain their shapes upon infusibilization treatment by oxidation, said infusibilization treatment (hereinafter called xe2x80x9coxidation treatmentxe2x80x9d) being a step to be conducted subsequent to pulverization of the heat-treated product. If the softening point of the heat-treated product exceeds 370xc2x0 C., handling such as draw-off of the heat-treated product from the vessel after the heat treatment becomes difficult, and/or by pulverization as next step, fine particles are obtained with a greater aspect ratio. Softening points outside the above range are therefore not preferred.
The addition of the boron compound to the feed pitch in the above-described manner makes it possible to form high softening-point pitch, which contains 5 to 98 vol. % of optically isotropic portions having strong reducing power to the boron compound and shows high graphitizability, because by the addition of the boron compound, the viscosity of the resulting mixture under the heat treatment increases to inhibit joining of mesophase portions as optically anisotropic structures.
Such optically isotropic portions in the high softening-point pitch have good wetting property to the added boron compound, can easily form the carbide of boron, and also has a high formation rate of boron-substituted graphite. If the proportion of these optically isotropic portions is lower than 5 vol. %, the overall formation rate of boron-substituted graphite becomes slower. If the proportion of these optically isotropic portions is higher than 98 vol. %, on the other hand, the graphitizability is deteriorated.
In a further preferred embodiment of the present invention, the above-described boron compound can be evenly dusted on highly-crystalline graphite, for example, on natural graphite (flaky) or artificial graphite the particle size of which is very small, and the graphite with the boron compound dusted thereon can then be mixed in high softening-point pitch which contains 5 to 98 vol. % of optically isotropic portions. This makes it possible to allow the boron compound to spread more evenly into the pitch, and further, the highly-crystalline graphite promotes the graphitization of the carbonaceous material as the raw material.
To have the boron compound evenly dusted on the highly-crystalline graphite, fine particles of the highly-crystalline graphite are evenly dispersed in a solution of the boron compound, for example, boric acid, boron oxide or the like in a solvent capable of exhibiting wetting property to graphite, such as ethanol or a liquid organoboron compound, and organic substances such as the solvent are then eliminated by processing such as drying under reduced pressure or thermal decomposition, whereby fine particles of highly-crystalline graphite, said fine particles carrying the boron compound evenly spread and dusted thereon, can be obtained. Concerning the proportions of the highly-crystalline graphite and boron compound to be used upon conducting the dusting, it is preferred that the boron compound amounts to 0.1 to 70 wt. % in terms of boron element of the total weight of both materials.
Upon mixing the resulting mixture of the highly-crystalline graphite and the boron compound in the high softening-point pitch in which the optically isotropic portions are contained in the proportion of from 5 to 98 vol. %, the amount of the mixture, similarly to the above-described case, may range from 0.1 to 7 wt. %, preferably from 1 to 5 wt. % in terms of boron on the basis of the high softening-point pitch. The mixing of the highly-crystalline graphite, on which the boron compound is evenly spread and dusted, with the high melting-point pitch may be effected by adding the former to the latter upon subjecting the feed pitch to heat treatment, kneading both of them under heat in a kneader or the like, or mixing both of them as fine particles in a ball mill or the like.
Upon adding the boron compound to the feed carbonaceous material in the present invention, it is preferred, as described above, to evenly disperse the boron compound in high softening-point pitch, said pitch containing 5 to 98 vol. % of optically isotropic portions having strong reducing power to the boron compound, to form the resulting mixture into fine particles and then to use the fine particles as a raw material for graphitization.
b. Pulverization Step of the Heat-treated Product
The heat-treated product obtained as described above is next pulverized such that the resulting fine particles have particle sizes under 200 mesh. The average particle size is 50 xcexcm or smaller, with a range of from 5 to 30 xcexcm being preferred. No particular limitation is imposed on the grinding or milling machine, and a grinding or milling machine such as a jet mill, a ball mill, an agitation mill or a high-speed rotary mill can be used.
c. Oxidation Treatment
The fine particles are then subjected to oxidation treatment to insolubilize them. This treatment is necessary to avoid fusion and cohesion of the fine particles during the subsequent carbonizing and carbide-forming step and graphitization step. This oxidation treatment may preferably be conducted in an oxidizing furnace or kiln at an oxygen concentration of from 16 to 18 wt. % or so while causing nitrogen gas to flow through the oxidizing furnace or kiln, although the oxidation treatment may be conducted at a temperature of from 140 to 300xc2x0 C. in air. To prevent the fine particles from fusing and cohering together into aggregates, it is preferred, upon oxidation, to divide the oxidizing furnace or kiln into a multiplicity of sections to permit precise temperature control; or for keep the fine particles out of contact with a heat source, to treat the fine particles in a fluidized bed or to effect in the form of a thin layer the flow of the fine particles through the oxidizing furnace or kiln. Although some fusion-cohered aggregates occur by this oxidation treatment, these fusion-cohered aggregates can be reused provided that they are pulverized again.
Concerning the degree of oxidation in this oxidation treatment, it is desired to set oxidation conditions such that the oxidized product contains about 2 to 10 wt. % of oxygen. A proportion of oxygen lower than the above range, in other words, insufficient oxidation is not preferred in that fusion and cohesion of fine particles takes place in the subsequent carbonization treatment. Excessive oxidation, on the other hand, is not preferred in that the specific surface area of the fine particles increases or the non-crystallinity of the fine particles increases.
The fine particles, which have been subjected to the oxidation treatment as described above, are somewhat rounded without sharp corners which the fine particles had before the oxidation treatment, and, although the resulting fine particles may not be described to such an extent as being spherical, they have been converted into somewhat rounded fine particles and their aspect ratio falls within a range of from 1 to 2.
d. Carbonization Step
Finally, carbonizing and carbide-forming treatment of the fine particles is conducted by a method known per se in the art. This carbonization treatment is conducted at 600 to 1,200xc2x0 C. As the treatment time, a suitable time should be selected depending on the facilities. Further, as an example of the atmosphere during the carbonization, a reducing gas can be mentioned. In principle, any inert atmosphere can be used without problems insofar as carbon is not oxidized there. This carbonization treatment can also be conducted continuously, and as various conditions and facilities for the carbonization, a variety of various conditions and facilities known to date can be used as are.
dxe2x80x2. Treatment for the Prevention of Fusion and Cohesion of the Fine Particles
To prevent the fine particles from fusing and cohering during graphitization which is a next step, fine particles of highly-crystalline graphite are added and mixed with the above-mentioned oxidized product or carbonized product such that the fine particles of the highly-crystalline graphite amount to 0.5 to 30 wt. % of the whole amount of the resulting mixture. As these fine particles of the highly-crystalline graphite, it is preferred to use one having an average particle size of from 0.1 to 10 xcexcm. One having an average particle size smaller than 0.1 xcexcm is not economical because it requires special pulverization. One having an average particle size greater than 10 xcexcm, on the other hand, is not effective for the prevention of fusion and cohesion. The mixing can be performed by a conventional method, for example, in a V-type blender or Henschel mixer.
e. Graphitization Step
Graphitization of the fine particles is conducted by heating the fine particles to a graphitization temperature in 100 hours in an inert atmosphere unreactive with boron, and, after graphitization at 2,200xc2x0 C. or higher, cooling the graphitized fine particles to 100xc2x0 C. from the graphitization temperature in 100 hours. The inert gas unreactive with boron can be a rare gas, such as helium or argon, or a gas composed of such a rare gas and containing nitrogen to such an extent as not causing nitrifing of boron. Use of a gas other than these boron-unreactive gases results not only in inclusion of a boron compound, which is to be formed through a reaction with the gas, in the boron-substituted graphite to be obtained finally but also in inhibition of spreading of boron as a solid solution into graphite.
Concerning the graphitization temperature, graphitizability is known to be improved further in general as the graphitization temperature rises. It is suitable to set the graphitization temperature at 2,200xc2x0 C. or higher where boron spreads at a high rate as a solid solution into the carbon structure. On the other hand, the retention time of the graphitization temperature may be 0 to 48 hours, preferably 1 to 12 hours. If the retention time of this temperature is too short, for example, 0 hour, the graphitization is not allowed to proceed to any sufficient extent. If the retention time exceeds 48 hours, the added boron and the boron, which have already spread as the solid solution, undergo evaporation. Retention time outside the above range is therefore not suited. During this graphitization time, evaporation of the boron compound, conversion of the boron compound into boron carbide, and spreading of boron as a solid solution into graphite take place.
To produce boron-substituted graphite optimal as a negative-electrode material for lithium-ion secondary batteries, the cooling rate from the graphitization temperature to 100xc2x0 C. is important. Use of a higher cooling rate makes it possible to allow boron, which has spread as a solid solution, to reprecipitate in a smaller amount as B4C on graphite surfaces and moreover, makes the reprecipitatation of such B4C take place with a smaller particle size. If the cooling to the temperature of 100xc2x0 C. is conducted taking more than 100 hours, B4C precipitates in a greater amount and moreover, with a greater particle size, leading to an increase in irreversible capacity when employed as a negative-electrode material in a lithium-ion secondary battery. Cooling rates outside the above range are therefore not preferred.
As industrial graphitization furnaces or kilns, Acheson furnaces are primarily used these days. With furnaces of this type, however, control of the atmosphere, cooling rate and the like is difficult. They are hence not suited for the production of boron-substituted graphite having good battery properties or characteristics. To meet the above-described conditions, a continuous graphitization furnace of such a design that graphite crucibles with fine particles placed therein are continuously fed into the graphitization furnace and are then cooled or a continuous graphitization furnace of the kiln type or the shaft type which permits continuous charging of fine particles is most suitable. It is however not necessary to use a furnace or kiln of such a design insofar as graphitization conditions such as those described above can be assured.
[Various Physical Property Values of Boron-substituted Graphite]
The boron-substituted graphite according to the present invention obtained as described above is in the form of highly-crystalline boron-substituted fine graphite particles, which have a graphite layer spacing (d002) of 0.337 nm or smaller, a crystalline size (Lc) of 30 nm or greater in the direction of c-axis, and a crystalline size (La) of 40 nm or greater in the direction of a-axis. Further, a boron 1s spectrum as measured by XPS includes around 186 eV a B 1s peak ascribed to substituted boron in the form of a solid solution, and the percentage of boron determined from an intensity ratio of a B 1s peak appearing around 188 eV and ascribed to boron of B4C accounts for 5 atom % or less of surface layer elements as detected by XPS.
Further, the percentage of nitrogen-bonded boron, a peak of which appears around 190 eV in the boron 1s spectrum as measured by XPS may preferably account for 10 atom % or less of the surface layer elements as detected by XPS. It is also preferred that, when binding energy of a gold 4f7/2 peak is assumed to be 84.0 eV, a carbon 1s peak of graphite in the carbon 1s spectrum as measured by XPS is smaller in binding energy than 284.3 eV and appears around 282.5 eV.
Preferably, the boron-substituted graphite contains boron in a proportion of from 0.01 to 5 wt. %, more preferably in a proportion of from 0.5 to 3 wt. %, both in terms of boron element, and is in the form of very fine particles having a specific surface area of 2.0 m2/g or smaller. When such boron-substituted graphite is used as a negative-electrode material in lithium-ion secondary batteries, the resulting batteries have low reactivity with an electrolytic solution and a relatively small irreversible capacity.
[Measurement of XPS]
Measurement of XPS is performed as will be described hereinafter. Graphite powder is fixed on a sample holder for XPS analysis without touching it with a bare hand. As an illustrative fixing method, the graphite powder may be filled in a recess of a holder or may be lightly compression-bonded onto a soft metal such as indium. The holder is next brought into an analysis chamber to conduct a measurement. Before the measurement, the sample should not be subjected to any surface treatment (such as washing with an organic solvent or ion sputtering). The measurement is conducted in accordance with general XPS measurement procedures [see, for example, xe2x80x9cX-ray Photoelectron Spectroscopyxe2x80x9d, Maruzen Co., Ltd. (1998)]. No particular limitation is imposed on the X-ray source. Binding energy is calibrated using a standard sample. In the present invention, gold was used, and the binding energy of a gold 4f7/2 peak was set at 84.0 eV. Errors in binding energy in an analyzer are not greater than +0.05 eV. Levels of binding energies are considered to fall within a dispersion range of +0.5 eV although the dispersion range varies depending on the analyzer maker. It is therefore easy to distinguish the three states of boron, namely, solid-solution boron, boron carbide and boron nitride in a boron 1s spectrum.
To calculate the elemental composition of a surface layer, on the other hand, the integrated intensities of peaks appeared in the boron 1s spectrum are first calculated. A peak may appear in an asymmetrical form in some instances, and in such a case, its integrated intensity should be calculated by also taking the asymmetry into consideration. As a method for determining the integrated intensities of peaks of boron, it is popular, but not limited, to define the peaks of solid-solution boron, boron carbide and boron nitride components by Gaussian functions, Lorentz functions or the like and then fitting a found spectrum to the thus-defined peaks. To calculate the composition of the surface layer, relative sensitivity coefficients associated with the analyzer are used. In the present invention, calculations were made using the following relative sensitivity coefficientsxe2x80x94carbon 1s: 1.00, boron 1s: 0.486, nitrogen 1s: 1.80, and oxygen 1s: 2.93. When no particular elements other than those mentioned here have been added to graphite, it is sufficient to conduct quantitative calculations on these four elements only. When some graphite particles are coated with an element or compound other than those mentioned above, the thickness of the coating layer should be taken into consideration.
2. Production Process of Silicon-containing Carbonaceous Material
A silicon-containing carbonaceous material is produced by adding silicon or a silicon compound to highly-crystalline graphite, which is selected from a graphitized product of a carbonaceous material and/or natural graphite, or the above-described boron-substituted graphite of the present invention such that the silicon or silicon compound amounts to 0.1 to 30 wt. % of the whole resulting mixture, and then subjecting the mixture to heat treatment at 350 to 1,500xc2x0 C. in an inert atmosphere, reducing atmosphere or slightly oxidizing atmosphere. Examples of the carbonaceous material useful in this process can include highly-crystalline graphites such as those obtained by carbonizing or graphitizing thermosetting resins, such as phenol resins and furan resins, or coal or petroleum pitch, natural graphite, graphite formed as a decomposition product upon production of Sic, and kish graphite; and carbonaceous materials such as the boron-substituted graphite of the present invention.
On the other hand, illustrative of the silicon or the silicon compound are monocrystalline silicon, polycrystalline silicon, amorphous silicon, and silicon oxide. The mixing of the carbonaceous material with the silicon or silicon compound can be conducted in a manner known per se, for example, in a V-type blender or Henschel mixer. The silicon or silicon compound may be added in an amount of from 0.1 to 30 wt. % in terms of silicon element on the basis of the resulting mixture. If the amount is less than 0.1 wt. %, the effects of silicon are not exhibited. If the amount is greater than 30 wt. %, the resulting silicon-containing carbonaceous material has a very large irreversible capacity.
[Applications to Batteries]
A description will next be made of applications of the boron-substituted graphite and silicon-containing carbonaceous material to lithium-ion secondary batteries. Each active material, which makes up its corresponding electrode plate, is formed from an electrode coating formulation composed at least of the active material and a binder. By using as a negative-electrode active material the above-described boron-substituted graphite or silicon-containing carbonaceous material of this invention and also using as a positive-electrode active material, for example, one or a combination of plural compounds out of lithium oxides such as LiCoO2 and LiMn2O4 and chalcogen compounds such as TiS2, MnO2, MoO3 and V2O5, a lithium-ion secondary battery capable of producing a service voltage as high as 4 volts can be obtained. It is preferred to evenly disperse these active materials in the resulting coating formulations, respectively. For this purpose, it is preferred to use, as each of positive and negative active materials, fine particles having particle sizes in a range of from 1 to 100 xcexcm and an average particle size of from 5 to 40 xcexcm or so, more preferably from 10 to 25 xcexcm or so.
As the binder in each active material layer, a binder can be selected as desired, for example, from thermoplastic resins, specifically polyester resins, polyamide resins, polyacrylate ester resins, polycarbonate resins, polyurethane resins, cellulose resins, polyolefin resins, polyvinyl resins, fluorinated resins, polyimide resins and the like; and can then be used.
Each active material which makes up its corresponding electrode plate can be prepared in a manner as will hereinafter be described. Firstly, the binder selected as desired from the above-described materials and the fine particulate active material are kneaded or are dispersed and dissolved by using a suitable dispersant, whereby an electrode coating formulation is prepared. Using the coating formulation so obtained, a charge collector is then coated. As a coating method, gravure, gravure reverse, die coating, slide coating or the like is used. After that, through a drying step in which the coating formulation so applied is dried, an active layer of a desired thickness is formed. In this manner, positive and negative electrode plates are obtained.
As the charge collectors used for the electrode plates, metal foils such as aluminum or copper foils can be used preferably. These metal foils are about 10 to 30 xcexcm in thickness. Upon fabricating a lithium-ion secondary battery by using the positive and negative electrode plates prepared as described above, a non-aqueous electrolytic solution with a lithium salt dissolved as a solute in an organic solvent is used as an electrolytic solution. Examples of organic solvents usable here can include cyclic esters, linear esters, cyclic ethers, chain ethers, and the like. For example, propylene carbonate or the like can be mentioned as a cyclic ester, tetrahydrofuran or the like can be mentioned as a cyclic ether, and 1,2-dimethoxyethane or the like can be mentioned as a linear ether.
Examples of the solute, i.e., the lithium salt, which together with the organic solvent forms the non-aqueous electrolytic solution, can include inorganic lithium salts such as LiClO4, LiBF4, LiPF6, LICl and LiBr, and organic lithium salts such as LiB(C6H5)4, LiN(SO2CF3)2, LiC(SO2CF3)3, LiOSO2CF3, LiOSO2C2F5, LiOSO2C3F7, LiOSO2C4F9, LiOSO2C5F11, LiOSO2C6F13 and LiOSO2C7F15.
The present invention will next be described specifically by Examples and Comparative Examples.

Production process of material for lithium-ion secondary batteries, material obtained by the process, and batteries


A method is provided for forming conductive layers in semiconductor channels and vias by using ramped current densities for the electroplating process. The lower density currents are used initially to deposit a fine grain conductive layer in the vias and then higher densities are used to deposit a large grain conductive layer in the channel.

The present invention relates generally to semiconductors and more specifically to electroplating of conductors used in semiconductors.
In the manufacturing of integrated circuits, after the individual devices, such as the transistors, have been fabricated in the silicon substrate, they must be connected together to perform the desired circuit functions. This connection process is generally called xe2x80x9cmetalizationxe2x80x9d, and is performed using a number of different photolithographic and deposition techniques.
One metalization process, which is called the xe2x80x9cdamascenexe2x80x9d technique, starts with the placement of a first channel dielectric layer, which is typically an oxide layer, over the semiconductor devices. A first damascene step photoresist is then placed over the oxide layer and is photolithographically processed to form the pattern of the first channels. An anisotropic oxide etch is then used to etch out the channel oxide layer to form the first channel openings. The damascene step photoresist is stripped and a barrier layer is deposited to coat the walls of the first channel opening to ensure good adhesion and to act as a barrier material to prevent diffusion of such conductive material into the oxide layer and the semiconductor devices (the combination of the adhesion and barrier material is collectively referred to as xe2x80x9cbarrier layerxe2x80x9d herein). A seed layer is then deposited on the barrier layer to form a conductive material base, or xe2x80x9cseedxe2x80x9d, for subsequent deposition of conductive material. A conductive material is then deposited in the first channel openings and subjected to a chemical-mechanical polishing process which removes the first conductive material above the first channel oxide layer and damascenes the conductive material in the first channel openings to form the first channels.
For multiple layers of channels, another metalization process, which is called the xe2x80x9cdual damascenexe2x80x9d technique, is used in which the channels and vias are formed at the same time. In one example, the via formation step of the dual damascene technique starts with the deposition of a thin stop nitride over the first channels and the first channel oxide layer. Subsequently, a separating oxide layer is deposited on the stop nitride. This is followed by deposition of a thin via nitride. Then a via step photoresist is used in a photolithographic process to designate round via areas over the first channels.
A nitride etch is then used to etch out the round via areas in the via nitride. The via step photoresist is then removed, or stripped. A second channel dielectric layer, which is typically an oxide layer, is then deposited over the via nitride and the exposed oxide in the via area of the via nitride. A second damascene step photoresist is placed over the second channel oxide layer and is photolithographically processed to form the pattern of the second channels. An anisotropic oxide etch is then used to etch the second channel oxide layer to form the second channel openings and, during the same etching process to etch the via areas down to the thin stop nitride layer above the first channels to form the via openings. The damascene photoresist is then removed, and a nitride etch process removes the nitride above the first channels in the via areas. A barrier layer is then deposited to coat the via openings and the second channel openings. Next, a seed layer is deposited on the barrier layer. This is followed by an electroplating of the conductive material on the seed layer in the second channel openings and the via openings to form the second channel and the via. A second chemical-mechanical polishing process leaves the two vertically separated, horizontally perpendicular channels connected by a cylindrical via.
The use of the damascene techniques eliminates metal etch and dielectric gap fill steps typically used in the metalization process. The elimination of metal etch steps is important as the semiconductor industry moves from aluminum to other metalization materials, such as copper, which are very difficult to etch.
One drawback of using copper is that copper electroplating is a slow process, which means that manufacturing, throughput is relatively low.
Another drawback of using copper is that copper is subject to electromigration, which means that copper migrates under the influence of current flow. This means that areas where the current density is relatively high, such as in vias, there is a tendency to form voids. This tends to increase current density further which increases the size of the voids until open circuits occur.
Separate solutions for both problems have been long sought but have eluded those skilled in the art. As the semiconductor industry is moving from aluminum to copper and other type of materials with greater electrical conductivity and thinner channels and vias, it is becoming more pressing that solutions be found.
The present invention provides a method for forming conductive layers in semiconductor channels and vias by using ramped current densities for the electroplating process. The lower density currents are used initially to deposit a fine grain conductive layer in the vias and then higher densities are used to deposit a large grain conductive layer in the channel. This speeds up the overall manufacturing process while the fine grain structure increases electromigration resistance.
The present invention provides a method for forming conductive layers in semiconductor channels and vias by using ramped direct current for the electroplating process. This speeds up the overall manufacturing process and deposits a fine grain structure conductive layer which increases electromigration resistance.
The present invention provides a method for forming conductive layers in semiconductor channels and vias by using ramped forward pulse current for the electroplating process. This speeds up the overall manufacturing process and deposits a fine grain structure conductive layer which increases electromigration resistance.
The present invention provides a method for forming conductive layers in semiconductor channels and vias by using ramped reverse pulse current for the electroplating process. This speeds up the overall manufacturing process and deposits a fine grain structure conductive layer which increases electromigration resistance.
The above and additional advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed description when taken in conjunction with the accompanying drawings.

Variable grain size in conductors for semiconductor vias and trenches


Bicyclic carbohydrates for the treatment of infections caused by herpseviridae, and in particular cytomegalovirus. The invention consists of the novel bicyclic carbohydrates the generic structure of which is:

The invention relates generally to compounds active against viral diseases and, more specifically to bicyclic carbohydrate compounds that are useful in the prophylaxis and treatment of diseases caused by the alphaherpesvirina cytomegalovirus.
Cytomegalovirus (CMV) is the largest human herpes virus, and there is only one serotype. As with animal CMVs it is species specific; humans are the natural hosts and animal CMVs do not infect humans. The name refers to the multinucleated cells, which together with the intranuclear inclusions, are characteristic responses to infection with this virus. Transmission is via saliva, and CMVs were originally called 'salivary gland' viruses. Urine is an additional source of infection in children, and in infected pregnant women the virus can spread via the blood to the placenta and fetus. Semen and cervical secretions may also contain virus and it can therefore be spread by sexual contact. It is often present in milk in small quantities, but this is of doubtful significance in transmission. In hospitals it can be transmitted by blood transfusion and organ transplants. CMV infections are often asymptomatic, but can reactivate and cause disease when CMI (cell mediated immune response) defenses are impaired. After clinical silent infection of unknown cells in the upper respiratory tract, CMV spreads locally to lymphoid tissues and then systemically in circulating lymphocytes and monocytes to involve lymph nodes and the spleen. The infection then localizes in epithelial cells in salivary glands and kidney tubules, and in cervix, testes and epididymis, from where the virus is shed to the outside world (Table 1).
TABLE 1Cytomegalovirus infectionsSite of infectionResultCommentSalivary glandsSalivary transmissionImportance of kissing andcontaminated handsTubular epithe-Virus in urineProbable role of transmissionlium of kidneyCervix/Testis/Sexual transmissionUp to 107 infectious doses/mlepididymisof semen in an acutelyinfected maleLymphocytes/Virus spread throughProbable site of persistentMacrophagesbody via infected cellsinfectionMononucleosis mayoccurImmunosuppressiveeffectPlacenta/FetusCongenitalGreatest damage in fetus afterabnormalitiesprimary maternal infectionrather than reactivation
Infected cells may be multinucleated or bear intranuclear inclusions, but pathologic changes are minor and infection is generally asymptomatic. In young adults, a glandular fever type illness can occur, but without heterophil antibodies. There is fever and lethargy, and abnormal lymphocytes and mononucleosis in blood smears. The virus inhibits T cell responses and there is a temporary reduction in their immune reactivity to other antigens. Although specific antibodies and CMI responses are generated, these fail to clear the virus, which often continues to be shed in saliva and urine for many months. The infection is, however, eventually controlled by CMI mechanisms, although infected cells remain in the body throughout life and can be a source of reactivation and disease when CMI defenses are impaired. CMV owes its success in our species to its ability to evade immune defenses (Cann A. J. (1997) Principles of Molecular Virology. Second Edition. Academic Press, San Diego, pp. 65–67; Mims C., Playfair J., Roitt I., Wakelin D. and Williams R. (1998) Medicinal Microbiology. Second Edition. Mosby International Limited, pp.347–348).
Ganciclovir is an anti-CMV drug that works by inhibiting CMV's DNA polymerase enzyme. It can prevent CMV from reproducing and infecting new cells, but it cannot eliminate it from the body. Ganciclovir is manufactured by Roche under the trade name Cymevene. In the US its trade name is Cytovene. Ganciclovir now comes in several formulations: oral, intravenous and intravitreal (into the eye). It is either given intravenously on a long-term basis through a catheter or in a pill form. In the case of administration by catheter, one end of a tube is surgically inserted into a large vein in the chest, the other end of the tube remains outside the chest or has an injectable port just under the skin. Although slightly less efficient, an oral form of ganciclovir is also approved by the FDA for prevention and maintenance treatment of CMV.
Unfortunately, ganciclovir also suppresses bone-marrow production of the white blood cells called neutrophils. This condition is called neutropenia. People taking ganciclovir require close monitoring to ensure blood disorders are promptly detected. It can also harm the kidneys, reduce testosterone levels, and cause nausea, vomiting, diarrhea and rash. More than 10% of IV ganciclovir recipients have to stop treatment because of these side effects. In addition, the development of strains of CMV that are resistant to ganciclovir has been reported. These do not seem to develop any faster with oral ganciclovir than with the intravenous formulation (www.aidsmap.com).
Alternative compounds with activity against herpes viruses such as cytomegalovirus are needed.

Bicyclic carbohydrate compounds useful in the treatment of infections caused by herpesviridae

Abstract: wherein R1 is either -Bn or -Ph; R2 and R3 are either -alkyl, -aryl, -allyl, or —H; R4 and R5 form a ring and are either —CH(Ph)- or —CH(aryl)- and X is either O, N or S.


A disposable urine specimen collection cup has a two-position locking handle incorporated and molded into it. The elongated handle is formed integrally as part of the cup. In its first position, the handle is situated in a generally parallel position relative to the outer surface of the cup. The handle may be located within a recess which is defined along one side of the specimen collection cup. When ready for use, the handle is pulled outwardly from the cup, raised and locked into place. The handle is situated in a generally perpendicular position relative to the outer surface of the cup. The handle folds downwardly against the side of the cup for restorage of the cup and contents after collection of the specimen is completed.

This invention relates generally to devices used in the health care industry. More particularly, it relates to a urine specimen collection cup having a retractable support arm for holding the cup in a sanitary, sample-taking orientation relative to the patient when urine specimens are taken.
The physical, chemical or microscopic analysis of human urine, or urinalysis, is an essential tool in the health care industry. Urinalysis can provide a wide range of information concerning the health and well being of a patient. The examination of urine color and clarity, the measurement of urine acidity and the detection of the presence of protein, sugar, bacteria and other matters found in urine can tell a great deal about the physical condition of the subject patient.
Urinalysis is performed ideally by using a fresh urine specimen, preferably the first voiding of the day since such specimens are most concentrated and more likely to reveal abnormalities in the urine. All urine tests are also performed ideally by using clean and uncontaminated collection vessels or containers. Additionally, it is recognized that microscopic urinalysis is best performed within the first one-half hour after collection of the specimen since allowing the sample to stand may cause bacterial overgrowth and even dissolution of cellular elements. In short, collection protocol requires that all specimens be collected in sterile containers, sealed against outside contamination and then refrigerated as soon as possible after collection.
Bacteriologic study of urine specimens poses a particular problem due to the inevitable contamination caused by the presence of organisms which reside in the vicinity of the human urethral opening. This contamination can be avoided by catheterization of the urinary bladder, but such is an extreme measure and clearly not recommended for routine examinations. Very reliable bacteriologic urine studies are possible, however, without catheterization by utilizing the so-called xe2x80x9cclean-catch mid-streamxe2x80x9d technique. For women, collecting a urine specimen in this manner involves partial voiding and then placement of a urinary collection cup between the legs to catch the xe2x80x9cmid-streamxe2x80x9d urine during continued voiding. This technique is difficult to accomplish without the patient soiling her hands during the urine collection process and without the risk of the patient""s hands contacting the collection cup during collection, thus risking inaccurate results due to bacteriologic contamination. In short, eliminating contact with the urine stream simple provides greater hygiene for the patient and reliability for the health care provider charged with handling and measuring the specimen contained within the cup.
It is, therefore, a principal object of this invention to provide a new, useful and uncomplicated urine specimen collection cup which eliminates the inconveniences, unsanitary practices and ineffective results common with convention urine collection devices. It is another object of this invention to provide such a cup which is manufactured to be disposable. It is still another object of this invention to provide such a cup which allows the patient to more easily hold the cup in specimen-collecting relation to her body and to avoid the risk of dropping the cup into the toilet. It is still another object of the present invention to provide such a cup which would make urine collection easier and more convenient and make patients feel more at ease with the process, thus reducing the stress associated with medical examinations. It is still another object of the present invention to provide such a cup which is particularly beneficial for pregnant or obese women who experience difficulty with reaching around the abdomen to hold a specimen cup. It is still another object of the present invention to provide such a cup which minimizes the risk of contamination thereby avoiding the need to repeat the talking of urine samples and reducing costs to patients and the health care industry in general.
The present invention has obtained these objects. It provides for a disposable urine specimen collection cup which has a two-position locking handle incorporated and molded into it. In the preferred embodiment, the elongated handle is formed within a recess at one side of the specimen collection cup. When ready for use, the handle is pulled outwardly from the cup, raised and locked in place. The handle folds down against the side of the cup for re-storage of the cup and contents after collection of the specimen is completed. The foregoing and other features of the urine sample collection cup of the present invention will be further apparent from the detailed description which follows.

Cup to assist with urine specimen sampling


An example method includes receiving a selection of a media content, applying customized parental control rules associated with a user to the media content, providing a notification to apply a parental control associated with the customized parental control rules to the media content, receiving a confirmation to apply the parental control, and controlling the media content in accordance with the parental control that is applied.

Content may have general descriptions of what may be included in the content. For example, content may have rating that suggests appropriate age groups to view the content. In addition, content may have general and broad descriptions associated with the rating, such as language, violence, and the like. However, content with the same ratings and similar descriptions may still be very different. Such lack of granularity does not allow for effective parental control for content access.
To facilitate understanding, similar reference numerals have been used, where possible, to designate elements that are common to the figures.


A memory device configured to support multiple memory densities is provided. The memory device includes a first plurality of electrical contacts corresponding to a first command/address channel, a second plurality of electrical contacts corresponding to a second command/address channel, a third plurality of electrical contacts corresponding to a first data bus, a fourth plurality of electrical contacts corresponding to a second data bus, and mode selection circuitry configured to place the memory device in the first mode or the second mode. In the first mode, the first plurality of memory cells is operatively coupled to the first and third pluralities of electrical contacts and the second plurality of memory cells is operatively coupled to the second and fourth plurality of electrical contacts. In the second mode, the first and second pluralities of memory cells are both operatively coupled to the first and third pluralities of electrical contacts.

Semiconductor devices are often provided in packages with multiple connected dies, in which circuit elements of the dies are connected in various ways. The semiconductor dies are often designed to be packaged in a particular configuration such that the circuit elements are configured to only support a particular memory density of the package. As newer generations of memory are developed, the memory density in which memory packages are offered changes over time. For example, the memory density for one generation of memory packages may be 8 Gb, and the memory density for a subsequent generation of memory packages may be 16 Gb. Semiconductor manufacturers supplying the memory dies to be implemented on both the older and newer packages have traditionally designed a first memory die configured to support the first memory density (e.g., 8 Gb) and a second memory die to support the second memory density (e.g., 16 Gb). One drawback of this approach is that semiconductor manufacturers endure significant costs from the design, production, marketing, and shipment of two separate memory dies throughout the transition period from one generation to another.

Semiconductor dies supporting multiple packaging configurations and associated methods


The invention is a consortium of thermophilic methanotrophic organisms in culture medium containing said consortium reproduced at temperatures of 50.degree. C. to 80.degree. C., said consortium being comprised primarily of ovoid or rod-shaped organisms. The consortium can be instilled into soil or water to degrade pollutants, especially hydrocarbons and substituted hydrocarbons.

A group of aerobic microorganisms known as methanotrophs have previously been used to degrade organic contaminants. This group of organisms produces monooxygenases which oxidize methane and, in the absence of methane, after the enzyme has been produced, will incidently oxidize other compounds such as halogenated hydrocarbons, alkanes, alcohols, etc.
One of the more prevalent contaminants which have been degraded by co-metabolisms using methanotrophs is trichloroethylene. (TCE), an organic solvent that is used widely for metal processing, dry cleaning and in production of coatings. Because of leaks, spills and dumping, TCE is frequently found in subsurface soil environments. TCE is one of the most commonly found pollutants at hazardous waste sites. TCE and other chlorinated hydrocarbons are frequent pollutants of ground water. Most attempts to remediate the contamination of soils and aquifers have involved use of pump or vacuum means to bring the contaminated material to the surface for treatment. These means have resulted in limited removal of contaminants. The prior art practices are expensive and generally have no end-point to their operations. Limitations relating to hydraulic conductivity, soil matrix, desorption and residual saturation or pockets of contaminants present real problems when practicing the prior art methods of remediation.
An electrokinetic process developed by Casagrande has been used to dewater soils. This process has been used to remove contaminants from soil and aquifers. The process utilizes a direct current (DC electric field to induce the movement of water and dissolved ions as a means of transporting the contaminant. The method is beneficial only when contaminants are reasonably soluble in water (for example, benzene, toluene, xylene, phenol and chlorinated solvents). Moreover, the electrokinetic process results in transport, not degradation, of the contaminants. Therefore, electrokinetic application to soil provides only an incomplete solution to problems of contamination of soil and water. Ho has applied the electrokinetic methods to movement and capture of p-nitrophenol (PNP) with granular activated carbon (GAC) filled cassettes. However, the problems relating to removing and disposing of the contaminated cassettes remain unsolved.

Thermophilic methanotrophs for high temperature oxidations

The United States of America as represented by the Administrator of the Environmental Protection Agency


An x-ray generator includes an x-ray tube voltage regulation system which automatically adapts to line impedance and fluctuations in the network voltage, so as to maintain the x-ray tube current at a maximum value. The x-ray tube current is set by the x-ray tube voltage, the x-ray tube current is regulated so that a maximally allowable line voltage drop is not upwardly exceeded. The x-ray tube current, consequently, always has its maximum value, given the prevailing circuit conditions, so that the tube power is also at a maximum value. The current is set so as to achieve a desired mAs product, which is in turn determined by the radiation dose which the operator desires.

1. Field of the Invention
The present invention is directed to an x-ray generator of the type wherein the x-ray tube voltage and the x-ray tube current are generated and regulated within the x-ray generator.
2. Description of the Prior Art
For an x-ray exposure, the x-ray tube voltage and the x-ray tube current are generated in an x-ray generator, which includes a network connected between the mains voltage and the tube. A current flows from the line to the x-ray tube, which results in a voltage drop across the line impedance. If the line impedance lies outside the specified values, or if the network experiences a significant under-voltage ("brown-out") or a high non-linear distortion factor, in known x-ray generators the voltage drop may be large enough to trigger the under-voltage monitor which is standard in such generators, thereby causing shut-down of the system. This necessitates a re-start of the system with lower power than would normally be used to create an x-ray exposure. If this situation occurs frequently, the operator must work with lower power for a significant time. Since the generation of a suitable x-ray exposure, under given conditions, usually requires a specified radiation dose, which is set by selecting a suitable mAs product. In order to achieve the same product with a lower power, a longer exposure time is needed. If the above situation arises frequently, the operator may be forced to work with lower power for a considerable time.

X-ray generator with x-ray tube voltage regulation for maintaining the x-ray tube current at a maximum value


In an identifying device for performing personal identification using biometrics information such as an iris, face, blood vessel pattern, auricle, fingerprint, palm print, hand print or the like, in order to surely discriminate a living body from a non-living body and to surely preclude illegal use by impersonation using a forged fingerprint or the like, a biometrics information input section samples/inputs biometrics information for verification as image information from a living body portion relatively moving with respect to this biometrics information input section, and living-body detection surfaces in a living-body detecting means is arranged in contact with or in the proximity to the living body portion being moved with respect to the biometrics information input section so as to input the biometrics information for verification.

Small-sized information equipment including a cellular phone and a Personal Digital Assistant (PDA) has become capable of connection to a network and storage of a large amount of personal information with recent sophistication of functions, and a demand for improvement of security function in such equipment is extremely high.
In order to ensure security in such equipment, personal identification using a password or ID (IDentifiacton) card, which has been widely used, may be employed. However, the password or ID card has a high risk of plagiarism, and realization of more reliable personal identification (identification that a user of equipment is the user himself/herself registered in advance) is in a strong demand. Personal identification by biometrics information is highly reliable and considered to be able to satisfy the above demand. Particularly, use of a fingerprint as the biometrics information is convenient.
When the fingerprint is used as the biometrics information for personal identification, a fingerprint (pattern consisting of ridge lines, which can contact with a sampling surface of a fingerprint sensor, and valley lines, which do not contact with the sampling surface) is sampled by a capacitance type fingerprint sensor or an optical fingerprint sensor from a finger of a person to be identified as image information. Then, by extracting characteristic information (position information on branch points and endpoints, for example) from a foreground of the fingerprint image (ridge line image, for example) and by verifying the extracted characteristic information with registered characteristic information of the person to be identified that was registered in advance, determination is made if the person to be identified is the person himself/herself, that is, personal identification is performed.
A general fingerprint sensor for sampling a fingerprint image from a person to be identified (hereinafter referred to as planar finger sensor in some cases) usually has a sensor surface (sampling surface) larger than the size of a finger. However, in order to mount a fingerprint sensor in small-sized information equipment such as a cellular phone and PDA, the size of the sensor surface is made smaller than that of a finger and a plurality of partial images continuously sampled through the sensor surface are integrated to obtain an image of the entire fingerprint.
Such a situation is handled by a sweep type fingerprint sensor. This sweep type fingerprint sensor has a rectangular sampling surface (sensor surface/image pickup surface) with the length sufficiently shorter than that of a finger and having a small area. Attempts are made such that, by moving a finger with respect to the sampling surface or by moving the sampling surface (fingerprint sensor) with respect to the finger, a plurality of partial images of a fingerprint of the finger is continuously sampled and the entire fingerprint image of the finger is reconfigured from the sampled plural partial images. Note that, the above relative movement of the finger with respect to the sampling surface is referred to as "Sweep". Moreover, information of minutiae (branch points or end points of ridge lines) is extracted/generated from the reconfigured fingerprint image, and the above personal identification is performed based on the information.
In a personal identification system using a fingerprint as above, illegal use using a forged fingerprint has been pointed out as one of problems in realizing more reliable personal identification. That is, in the system using fingerprints, there is a possibility that a finger having a forged fingerprint is artificially made and impersonation might be committed using the artificial finger. And the illegal use by impersonation might undermine reliability of the system.
When silicon or rubber is used as a material for the artificial finger, since these materials do not conduct electricity and a capacitance type fingerprint sensor does not have a function to sample a fingerprint image from an artificial finger made of silicon or an artificial finger made of rubber, the above illegal use can not be committed. The optical fingerprint sensor can not sample a fingerprint image from an artificial finger made of silicon or an artificial finger made of rubber in principle, either.
However, it is pointed out that, if gummy substance (substance having the same water content as a human finger, obtained by gelatinizing a gelatin solution) with composition extremely close to that on a human skin is used as the material for the artificial finger, since the gummy substance conducts electricity, the capacitance type fingerprint sensor or optical fingerprint sensor can sample a fingerprint image from the artificial finger made of gummy substance, which enables illegal use by impersonation.
Then, the above-mentioned planar fingerprint sensor has employed a method to detect if a finger, for which a fingerprint image is being sampled, is a living body or not while the finger is placed on a sensor surface of the planar fingerprint sensor to prevent impersonation (illegal use using a forged fingerprint) by an artificial finger (forged fingerprint (See the following Patent Documents 1 to 8, for example).
Patent Document 1: Japanese Patent Laid-Open (Kokai) No. Sho 62-74173
Patent Document 2: Japanese Patent Laid-Open (Kokai) No. Hei 2-110780
Patent Document 3: Japanese Patent Laid-Open (Kokai) No. Hei 2-144684
Patent Document 4: Japanese Patent Laid-Open (Kokai) No. Hei 2-144685
Patent Document 5: Japanese Patent Laid-Open (Kokai) No. Hei 2-259969
Patent Document 6: Japanese Patent Laid-Open (Kokai) No. Hei 6-187430
Patent Document 7: Japanese Patent Laid-Open (Kokai) No. Hei 11-45338
Patent Document 8: Japanese Patent Laid-Open (Kokai) No. 2000-172833
On the other hand, with the above-mentioned sweep type fingerprint sensor, the finger should be moved with respect to the rectangular sampling surface in a strip state to sample a fingerprint image, and the sweep type fingerprint sensor can not detect if the finger, for which the fingerprint is to be sampled, is a living body or not with the methods disclosed in the above Patent Documents 1 to 8. A detection surface for detecting a living body may be provided in addition to the rectangular sampling surface so that fingerprint sampling and living-body detection can be performed separately. However, in this case, illegal use by impersonation is possible by using a real finger (living body) on the detection surface while using a forged fingerprint on the rectangular sampling surface. Therefore, reliable detection on whether the finger, for which a fingerprint image is just being sampled, on the rectangular sampling surface of the sweep type fingerprint sensor is a living body or not is in demand.
Moreover, personal identification using image information of iris, face, auricle or the like as biometrics information is known other than the personal identification using a fingerprint as biometrics information. In this case, a picture of an iris, face, auricle or the like is taken by a camera and characteristic information is extracted from the captured image, and the extracted characteristic information is verified with registered characteristic information of a person to be identified, which is registered in advance, so as to determine if the person to be identified is the person himself/herself, that is, to perform personal identification. However, even in this personal identification, illegal use by impersonation is possible by presenting a display device displaying a high-definition dynamic image or a still image or presenting a printed matter on which a high-definition image is printed out. Therefore, even in the case of personal identification using image information of iris, face, auricle or the like as biometrics information, reliable detection on whether the iris, face, auricle or the like being captured by a camera as biometrics information is a forged one such as a display or a printed matter is in demand.
The present invention was made in view of the problems stated above and has an object to surely preclude illegal use by impersonation using a forged fingerprint or the like and to realize more reliable personal identification by enabling reliable detection on whether a living body portion, for which a fingerprint image is being sampled, for example by a sweep type fingerprint sensor, is a living body or not, so that a non-living body such as an artificial finger made of gummy substance or the like and a living body can be surely discriminated.
Moreover, the present invention has an object to surely preclude illegal use by impersonation using a forged one or the like and to realize more reliable personal identification by enabling reliable detection on whether an iris, face, auricle or the like being captured by a camera, for example, as biometrics information is a forged one such as a display or a printed matter so that a forged one and a living body can be surely discriminated.

Identifying device by biometrics information


The present invention discloses boronic acids and esters of phospholipid ether analogs and methods for their synthesis and use. The boronic acids and esters of phospholipid ether analogs described herein can be used in treating cancer and in particular can be used in conjunction with radiation therapy, such as external beam radiation therapy and neutron capture therapy to specifically target and kill cancer cells.

Cancer is a class of diseases characterized by the uncontrolled division of the affected cells and the ability of these cells to spread, either by invasion, the direct growth of the cancer or neoplastic cells into unaffected tissue or by metastatic growth, the implantation of metastatic cells into distant sites. While there are various therapies and pharmaceuticals developed to treat cancer, the variability of the disease, from tissue to tissue and its ability to develop metastatic growths in distant location together with its resistance to drugs and therapies has resulted in an enormous amount of research to identify therapies or drugs that are effective in a wide variety of cancers and that are non-toxic or at least non-fatal to healthy cells.
Phospholipids are the major lipid component of cell membranes. Ether phospholipids are a minor phospholipid subclass differing by having an ether linkage at the C-1 carbon of the glycerol backbone rather than the normal ester bond. Alkyl phosphocholines (APC), for example, hexadecylphosphocholine (HPC), are another subclass of compounds that have shown antineoplastic targeting activity. Assessment of this new class of PLE analogs as cancer treatments in several animal tumor models provided by the inventors revealed that NM404 (18-[4-Iodophenyl]-octadecyl phosphocholine) and similar PLE and APC analogs, specifically accumulate and are selectively retained in primary and/or metastatic tumors. While some compounds such as, fluorodeoxyglucose (FDG) are commonly used in imaging applications for its high uptake in cancer tissues, FDG also accumulates in inflammatory and granulomatous lesions thereby giving false positives, does not accumulate in bone metastases of prostate cancer and further, is rapidly cleared in the urine thereby resulting in a short time frame for use and also in high background in the kidneys and bladder. Further, FDG also has no therapeutic potential and its clinical use is solely as a means of imaging it incorporation into high metabolic tissues. Thus, FDG can not begin to approach the specificity and versatility of PLE and APC analogs.
Further investigation of radioiodinated PLE and APC analogs, such as radioiodinated NM404 has demonstrated, in 37 of 37 models investigated, a remarkable tumor selectivity of these compounds in a wide variety of tumor models. See, for example, U.S. patent application Ser. Nos. 10/906,687, 11/177,740, 11/316,620 and 11/382,645. Due to deficiencies in metabolic phospholipase enzymes in the membranes of malignant tumor cells, the prevailing hypothesis for this specificity is that phospholipid ether analogs become trapped exclusively in tumor cell membranes because of their inability to become metabolized and eliminated by the cancerous cell. Thus, the differential clearance rates of phospholipid ethers from normal cells versus neoplastic tumor cells are responsible for this specificity. Results obtained in a variety tumor models indicate that PLE and APC analogs, such as, NM404 are sequestered and selectively retained by viable tumor cells and localize in both primary and metastatic lesions regardless of anatomic location including those found in lymph nodes.
One recognized treatment for cancer is radiotherapy which uses ionizing radiation to kill cancer cells. Such treatments can be given in a variety of ways, such as X-rays, gamma rays, neutron beams or implanted particles. While radiation therapy is used in over half of all cancer patients it is limited by its inability to specifically and precisely target cancer cells and thereby limit its toxicity to healthy tissue. In an effort to limit radiation administered to healthy tissues during treatment by external radiation, methods for internal radiation treatment are being developed. For example, endocavitary radiation therapy (Endo RT) and endo-luminal RT can be performed on select individual and is preformed by the insertion of a contact X-ray tube into a tumor or into tubular structures such as the bronchi or esophagus to limit the deleterious effect of radiation on healthy cells. However, with both external radiation and with endo radiation therapy the radiation dose is delivered non-specifically to the region proximate to the tumor but not delivered specifically or selectively to the metastatic cells. Further, in an effort to solve the problem of non-specific radiation, radioimmunotherapy—radioactive antibodies—have been developed that are specific for epitopes displayed by neoplastic cells. However, while antibodies have exquisite specificity, their specificity is directed to only to a single cognate epitope which is specific for each neoplastic cell type. Thus, neither of the methods described above are adequate for the systemic administration of cancer therapies specifically directed to neoplastic cells.
Boron neutron capture therapy (BNCT) is a binary radiation therapy having two components each of which, independently, has only minor effects on cells. BNCT utilizes the neutron capture by which a neutron collides with an atomic nucleus, boron, to produce alpha particles, lithium nuclei and ionizing radiation. Both the alpha particle and the lithium ion produce closely spaced ionizations in the vicinity of the reaction, approximately 10 μm, or the diameter of a cell. Therefore, the ability to target and sequester the boron atom in the cancer cell would allow the products of the neutron bombardment to specifically irradiate cancer cells.
External beam radiation therapy is similar to BNCT in that linear accelerators are used to produce a beam of electrons that can be focused to hit a desired target. When the target is an appropriate alloy (such as 10B), collision results in the liberation of gamma radiation. Gamma rays are characterized by a short wavelength and high energy. Due to their high energy, the liberated gamma rays provide lethal radiation only to adjacent tissue.
Currently, one limitation of BNCT and external beam radiation is the ability to specifically target cancer cells and limit the deleterious effects of the radiation in surrounding healthy tissue.

Compositions of phospholipid ether boronic acids and esters and methods for their synthesis and use


A method for producing a color conversion table by which a color image signal to be handled in an image input system is converted to a N bit color image signal to be handled in an image output system, comprising the step of producing a color conversion table from which a N+α bit color output value, exceeding a color gamut of the color image signal to be handled in the image output system can be read out corresponding to a color input value of the color image signal to be handled in the input system.

1. Field of the Invention
The present invention relates to a method of producing a color conversion table for color conversion from the color image signal to be handled in an input system into a color image signal to be handled in an output system, image processing apparatus, method of image processing, image forming apparatus and recording media.
2. Description of Related Art
In recent years, a color printer, color copying machine and combination machine thereof have come into frequent use. In many cases, the color image forming apparatus used in these machines incorporates a 3D color information conversion table (3D Lookup Table; also called the RGB→4 CMYK3D−LUT in the following description) for color conversion from the image information of red (R), green (G) and blue (B) in a signal processing system into the image data of a CMYK signal processing system. This is because the image forming apparatus adopts the structure wherein the operation is performed according to the image data of the CMYK signal processing system.
The RGB→CMYK3D−LUT is created by matrix processing or interpolation arithmetic processing according to the color measurement value of n3 patch documents (XYZ or LAB) wherein patches are arranged so as to increase the intensity of each of the RGB colors, and the scanner signal (RGB). Then the RGB→CMYK3D−LUT is used to convert the RGB signal into the XYZ output signal or Lab output signal.
The Patent Document 1 discloses an image processing apparatus related to the image forming apparatus handling the aforementioned color image data. This image processing apparatus applies processing of color gamut compression to the color reproduction area of an output device for the image data inputted from an input device. The image data subjected to color gamut compression is outputted to the output device.
FIGS. 17A and 17B show the color coordinate system representing an example of the CMY→Lab3D−LUT and RGB→Lab3D−LUT in the conventional Lab color coordinate system.
The vertical axis in FIG. 17A represents a brightness L* axis, and the horizontal axis denotes a chromaticity b* axis. Chromaticity a* axis is found at the intersection between the brightness L* axis and chromaticity b* axis. In FIG. 17A, the first lattice pattern I corresponds to the RGB→Lab3D−LUT H wherein the color image signals R, G and B of the RGB signal processing system is represented in 256 gradations. The contour line of the lattice pattern I shows the color gamut boundary that can be handled by the RGB signal processing system.
In this example, the lattice pattern. II displayed so as to be included in the lattice pattern I corresponds-to the CMY→Lab3D−LUT wherein the color image signals C, M, Y and K handled by the CMYK signal processing system are expressed in 256 gradations. The contour line of the lattice pattern II shows the color gamut boundary (hereinafter also referred to as "printer color gamut") handled by the CMYK signal processing system. In this displayed example, if that the area inside the printer color gamut is defined as "inside the printer color gamut", and the area outside the printer color gamut as "outside the printer color gamut", a decision step is taken to determine if a target for arithmetic processing is located inside or outside the printer color gamut.
The circle showed in a broken line of FIG. 17B is an enlarged view of the area close to the printer color gamut in FIG. 17A. The RGB→Lab3D−LUT shown in FIG. 17B exhibits the case when the lattice point is located across the printer color gamut. In this example, the lattice points a and b are located outside the printer color gamut. The lattice points c and d are found inside the printer color gamut. This is the case where a non-lattice point (arithmetic processing reference point) e is given in the area enclosed by these four lattice points a, b, c and d and outside the printer color gamut. In this case, in the image processing apparatus disclosed on Patent Document 1, when the input RGB value outside the printer color gamut is subjected to color conversion and interpolation as shown in FIG. 17B, then processing of compression is applied by the output CMYK values of four lattice points a, b, c and d, so that interpolation is carried out inside the printer color gamut.
FIG. 18 is a flowchart representing and example of the conventional RGB→CMYK3D−LUT. In the Step F1 of the flowchart shown in FIG. 18, the input data and Lab data are read out from a predetermined image memory and are displayed on the RAM. The input data and Lab data are displayed on the RAM, so that the RGB→Lab3D−LUT is created.
CMY data is read out from the image memory in the Step F2, and is displayed on the RAM. The CMY data is displayed on the RAM, so that the CMYK→4 Lab4D−LUT is created. Then the system goes to the Step F3 and the CMY→Lab3D−LUT is created from the CMYK→Lab4D−LUT, based on the GCR algorithm.
After that, the system goes to the Step F4 to set the Lab value obtained in the Lab coordinate system. In this case, the CMY value corresponding to each Lab value of the RGB→Lab3D−LUT is calculated from the CMY→Lab3D−LUT. Then the system goes to the Step F5 to search the CMY→Lab3D−LUT to find out the Lab value preset (inputted in advance). A decision step is taken to determine if this Lab value is located inside or outside the color gamut area of the CMY→Lab3D−LUT (color gamut area outside/inside decision step). If it has been determined in this decision step that the target of arithmetic processing Pin is located outside the printer color gamut, the system goes to Step F6 where the process of compression is carried out.
If it has been determined in the aforementioned Step F5 that the target of arithmetic processing pin is located inside the printer color gamut, the system goes to Step F7 where CMY value is found out by checking the CMY→Lab3D -LUT using the preset Lab value. The CMY value corresponding to this step of checking is calculated. Then the system goes to Step F8, where a decision step is taken to determine if the process of calculating the CMY value corresponding to the preset (inputted in advance) Lab value has been completed or not. If it has not yet completed, the system goes back to Step F4 and the aforementioned procedure is repeated. Upon completion of calculation of the CMY values for all the Lab values, the RGB→CMYK3D−LUT is created. Then the system goes to Step F9 where the RGB→CMY3D−LUT is converted into the RGB→CMYK3D−LUT by the GCR. This allows the RGB→CMYK3D−LUT to be created.
[Patent Document 1] Official Gazette of Japanese Patent Tokkai 07-236069
The conventional color image forming apparatus has the following problems:
i. In the color image forming apparatus to which the image processing apparatus disclosed in the Patent Document 1 applied, if the scanner color gamut is wider than the printer color gamut and the target of arithmetic processing (point e) is situated outside the printer color gamut, then the point e (the target of arithmetic processing) outside the printer color gamut is compressed inside the printer color gamut, as shown in FIG. 17B. Thus, when the input RGB value outside the printer color gamut has been converted by a color conversion interpolator, it will be inside the printer color gamut.
ii. In this connection, if the target of arithmetic processing outside the printer color gamut is interpolated inside the color gamut boundary, color difference may be further increased close to the color gamut boundary. Thus, effective use of the printer color gamut cannot be achieved in some cases.
iii. If the target of arithmetic processing outside the printer color gamut is interpolated inside the printer color gamut, unwanted colors may be mixed and color image quality may deteriorate due to color mixture.

Method of producing a color conversion table, image processing apparatus, method of image processing, image forming apparatus and recording media

Konica Minolta Business Technologies, Inc.