Systems and methods are disclosed herein to detect pixels exhibiting anomalous behavior in captured image frames. In some examples, temporal anomalous behavior may be identified, such as flickering pixels exhibiting large magnitude changes in pixel values that vary rapidly from frame-to-frame. In some examples, spatial anomalous behavior may be identified, such as pixels exhibiting values that deviate from an expected linear response in comparison with other neighbor pixels.

Various types of imaging devices are used to capture images (e.g., image frames) in response to electromagnetic radiation received from desired scenes of interest. Typically, these imaging devices include sensors arranged in a plurality of rows and columns, with each sensor providing a corresponding pixel of a captured image frame.
From time to time, one or more pixels may exhibit anomalous behavior due to hardware imperfections, manufacturing tolerances, and/or other causes. For example, some pixels may appear to flicker from frame-to-frame. As another example, some pixels may deviate from an expected response in comparison with other pixels. Such anomalies can be distracting and provide a misleading representation of the imaged scene.
Although anomalous pixels may sometimes be recognizable by a human being viewing the resulting image frames, it is generally impractical and cumbersome to rely on human detection. Moreover, existing machine-based approaches are frequently unsatisfactory in achieving reliable detection of anomalous pixels in an efficient and rapid manner.

This patent is subject to a terminal disclaimer.


A method for preventing the unwanted maloperation of a protective relay system that is caused by the imprecise detection of an actual secondary current value resulting from a measured secondary current being distorted comprises the steps of calculating difference values for sampled secondary currents; comparing absolute values of the difference values with a predetermined critical value, and determining a saturation starting moment of a current transformer when one of the absolute values exceeds the predetermined critical value; obtaining a magnetizing current at the saturation starting moment using the difference values if the saturation starting moment is determined, and obtaining a magnetic flux value in a steel core of the current transformer from a magnetization curve using the magnetizing current; calculating a magnetic flux value at a time after the saturation starting moment using a secondary current value measured at that time and the magnetic flux value obtained at the saturation starting moment so as to obtain a secondary current value consistent with a current transformation ratio at that time; obtaining a magnetizing current at that time from the magnetization curve using the magnetic flux value calculated at that time; and obtaining the secondary current value consistent with the current transformation ratio by adding the obtained magnetizing current and the measured secondary current value.

A current transformer is an apparatus for measuring a current flowing through a power system and inputting the measured current to a protective relay system. As shown in FIG. 1, the current transformer comprises a core 34 for concentrating a magnetic flux generated by a primary current flowing through a line 32 and a secondary coil 36 adapted to surround the core 34 for generating a secondary current using a magnetic flux induced to the core 34. A current flowing through the line 32 functioning as a primary coil induces a current proportional to the former current to the secondary coil 36, and the magnitude of current is determined according to a current transformation ratio. In this case, a steel core current transformer, in which the core 34 is steel, is chiefly used to maximize an interlinkage magnetic flux between the line 32 and the secondary coil 36.
FIG. 2 illustrates a schematic equivalent circuit of a current transformer. In this drawing, Lm denotes a magnetizing inductance, im denotes a magnetizing current, i1 denotes a secondary current (consistent with a current transformation ratio) induced to a secondary side by a primary current, and i2 denotes an actually measured secondary current. The magnetizing inductance Lm is not a constant, but has different values depending upon magnetizing currents. In particular, if a magnetic flux increases and exceeds a specific limit, the magnetizing inductance Lm varies considerably, which results from a variation in the internal state of a current transformer. In such a case, it is stated that the current transformer is saturated.
Since the magnitude of the magnetizing current im is small during normal operations, the measured primary current value of the current transformer is proportional to the primary current value thereof, so that a precise primary current value can be obtained from the measured secondary current value, thus causing no problem. However, if the magnetizing inductance value of the current transformer varies considerably by the saturation of the current transformer, the secondary current value varies considerably. If this phenomenon is described based on the equivalent circuit of FIG. 2, at the time of saturation, Lm value considerably decreases and, therefore, the magnetizing current im increases, so that the difference between the actually measured secondary current i2 and the secondary current i1 consistent with the current transformation ratio increases. Accordingly, a correlation between the actually measured secondary current i2 and the secondary current i1 becomes different after saturation. Meanwhile, the current transformer detects the value of a current flowing through the line using i2 even after saturation, so that it is imprecisely determined that the value of the current flowing through the line has decreased, thus causing the delay of the operation time of the protective relay system and the unwanted maloperation of the protective relay system.
FIGS. 6a and 6b are examples of magnetization curves showing correlations between magnetizing currents and interlinkage fluxes before and after saturation. FIG. 6a shows the transition of a magnetization curve in unsaturated and saturated regions. The slope of the magnetization curve represents magnetizing inductances Lm. FIG. 6b shows an example of an actual magnetization curve. As shown in FIGS. 6a and 6b, magnetizing inductances are considerably different before and after saturation.
For a conventional technology of compensating for current distortion resulting from the saturation of a current transformer, which is a main reason for the unwanted maloperation of a protective relay system, and obtaining a secondary current consistent with an actual current transformation ratio, there is proposed a method of calculating a magnetic flux in a steel core constituting part of a current transformer at the time of saturation and compensating for the distorted secondary current using the calculated magnetic flux to obtain a secondary current consistent with a current transformation ratio. However, the conventional method can be applied only to the case where a remanent magnetic flux does not exist at an early stage. In the case where a remanent magnetic flux exists at an early stage, the application of the conventional method is limited, if the initial value of the remanent magnetic flux is not known. In most applications, it is difficult to measure and estimate the value of the remanent magnetic flux using existing technology, so that the above-described disadvantage becomes fatal.

Method for compensating secondary current of current transformers


The present invention describes a method for producing an L-amino acid comprising culturing a microorganism having an ability to produce an L-amino acid in a medium, whereby the L-amino acid accumulates in the medium, and collecting the L-amino acid from the medium, whereby said microorganism comprises a methanol-utilizing bacterium having the Entner-Doudoroff pathway in which 6-phosphogluconate dehydratase activity and/or 2-keto-3-deoxy-6-phosphogluconate aldolase activity is enhanced.

1. Technical Field of the Invention
The present invention relates to a method for producing an L-amino acid, and a bacterium used therefor. More precisely, the present invention relates to a methane-utilizing bacterium having improved L-amino acid producing ability and a method for producing an L-amino acid utilizing the bacterium.
2. Description of the Related Art
Conventionally, L-amino acids such as L-lysine, L-glutamic acid, L-threonine, L-leucine, L-isoleucine, L-valine and L-phenylalanine are produced by fermentation utilizing coryneform bacteria belonging to the genus Brevibacterium, Corynebacterium or Microbacterium (Amino Acid Fermentation, the Japan Scientific Societies Press [Gakkai Shuppan Center], pp. 195–215, 1986). Furthermore, microorganisms of the genus Bacillus, Streptomyces, Penicillium (U.S. Pat. No. 3,220,929), Pseudomonas, Arthrobacter, Serratia, Aerobacter, Candida (U.S. Pat. No. 3,563,857), Escherichia (Japanese Patent Laid-open (Kokai) No. 5-244970) and the like can also be utilized in the production of L-amino acids.
To improve productivity of these microorganisms, bacterial strains isolated from nature, or artificial mutants of the bacterial strains, have been used. Furthermore, various techniques have been disclosed for increasing L-amino acid producing ability by enhancing L-amino acid biosynthesis enzymes using recombinant DNA techniques (U.S. Pat. Nos. 4,278,765, 4,346,170 and 6,040,160).
Methanol is a raw material often used in fermentation which is inexpensive and widely and easily available. Methods for producing L-amino acids by fermentation of methanol have been known using microorganisms that belong to the genus Achromobacter or Pseudomonas (Japanese Patent Publication (Kokoku) No. 45-25273), Protaminobacter (Japanese Patent Laid-open Publication (Kokai) No. 49-125590), Protaminobacter or Methanomonas (Japanese Patent Laid-open (Kokai) No. 50-25790), Microcyclus (Japanese Patent Laid-open (Kokai) No. 52-18886), Methylobacillus (Japanese Patent Laid-open (Kokai) No. 4-91793), Bacillus (Japanese translation of PCT international application Patent (Kohyo) No. 3-505284 (WO90/12105)) and the like. The inventors of the present invention to date have developed methods for producing L-amino acids using Methylophilus bacteria employing breeding techniques utilizing artificial mutagenesis and recombinant DNA (WO00/61723).
Techniques are also known for enhancing L-amino acid producing ability by introducing genes coding for glycolytic enzymes such as glucose-6-phosphate isomerase (International Patent Publication No. 01/02542 (WO 01/02542 A1)), fructose phosphotransferase (International Patent Publication No. 01/48146 (WO 01/48146 A1)) and enolase (International Patent Publication No. 01/02543 (WO 01/02543 A1)).
Many methanol-utilizing bacteria including enterobacteria have the Entner-Doudoroff pathway as one of their methanol metabolic pathways. This pathway involves 6-phosphogluconate dehydratase (abbreviated as "EDD" hereinafter), which catalyzes a reaction to produce 2-keto-3-deoxy-6-phosphogluconate from 6-phosphogluconic acid, and 2-keto-3-deoxy-6-phosphogluconate aldolase (abbreviated as "EDA" hereinafter), which cleaves 2-keto-3-deoxy-6-phosphogluconate to produce glyceraldehyde-3-phosphate and pyruvic acid. Genes coding for EDD and EDA have been cloned from Escherichia coli, Zymomonas mobilis and so forth, and their nucleotide sequences have been reported (Mol. Microbiol. 5, 2901–2911; J. Bacteriol. 172 (12), 7227–7240 (1990)). The nucleotide sequences of the gene coding for EDD (edd) and the gene coding for EDA (eda) of Escherichia coli are registered as GenBank accession number L20897. Furthermore, the nucleotide sequence of the eda gene of Zymomonas mobilis is registered as GenBank accession number X58364, and the nucleotide sequence of the edd gene is registered as GenBank accession number M60615 M37982 in the database.
There is clearly a need in the art for efficient, low-cost, productive methods of obtaining amino acids for both agricultural and nutritional uses. The relationship between the Entner-Doudoroff pathway and the productivity of L-amino acids has not previously been described. The present invention describes this relationship and a method of exploiting it.

Method for producing L-amino acid using methylotroph


A system and method for clock synchronization and position determination using entangled photon pairs is provided. The present invention relies on the measurement of the second order correlation function of entangled states. Photons from an entangled photon source travel one-way to the clocks to be synchronized. By analyzing photon registration time histories generated at each clock location, the entangled states allow for high accuracy clock synchronization as well as high accuracy position determination.

1. Field of the Invention
This invention relates to clock synchronization and position determination and, more specifically, to a system and method for accurate one way clock synchronization and position determination using entangled photon pairs.
2. Background of the Related Art
Accurate timing and positioning metrological measurements are important for both fundamental research and practical applications. In particular, distant clock synchronization has attracted a great deal of attention in recent years due to its essential role in the Global Positioning system (GPS) and telecommunications.
Modern clocks have been improved to such a level, that the resolution and accuracy of the comparison techniques have become the limiting factors to determine their relative rates and synchronization. There are two standard methods for synchronizing two distant clocks: the classic Einstein protocol and the Eddington slow transportation method. Both methods have certain limitations and difficulties in high accuracy nonlocal synchronization in which relativistic effects, such as the rotating disk problem, have to be taken into consideration. The Einstein protocol is a two-way method and, hence, it requires (1) an accurate knowledge of the one-way speed of light that, until now, has not been measured conclusively on rotating reference systems and (2) the light propagation path to be the same in each direction. The Eddington transportation method relies on the physical movement of a clock, therefore, this method is not practical for space applications.

System and method for clock synchronization and position determination using entangled photon pairs

University of Maryland, Baltimore County


A cache memory device by which a processing speed can be elevated and which comprises a primary cache memory containing two primary ways of WAY0 and WAY1 each retaining a bit LRU0 and a bit LRU1 taking either a value 0 or 1 together with data and an address, a primary old way determining circuit for determining, on the basis of patterns of the bit LRU0 and the bit LRU1, which is an old way retaining data which has not been accessed for the longest period of time in the primary ways WAY0 and WAY1, and a primary cache control circuit inverting only the bits (the bit LRU0 or the bit LRU1) retained in the old way which has been accessed.

The present invention relates to a cash memory device containing a cash memory of 2 way set associative method, and more particularly to a cash memory device having a function for replacing ways by means of an LRU (Least Recently Used) algorithm and the like.
With progress of computers, more speeding up in access is demanded. In response to such demand, a system provided with a cash memory device composed of cash memories thereby to intend speeding up in accessing of data increases. However, there is still a need for a cash memory device having a faster processing speed in these days where processing speed of computer increases dramatically.
In computer system, a cash memory and a cash memory device provided with a cash control section capable of high-speed reading/writing has been heretofore been used for eliminating differences in speed between a CPU and a main memory. In such a cash memory device, data transmission between the CPU and a cash memory (main memory) is carried out in line unit.
As a method for allowing data on a main memory to correspond to a line in a cash memory, there is a set associative method wherein the main memory and the cash memory are divided into a plurality of sets (a set of lines: called by the name of xe2x80x9cwayxe2x80x9d), and a certain data on the main memory shall be disposed on only a line contained in each way which has been previously determined. For example, if there are two ways, it is called by the name of xe2x80x9c2 way set associative methodxe2x80x9d.
Such cash memory holds a part of the data stored in the main memory, it is, for instance, memory of the above-mentioned 2 way set associative method. The cash memory is composed of tag RAM (Random Access Memory) retaining an address representing storage positions of data and data RAM retaining the above described data.
In each of two ways in tag RAM, a bit LRU which is used in determination of an old way is maintained in accordance with LRU algorithm. In LRU algorithm, a way which has not been referred to for the longest period of time in two ways is the one corresponding to the above described old way. Bits LRU retained in two ways, respectively, are used for determining a fact which way is an old way in the two ways.
Furthermore, in either a case where a cash hit which means that data to be read exists in cash memory arises, or a case where replacement which means that the data and addresses in cash memory should be updated arises, a cash control section accesses two ways, respectively, to update an old way, whereby bits LRU retained in the respective ways are updated. As a result, the old way shifts from an either way where cash hit (replacement) arose to the other way.
Meanwhile, as mentioned above, when bits LRU are updated as a result of arising of cash hit or replacement in a conventional cash memory device, a cash control section must access to two ways, respectively. More specifically, in case of updating bits LRU, two times of access are required in such that first, the cash control section accesses to either of two ways, and then, it accesses to the other way. Accordingly, there has been such a problem that a processing speed becomes slow by an amount of period of time required for accessing operations of two times in a conventional cash memory device.
It is an object of the present invention to provide a cash memory device by which a processing speed can be elevated.
In order to achieve the above described object, the invention described in a first aspect of the invention relates to a cash memory device utilizing an algorithm wherein replacement is conducted with respect to an old way retaining data which has not been accessed for the longest period of time, characterized in that the cash memory device is composed of a cash memory (corresponding to a primary cash memory 11 in the first embodiment which will be mentioned hereinafter) containing two ways each retaining bits taking a value 0 or 1 together with data and an address, respectively; an old way determining means (corresponding to a primary old way determining circuit 13 in the first embodiment which will be mentioned hereinafter) for determining which way of the two ways is the above described old way on the basis of patterns of two bits retained in the above described two ways; and a control means (corresponding to a primary cash control circuit 14 in the first embodiment which will be mentioned hereinafter) for inverting only the bits retained in a way which has been accessed in the two ways in the case when the present way which has been accessed is the above described old way, while maintaining values of the bits retained in the present way in the case when the way which has been accessed is not the above described old way.
According to the present invention, in the old way determining means, an old way is determined from two ways on the basis of patterns of two bits in 2-bit composition (combinations of xe2x80x9c0xe2x80x9d and xe2x80x9c1xe2x80x9d). Thus, when either of two ways is accessed, the control means determines whether or not the way which has been accessed is an old way on the basis of a result of determination by the old way determining means, and when the accessed way is an old way, only the bits retained in this accessed way are inverted. Accordingly, bits in the other way which has not been accessed are not inverted. Namely, in this case, the control means accesses one time to only either way of these two ways.
On one hand, when the way which has been accessed is not the above described old way, the control means maintains values of bits retained in this way. Namely, in this case, the control means accesses to neither of these two ways nor the other.
As described above, according to the invention as described in the first aspect of the invention, it is arranged in such that when an old way is accessed, only the bits retained in the old way in two bits which have been retained respectively in two ways are inverted, so that it is sufficient for only one time access in case of updating bits, whereby a processing speed can be elevated in comparison with two times access in the prior art.
Furthermore, a second aspect of the invention relates to the cash memory device as described in the first aspect of the invention, characterized in that when a way which was cash-hit or replaced is the above described old way, the aforesaid control means inverts only the bits retained in the aforesaid way which was cash-hit or replaced, while when the aforesaid way which was cash-hit or replaced is not the above described old way, values of the bits retained in the present way are maintained.
According to the present invention, an old way is determined from two ways on the basis of patterns of two bits in 2-bit composition (combinations of xe2x80x9c0xe2x80x9d and xe2x80x9c1xe2x80x9d) in the old way determining means. Then, when either of two ways is cash-hit or replaced, the control means determines whether or not the way which was cash-hit or replaced is an old way on the basis of a result of determination by the old way determining means, and when the aforesaid way is an old way, only the bits retained in the aforesaid way are inverted. Accordingly, bits retained in the other way are not inverted. Namely, in this case, the control means accesses to only either of two ways one time.
On the other hand, when the way which was accessed is not the aforesaid old way, the control means maintains values of bits retained in the way which was accessed. Namely, in this case, the control means does not accesses to both the ways of these two ways.
As described above, according to the second aspect of the invention, it is arranged in such that when an old way is cash-hit or replaced, only the bits retained in the old way in two bits which have been retained respectively in two ways are inverted. Accordingly, it is sufficient for only one time access in case of updating bits, whereby a processing speed can be elevated in comparison with two times access in the prior art.
Moreover, a third aspect of the invention relates to a cash memory device utilizing an algorithm wherein replacement is conducted with respect to an old way retaining data which has not been accessed for the longest period of time, characterized in that the cash memory device is composed of a cash memory (corresponding to a primary cash memory 11 in the first embodiment which will be mentioned hereinafter) containing two ways each retaining bits taking a value 0 or 1 together with data and an address, respectively; an old way determining means (corresponding to a primary old way determining circuit 13 in the first embodiment which will be mentioned hereinafter) for determining which way of the above described two ways is the above described old way on the basis of patterns of two bits retained in the aforesaid two ways; and a control means (corresponding to a primary cash control 14 in the first embodiment which will be mentioned hereinafter) for inverting only the bits retained in the aforesaid way in the case when the above described replacement has been conducted.
According to the present invention, an old way is determined from two ways based on patterns of two bits in 2-bit composition (combinations of xe2x80x9c0xe2x80x9d and xe2x80x9c1xe2x80x9d) in the old way determining means. When replacement is made with respect to an old way, only the bits retained in the old way are inverted. Therefore, bits in the other way are not inverted. Namely, in this case, the control means accesses to only either way of two ways one time.
As described above, according to the third aspect of the invention, it is arranged in such that when an old way is replaced, only the bits retained in the old way are inverted, so that it is sufficient for only one time access in case of updating bits, whereby a processing speed can be elevated in comparison with two times access in the prior art.
Furthermore, a forth aspect of the invention relates to a cash memory device as described in any one of the first to third aspects of the invention wherein a plurality of the above described cash memories are prepared so as to correspond to their rank levels.
According to the present invention, it is arranged in such that even if a plurality of cash memories are disposed so as to correspond to their rank levels such as upper level and lower level, only the bits retained in an old way are inverted. Accordingly, it is sufficient for only one time access in case of updating bits, whereby a processing speed can be elevated in comparison with two times access in the prior art.


A receiving apparatus includes a receiving unit configured to receive a signal including a program, an acquiring unit configured to acquire information representing a category of the program received by the receiving unit, a volume data generating unit configured to generate volume data related to a controlled volume in accordance with volume control performed when the program is being received by the receiving unit, and a memory unit storing volume data and category data in association with each other. The memory unit is read for retrieving the category data of the program currently being received and the sound volume is automatically set according to the volume data stored in the memory unit which is associated with the category data of the current program.

1. Field of the Invention
The present invention relates to a broadcast receiving apparatus and a broadcast receiving method which receive a broadcast signal to reproduce sound and, more particularly, to a broadcast receiving apparatus and a broadcast receiving method which control a volume of reproduced sound. The invention also relates to a sound reproducing apparatus and a sound reproducing method which reproduce sound on the basis of an input signal and, more particularly, to a sound reproducing apparatus and a sound reproducing method which control a volume of reproduced sound.
2. Description of the Related Art
As is well known, for example, in a television broadcast receiving apparatus or the like, a user can set a sound volume at a predetermined output level with an operation independently of a program to be received. For this reason, a TV program which is being watched is changed from, for example, a "news" program to a "movie" program, a sound volume also changes. Each time the programs are switched, a user must control the sound volume to an appropriate volume.
Jpn. Pat. Appln. KOKAI Publication No. 6-177686 discloses the configuration of a sound reproducing apparatus which automatically controls a sound volume by controlling tone quality while preventing a set volume from changing. However, Jpn. Pat. Appln. KOKAI Publication No. 6-177686 does not describe any measure which can prevent a change in volume occurring when programs are switched.

Broadcast receiving apparatus and method having volume control


An intelligent power supply system for a portable computer, the computer having a central processing unit (CPU), and being operable in response to power supplied from at least two chargeable batteries or an alternating current (AC) adapter, includes means for detachably coupling the batteries to the computer and a PC-CPU for controlling power supply independent of the CPU. The PC-CPU has means for receiving battery select information for controlling power supply and generating a control signal. The power supply system further includes battery control circuit means, connected to the AC adapter and the batteries, for selecting and controlling the AC adapter or one of the batteries based on the control signal. Accordingly, the proper battery for the usage can be installed in the portable computer operable on battery power, and the computer can be operated continuously on the battery power for a long period of time.

The present invention is directed to an ordinary computer, and, particularly, to a portable computer operable on an internal battery. More particularly, the present invention relates to a system and a method of providing concentrated management of the power supply of the portable computer.
Various types of portable computers operable on an internal battery have recently been developed. This type of computer needs to always recognize the power status of a driving power and the statuses of individual units of the computer in both cases where an AC adapter is used and where an internal battery is used. It is also necessary to eliminate various problems originated from power failure including the lower usable state of the internal battery (hereinafter called low battery status) when power is supplied from the battery.
The present applicant has proposed one example of such a portable computer which is disclosed in the prior application Ser. No. 541,978. In brief, according from the disclosed computer, the battery power supply is constituted of a single main battery detachable to the body of the portable computer and an exclusive power controller CPU (PC-CPU) is used to control the charging of the main battery with the power supplied from an AC adapter. According to the portable computer disclosed in the above application, however, the PC-CPU controls a single battery power supply. When a liquid crystal display with a back light (EL-LCD), a plasma display (PDP) or the like is driven on power from the AC adapter, it is always necessary to supply power to the battery via the AC adapter in light of the power dissipation of the display. In addition, a large-capacity battery needs to be installed in the body of the computer. This significantly increases the weight of the overall computer, deteriorating the portability and hindering continuous battery driving over a long period of time.

Intelligent power supply system for a portable computer


A silver halide color photographic lightsensitive material contains a coupler represented by formula (I) below in at least one layer on a support (in this formula, X represents a hydrogen atom or a group which can split off by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent, each of R1 and R2 represents an electron-attracting group having a Hammett""s substituent constant p value of 0.20 or more, and the sum of the p values of R1 and R2 is 0.65 or more, and each of G1 and G2 represents a nitrogen atom or a substituent). A pyrrolotriazole compound represented by formula (I) below is also provided.

This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 11-279838, filed Sep. 30, 1999, the entire contents of which are incorporated herein by reference.
The present invention relates to a pyrrolotriazole compound having a specific structure and a silver halide color photographic lightsensitive material which improves the color reproduction and dye image stability, suppresses various stains, and increases the processing stability by using the pyrrolotriazole cyan coupler.
It is well known that in silver halide color photographic lightsensitive materials, an aromatic primary amine-based color developing agent oxidized by using an exposed silver halide as an oxidizer reacts with couplers to form dyes such as indophenol, indoaniline, indamine, azomethine, phenoxazine, and phenazine, thereby forming images. This photographic scheme uses subtraction color processes and forms color images by yellow, magenta, and cyan dyes.
To form a cyan dye image, a phenol- or naphthol-based coupler is conventionally used. However, dyes formed from these couplers have unpreferable absorption in regions from yellow to magenta and hence deteriorate the color reproduction. So, solving this problem has been desired.
Especially in recent years, demands on so-called digital photography are increasing by which image information is converted into digital information, image processing is performed, and after that, a silver halide color photographic lightsensitive material is exposed on the basis of the information. In this digital photography, a silver halide color photographic lightsensitive material having a wide color reproduction range, in which formed dyes have no such unpreferable absorption as described above, is desired.
Also, reversal films are desired to have high saturation and a wide color reproduction range. However, a method which emphasizes the interlayer effect has drawbacks such as deterioration of the processing dependency. Therefore, it has been required to realize high saturation and wide color reproduction by couplers superior in hue.
As means for solving this problem, heterocyclic compounds as described in, e.g., U.S. Pat. Nos. 4,728,598 and 4,873,183 and European Patent Publication No. 0249453A2 have been proposed. Unfortunately, these couplers have fatal drawbacks such as low coupling activity and low dye image stability. As couplers which have solved these problems, pyrrolotriazole couplers described in U.S. Pat. No. 5,256,526 and European Patent 0545300 have been proposed. Although these couplers are superior in hue and coupling activity, color photographic lightsensitive materials using these couplers have no sufficient dye image stability. So, the couplers must be further improved. Also, the couplers have the problem (so-called blix fading) that the color generation reduces by leuco conversion of a dye (a dye is partially decolored by reduction) during bleach-fixing. Additionally, diverse cyan stains are produced. Furthermore, conventionally known pyrrolotriazole cyan couplers produce a magenta stain with time when processed using formalin.
It is, therefore, an object of the present invention to provide 1): a novel pyrrolotriazole compound having a specific structure, which is useful as a synthetic intermediate of coupler in a silver halide color photographic lightsensitive material and can be used as a useful intermediate of chemical, medicinal or agrichemical organic compound, and to provide 2): a silver halide color photographic lightsensitive material which improves the color reproduction and dye image stability by the use of the pyrrolotriazole cyan coupler and which reduces a cyan stain produced by the reaction with a residual color developing agent, causes blix fading little, minimizes a magenta stain, and improves the processing stability.
The present inventors extensively studied 2-position substituents and split-off groups of pyrrolotriazole-based couplers having good hue and have found that the above problems can be solved by a coupler, represented by the following formula, having an entirely new structure conventionally unknown. That is, the object of the present invention is achieved by the following means.
(1) A silver halide color photographic lightsensitive material comprising at least one layer on a support, wherein the at least one layer contains a coupler represented by formula (I) below:
wherein X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent; each of R1 and R2 represents an electron-attracting group having a Hammett""s substituent constant "sgr"p value of not less than 0.20, the sum of the "sgr"p values of R1 and R2 being not less than 0.65; and each of G1 and G2 represents a nitrogen atom or a substituent represented by formula (II), provided that one of G1 and G2 being a nitrogen atom and the other being a substituent represented by formula (II) below:
wherein R3 represents a member selected from the group consisting of a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, and substituted or nonsubstituted heterocyclic group; R4 represents a hydrogen atom or a substituent bonded by a carbon atom, R3 and R4 being capable of combining to form a ring; R5 represents a substituent, and n represents an integer of 0 to 4,
provided that a group represented by R1, R2, R3, R4, R5, or X may be a divalent group, and thereby the coupler represented by formula (I) may form a polymer, which is a dimer or a higher-order polymer, or may form a homopolymer or a copolymer by combining with a polymeric chain.
(2) The lightsensitive material according to (1), characterized in that the coupler represented by formula (I) is represented by formula (III) below:
wherein X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent; each of R1 and R2 represents an electron-attracting group having a Hammett""s substituent constant "sgr"p value of not less than 0.20, the sum of the "sgr"p values of R1 and R2 being not less than 0.65; R3 represents a member selected from the group consisting of a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, and substituted or nonsubstituted heterocyclic group; R4 represents a member selected from the group consisting of a hydrogen atom, substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, substituted or nonsubstituted acyl group, substituted or nonsubstituted alkyloxycarbonyl group, substituted or nonsubstituted aryloxycarbonyl group and substituted or nonsubstituted carbamoyl group, R3 and R4 being capable of combining to form a ring; and each of R11 to R14 independently represents a hydrogen atom or a substituent.
(3) A pyrrolotriazole compound represented by formula (I) below:
wherein X represents a member selected from the group consisting of a hydrogen atom, halogen atom, 1- to 32-carbon alkyloxy group, 6- to 32-carbon aryloxy group, 1- to 32-carbon alkylthio group, 6- to 32-carbon arylthio group, 2- to 32-carbon heterocyclic thio group, 2- to 32-carbon alkyloxycarbonyloxy group, 7- to 32-carbon aryloxycarbonyloxy group, 1- to 32-carbon carbamoyloxy group, 3- to 32-carbon heterocyclic carbonyloxy group, or 2- to 32-carbon, 5- or 6-membered nitrogen-containing heterocyclic group which bonds to a coupling active position by a nitrogen atom; each of R1 and R2 represents an electron-attracting group having a Hammett""s substituent constant "sgr"p value of not less than 0.20, the sum of the "sgr"p values of R1 and R2 being not less than 0.65; and each of G1 and G2 represents a nitrogen atom or a substituent represented by formula (II), provided that one of G1 and G2 being a nitrogen atom and the other being a substituent represented by formula (II) below:
wherein R3 represents a member selected from the group consisting of a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, and substituted or nonsubstituted heterocyclic group; R4 represents a hydrogen atom or a substituent bonded by a carbon atom, R3 and R4 being capable of combining to form a ring; R5 represents a substituent, and n represents an integer of 0 to 4,
provided that a group represented by R1, R2, R3, R4, R5, or X may be a divalent group, and thereby the coupler represented by formula (I) may form a polymer, which is a dimer or a higher-order polymer, or may form a homopolymer or a copolymer by combining with a polymeric chain.
(4) The pyrrolotriazole compound according to (3), characterized in that the compound represented by formula (I) is represented by formula (III) below:
wherein X represents a member selected from the group consisting of a hydrogen atom, halogen atom, 1- to 32-carbon alkyloxy group, 6- to 32-carbon aryloxy group, 1- to 32-carbon alkylthio group, 6- to 32-carbon arylthio group, 2- to 32-carbon heterocyclic thio group, 2- to 32-carbon alkyloxycarbonyloxy group, 7- to 32-carbon aryloxycarbonyloxy group, 1- to 32-carbon carbamoyloxy group, 3- to 32-carbon heterocyclic carbonyloxy group, or 2- to 32-carbon, 5- or 6-membered nitrogen-containing heterocyclic group which bonds to a coupling active position by a nitrogen atom; each of R1 and R2 represents an electron-attracting group having a Hammett""s substituent constant "sgr"p value of not less than 0.20, the sum of the "sgr"p values of R1 and R2 being not less than 0.65; R3 represents a member selected from the group consisting of a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, and substituted or nonsubstituted heterocyclic group; R4 represents a member selected from the group consisting of a hydrogen atom, substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, substituted or nonsubstituted acyl group, substituted or nonsubstituted alkyloxycarbonyl group, substituted or nonsubstituted aryloxycarbonyl group and substituted or nonsubstituted carbamoyl group, R3 and R4 being capable of combining to form a ring; and each of R11 to R14 independently represents a hydrogen atom or a substituent.
(5) The pyrrolotriazole compound according to (3), characterized in that the compound represented by formula (I) is represented by formula (IV) below:
wherein X represents a member selected from the group consisting of a hydrogen atom, halogen atom, substituted or nonsubstituted alkylthio group, substituted or nonsubstituted arylthio group, substituted or nonsubstituted heterocyclic thio group, substituted or nonsubstituted alkyloxycarbonyloxy group, substituted or nonsubstituted aryloxycarbonyloxy group, substituted or nonsubstituted carbamoyloxy group, and substituted or nonsubstituted heterocyclic carbonyloxy group; R3 represents a member selected from the group consisting of a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, and substituted or nonsubstituted heterocyclic group; R4 represents a member selected from the group consisting of a hydrogen atom, substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, and substituted or nonsubstituted aryl group, R3 and R4 being capable of combining to form a ring; R11 represents a member selected from the group consisting of a substituted or nonsubstituted acylamino group, substituted or nonsubstituted alkylsulfonylamino group, substituted or nonsubstituted arylsulfonylamino group, and nitro group; R12, R13, and R14 can be the same or different and each represents a member selected from the group consisting of a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkyloxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkyloxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkyloxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, and acyl group; R21, R22, R23, R24, and R25 can be the same or different and each represents a member selected from the group consisting of a hydrogen atom, substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, and substituted or nonsubstituted aryl group; and Z represents a non-metallic atom group required to form a 5- to 8-membered ring, the ring being able to be substituted, be a saturated ring, or have a unsaturated bond.
(6) The lightsensitive material according to (1), characterized in that each substituent of the formula (I) is as follows:
X represents a member selected from the group consisting of a hydrogen atom, halogen atom, alkyloxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic thio group, alkyloxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, heterocyclic carbonyloxy group, and 5- or 6-membered nitrogen-containing heterocyclic group which bonds to a coupling active position by a nitrogen atom; each of R1 and R2 represents a member selected from the group consisting of an acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, alkyl halide group, alkoxy halide group, aryloxy halide group, alkylamino halide group, alkylthio halide group, aryl group which is substituted by another electron attracting group having a "sgr"p value of 0.20 or more, heterocyclic group, halogen atom, azo group, and selenocyanate group; G1 and G2 represent a nitrogen atom and the substituent represented by the formula (II), respectively; and each of R3, R4, R5, and n has the same meaning as defined in (1).
(7) The lightsensitive material according to (6), characterized in that each substituent of the formula (I) is as follows:
X represents a hydrogen atom; and each of R1, R2, G1, G2, R3, R4, R5, and n has the same meaning as defined in (6).
(8) The lightsensitive material according to (2), characterized in that each substituent of the formula (III) is as follows:
X represents a hydrogen atom; each of R1 and R2 represents a member selected from the group consisting of an acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, alkyl halide group, alkyloxy halide group, alkylthio halide group, aryloxy halide group, aryl group substituted by two or more another electron-attracting groups having "sgr"p values of 0.20 or more, and 5- to 8-membered heterocyclic group having a nitrogen atom, oxygen atom, or sulfur atom; each of R11, R12, R13, and R14 represents a member selected from the group consisting of a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkyloxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkyloxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkyloxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, and acyl group; and each of R3 and R4 has the same meaning as defined in (2).
(9) The lightsensitive material according to (8), characterized in that each substituent of the formula (III) is as follows:
R3 and R4 combine to form a ring; and each of X, R1, R2, R11, R12, R13, and R14 has the same meaning as defined in (8).
(10) The lightsensitive material according to (1), characterized in that the coupler represented by formula (I) is represented by formula (V) below:
wherein X represents a member selected from the group consisting of a hydrogen atom, halogen atom, substituted or nonsubstituted alkylthio group, substituted or nonsubstituted arylthio group, substituted or nonsubstituted heterocyclic thio group, substituted or nonsubstituted alkyloxycarbonyloxy group, substituted or nonsubstituted aryloxycarbonyloxy group, substituted or nonsubstituted carbamoyloxy group, and substituted or nonsubstituted heterocyclic carbonyloxy group; R3 represents a member selected from the group consisting of a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, and substituted or nonsubstituted heterocyclic group; R4 represents a member selected from the group consisting of a hydrogen atom, substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, and substituted or nonsubstituted aryl group, R3 and R4 being capable of combining to form a ring; R11 represents a member selected from the group consisting of a substituted or nonsubstituted acylamino group, substituted or nonsubstituted alkylsulfonylamino group, substituted or nonsubstituted arylsulfonylamino group, and nitro group; R12, R13, and R14 can be the same or different and each represents a member selected from the group consisting of a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkyloxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkyloxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkyloxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, and acyl group; R21, R22, R23, R24, and R25 can be the same or different and each represents a member selected from the group consisting of a hydrogen atom, substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, and substituted or nonsubstituted aryl group; and Z represents a non-metallic atom group required to form a 5- to 8-membered ring, the ring being able to be substituted, be a saturated ring, or have a unsaturated bond.
(11) The lightsensitive material according to (10), characterized in that each substituent of the formula (V) is as follows:
R3 and R4 combine to form a ring; and each of X, R11, R12, R13, R14, R21, R22, R23, R24, and R25 has the same meaning as defined in (10).
Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out hereinafter.
The present invention will be described in detail below. A Hammett""s substituent constant "sgr"p value used in this specification will be briefly described below. The Hammett""s rule is an empirical rule proposed in 1935 by L. P. Hammett in order to quantitatively argue the effects of substituents on reaction or equilibrium of benzene derivatives. The rule is widely regarded as appropriate in these days. The substituent constants obtained by the Hammett""s rule include a "sgr"p value and "sgr"m value, and these values are described in a large number of general literature. For example, the values are described in detail in J. A. Dean ed., xe2x80x9cLange""s Handbook of Chemistryxe2x80x9d, the 12th edition, 1979 (McGraw-Hill) and xe2x80x9cThe Extra Number of The Domain of Chemistryxe2x80x9d, Vol. 122, pp. 96 to 103, 1979 (Nanko Do), the disclosures of which are incorporated herein by reference. In the present invention, each substituent is restricted or explained by the Hammett""s substituent constant "sgr"p. However, this does not mean that the present invention is limited to substituents having the already known values found in these literature. That is, the present invention includes, of course, substituents having values that fall within the above range when measured on the basis of the Hammett""s rule even if they are unknown in literature. A compound represented by formula (I) or (III) of the present invention is not a benzene derivative. However, the "sgr"p value is used as a measure indicating the electron effect of a substituent, regardless of the substitution position.
In the present invention, the "sgr"p value will be used in this sense in the remainder of the text. Also, xe2x80x9clipophilic nature,xe2x80x9d mentioned in the present invention means that the solubility in water is 10% or less at room temperature.
In this specification, a heterocyclic ring is a ring internally having a hetero atom and can also have aromatic nature. Examples of the hetero atom are N, S, O and P. This heterocyclic ring can further have a substituent. Also, substituents mentioned in this specification and substituents which an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, and heterocyclic ring can have can be any substitutable groups unless specified otherwise. Examples of the substitutable groups are an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, acyl group, acyloxy group, acylamino group, alkyloxy group, aryloxy group, heterocyclic oxy group, alkyloxycarbonyl group, aryloxycarbonyl group, heterocyclic oxy carbonyl group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonamide group, arylsulfonamide group, alkylamino group, arylamino group, alkylsulfinyl group, arylsulfinyl group, alkylthio group, arylthio group, mercapto group, hydroxy group, cyano group, nitro group, hydroxyamino group, and halogen atom.
A cyan coupler represented by formula (I) of the present invention will be described in detail below.
In a cyan coupler of the present invention, X represents a hydrogen atom or a group which can split off by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent. Preferred examples of the group which can split off are a halogen atom, alkyloxy group, aryloxy group, acyloxy group, alkylsulfonyloxy or arylsulfonyloxy group, acylamino group, alkylsulfonamide or arylsulfonamide group, alkyloxycarbonyloxy group, aryloxycarbonyloxy group, alkylthio group, arylthio group, heterocyclic thio group, carbamoylamino group, carbamoyloxy group, heterocyclic carbonyloxy group, 5- or 6-membered nitrogen-containing heterocyclic group, imide group, and arylazo group. These groups can be further substituted by substituents enumerated for R1 and R2 in formula (I) to be described later.
More specifically, examples of X are a hydrogen atom, halogen atom (e.g., a fluorine atom, chlorine atom, and bromine atom), alkyloxy group (e.g., ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methanesulfonylethoxy, and ethoxycarbonylmethoxy), aryloxy group (e.g., 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarbonylphenoxy, 3-acetylaminophenoxy, and 2-carboxyphenoxy), acyloxy group (e.g., acetoxy, tetradecanoyloxy, and benzoyloxy), alkylsulfonyloxy or arylsulfonyloxy group (e.g., methanesulfonyloxy and toluenesulfonyloxy), acylamino group (e.g., dichloroacetylamino and heptafluorobutyrylamino), alkylsulfonamide or arylsulfonamide group (e.g., methanesulfonylamino, trifluoromethanesulfonylamino, and p-toluenesulfonylamino), alkyloxycarbonyloxy group (e.g., ethoxycarbonyloxy and benzyloxycarbonyloxy), aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy), alkylthio group, arylthio group, heterocyclic thio group (e.g., dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, and tetrazolylthio), carbamoylamino group (e.g., N-methylcarbamoylamino and N-phenylcarbamoylamino), carbamoyloxy group (e.g., N,N-diethylcarbamoyloxy, N-ethylcarbamoyloxy, and N-ethyl-N-phenylcarbamoyloxy), heterocyclic carbonyloxy group (e.g., morpholinocarbonyloxy and piperidinocarbonyloxy), 5- or 6-membered nitrogen-containing heterocyclic group (e.g., imidazolyl, pyrazolyl, triazolyl, tetrazolyl, and 1,2-dihydro-2-oxo-1-pyridyl), imide group (e.g., succinimide and hydantoinyl), and arylazo group (e.g., phenylazo and 4-methoxyphenylazo). In addition, X sometimes takes the form of a bis coupler obtained by condensing a 4-equivalent coupler by aldehydes or ketones, as a split-off group bonded via a carbon atom. X can also contain photographically useful groups such as a development inhibitor and development accelerator.
X is preferably a hydrogen atom, halogen atom, 1- to 32-carbon alkyloxy group, 6- to 32-carbon aryloxy group, 1- to 32-carbon alkylthio group, 6- to 32-carbon arylthio group, 2- to 32-carbon alkyloxycarbonyloxy group, 7- to 32-carbon aryloxycarbonyloxy group, 1- to 32-carbon carbamoyloxy group, 3- to 32-carbon heterocyclic carbonyloxy group, or 2- to 32-carbon, 5- or 6-membered nitrogen-containing heterocyclic group which bonds to a coupling active position by a nitrogen atom. X is more preferably a hydrogen atom, halogen atom, alkylthio group, arylthio group, alkyloxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, or heterocyclic carbonyloxy group. X is particularly preferably a hydrogen atom, halogen atom, arylthio group, carbamoyloxy group, or heterocyclic carbonyloxy group. X is further preferably a hydrogen atom or heterocyclic carbonyloxy group, and most preferably, a hydrogen atom.
A cyan coupler of the present invention forms a cyan image because both R1 and R2 are electron-attracting groups having "sgr"p values of 0.20 or more and the sum of the "sgr"p values of R1 and R2 is 0.65 or more. The sum of the "sgr"p values of R1 and R2 is preferably 0.70 or more, and the upper limit is about 2.0.
Each of R1 and R2 is an electron-attracting group having a Hammett""s substituent constant "sgr"p value of 0.20 or more, preferably 0.30 or more. The upper limit of the "sgr"p value is 1.0 or less.
Practical examples of an electron-attracting group having a "sgr"p value of 0.20 or more represented by R1 and R2 are an acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, alkyl halide group, alkoxy halide group, aryloxy halide group, alkylamino halide group, alkylthio halide group, aryl group which is substituted by another electron attracting group having a "sgr"p value of 0.20 or more, heterocyclic group, halogen atom, azo group, and selenocyanate group.
Of groups represented by R1 and R2, those which can further have substituents can further have substituents such as a halogen atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkyloxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkyloxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkyloxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, and acyl group.
More specific examples of substituents of R1 and R2 are a halogen atom (e.g., a chlorine atom and bromine atom), alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group (e.g., a 1- to 32-carbon, straight-chain or branched-chain alkyl group, 7- to 38-carbon aralkyl group, 2- to 32-carbon alkenyl group, 2- to 32-carbon, straight-chain or branched chain alkynyl group, 3- to 32-carbon, straight-chain or branched-chain cycloalkyl group, and 3- to 32-carbon, straight-chain or branched-chain cycloalkenyl group; more specifically, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl, 3-{4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecaneamido}phenyl}propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, and 3-(2,4-di-t-amylphenoxy)propyl), aryl group (e.g., phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, and 4-tetradecaneamidophenyl), heterocyclic group (e.g., imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, and 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkyloxy group (e.g., methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, and 2-methanesulfonylethoxy), aryloxy group (e.g., phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, and 3-methoxycarbamoyl), acylamino group (e.g., acetamide, benzamide, tetradecaneamide, 2-(2,4-di-t-amylphenoxy)butaneamide, 4-(3-t-butyl-4-hydroxyphenoxy)butaneamide, and 2-{4-(4-hydroxyphenylsulfonyl)phenoxy}decaneamide), alkylamino group (e.g., methylamino, butylamino, dodecylamino, diethylamino, and methylbutylamino), anilino group (e.g., phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5-{2-(3-t-butyl-4-hydroxyphenoxy)dodecaneamido}anilino), ureido group (e.g., phenylureido, methylureido, and N,N-dibutylureido), sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino and N-methyl-N-decylsulfamoylamino), alkylthio group (e.g., methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, and 3-(4-t-butylphenoxy)propylthio), arylthio group (e.g., phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, and 4-tetradecaneamidophenylthio), alkyloxycarbonylamino group (e.g., methoxycarbonylamino and tetradecyloxycarbonylamino), sulfonamide group (e.g., methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, and 2-methoxy-5-t-butylbenzenesulfonamide), carbamoyl group (e.g., N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl, and N-{3-(2,4-di-t-amylphenoxy)propyl}carbamoyl), sulfamoyl group (e.g., N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, and N,N-diethylsulfamoyl), sulfonyl group (e.g., methanesulfonyl, octanesulfonyl, benzenesulfonyl, and toluenesulfonyl), alkyloxycarbonyl group (e.g., methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, and octadecyloxycarbonyl), heterocyclic oxy group (e.g., 1-phenyltetrazole-5-oxy and 2-tetrahydropyranyloxy), azo group (e.g., phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, and 2-hydroxy-4-propanoylphenylazo), acyloxy group (e.g., acetoxy), carbamoyloxy group (e.g., N-methylcarbamoyloxy and N-phenylcarbamoyloxy), silyloxy group (e.g., trimethylsilyloxy and dibutylmethylsilyloxy), aryloxycarbonylamino group (e.g., phenoxycarbonylamino), imide group (e.g., N-succinimide, N-phthalimide, and 3-octadecenylsuccinimide), heterocyclic thio group (e.g., 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, and 2-pyridylthio), sulfinyl group (e.g., dodecanesulfinyl, 3-pentadecylphenylsulfinyl, and 3-phenoxypropylsulfinyl), phosphonyl group (e.g., phenoxyphosphonyl, octyloxyphosphonyl, and phenylphosphonyl), aryloxycarbonyl group (e.g., phenoxycarbonyl), and acyl group (e.g., acetyl, 3-phenylpropanoyl, benzoyl, and 4-dodecyloxybenzoyl).
Note that in each of R1 and R2, alkyl of a group having an alkyl portion means straight-chain or branched-chain alkyl or cycloalkyl. Note also that substituted alkyl groups include aralkyl, alkenyl, alkynyl, and cycloalkenyl.
Accordingly, an alkyloxycarbonyl group includes a straight-chain or branched-chain alkyloxycarbonyl group, aralkyloxycarbonyl group, alkenyloxycarbonyl group, alkynyloxycarbonyl group, cycloalkyloxycarbonyl group, and cycloalkenoxycarbonyl group.
R1 and R2 will be described in more detail below. Examples of an electron-attracting group having a "sgr"p value of 0.20 or more are an acyl group (e.g., acetyl, 3-phenylpropanoyl, benzoyl, and 4-dodecyloxybenzoyl), acyloxy group (e.g., acetoxy), carbamoyl group (e.g., carbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N-(4-n-pentadecaneamido)phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, and N-{3-(2,4-di-t-amylphenoxy)propyl}carbamoyl), alkyloxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, iso-propyloxycarbonyl, tert-butyloxycarbonyl, iso-butyloxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, and cyclohexenoxycarbonyl), aryloxycarbonyl group (e.g., phenoxycarbonyl), cyano group, nitro group, dialkylphosphono group (e.g., dimethylphosphono), diarylphosphono group (e.g., diphenylphosphono), diarylphosphinyl group (e.g., diphenylphosphinyl), alkylsulfinyl group (e.g., 3-phenoxypropylsulfinyl), arylsulfinyl group (e.g., 3-pentadecylphenylsulfinyl), alkylsulfonyl group (e.g., methanesulfonyl and octanesulfonyl), arylsulfonyl group (e.g., benzenesulfonyl and toluenesulfonyl), sulfonyloxy group (methanesulfonyloxy and toluenesulfonyloxy), acylthio group (e.g., acetylthio and benzoylthio), sulfamoyl group (e.g., N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, and N,N-diethylsulfamoyl), thiocyanate group, thiocarbonyl group (e.g., methylthiocarbonyl and phenylthiocarbonyl), alkyl halide group (e.g., trifluoromethane and heptafluoropropane), alkyloxy halide group (e.g., trifluoromethyloxy), aryloxy halide group (e.g., pentafluorophenyloxy), alkylamino halide group (e.g., N,N-di-(trifluoromethyl)amino), alkylthio halide group (e.g., difluoromethylthio and 1,1,2,2-tetrafluoroethylthio), aryl group which is substituted by another electron-attracting group having a "sgr"p value of 0.20 or more (e.g., 2,4-dinitrophenyl, 2,4,6-trichlorophenyl, and pentachlorophenyl), heterocyclic group (e.g., 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, 5-chloro-1-tetrazolyl, and 1-pyrrolyl), halogen atom (e.g., chlorine atom and bromine atom), azo group (e.g., phenylazo), and selenocyanate group.
Of these substituents, those which can further have substituents can further have substituents as described above.
Preferred examples of R1 and R2 are a 2- to 32-carbon acyl group, 2- to 32-carbon acyloxy group, 1- to 32-carbon carbamoyl group, 2- to 32-carbon alkyloxycarbonyl group, 7- to 32-carbon aryloxycarbonyl group, cyano group, nitro group, 1- to 32-carbon alkylsulfinyl group, 6- to 32-carbon arylsulfinyl group, 1- to 32-carbon alkylsulfonyl group, 6- to 32-carbon arylsulfonyl group, 0- to 32-carbon sulfamoyl group, 1- to 32-carbon alkyl halide group, 1- to 32-carbon alkyloxy halide group, 1- to 32-carbon alkylthio halide group, 7- to 32-carbon aryloxy halide group, 7- to 32-carbon aryl group substituted by two or more another electron-attracting groups having "sgr"p values of 0.20 or more, and 5- to 8-membered, 1- to 36-carbon heterocyclic group having a nitrogen atom, oxygen atom, or sulfur atom.
More Preferred examples of R1 and R2 are 2- to 32-carbon alkyloxycarbonyl group, nitro group, cyano group, 6- to 32-carbon arylsulfonyl group, 1- to 32-carbon carbamoyl group, and 1- to 32-carbon alkyl halide group. R1 is most preferably a cyano group. R2 is particularly preferably a 2- to 32-carbon alkyloxycarbonyl group, and most preferably, a branched 4- to 32-carbon alkyloxycarbonyl group (particularly a cycloalkyloxycarbonyl group).
In a cyan coupler of the present invention, each of G1 and G2 represents a nitrogen atom or a substituent represented by formula (II). One of G1 and G2 is a nitrogen atom, and the other is a substituent represented by formula (II).
In formula (II), R3 represents a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, or substituted or nonsubstituted heterocyclic group, and R4 represents a hydrogen atom or a substituent bonded by a carbon atom. R5 represents a substituent. n represents an integer of 0 to 4.
More specifically, an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, and cycloalkenyl group represented by R3 are a 1- to 32-carbon, straight-chain or branched-chain alkyl group, 7- to 32-carbon aralkyl group, 2- to 32-carbon alkenyl group, 2- to 32-carbon alkynyl group, 3- to 32-carbon cycloalkyl group, and 3- to 32-carbon cycloalkenyl group. Practical examples are methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl, 3-{4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecaneamido}phenyl}propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, and 3-(2,4-di-t-amylphenoxy)propyl). An aryl group represented by R3 is preferably a 6- to 36-carbon aryl group, and-a monocyclic group is more preferable. Practical examples are phenyl, 4-t-butylphenyl, 2-methylphenyl, 2,4,6-trimethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,6-dichlorophenyl, 2-chlorophenyl, and 2,4-dichlorophenyl. A heterocyclic group represented by R3 is preferably a 5- to 8-membered, 1- to 36-carbon heterocyclic group having a nitrogen atom, oxygen atom, or sulfur atom. A heterocyclic group is more preferably a 5- or 6-membered ring bonded by a nitrogen atom. These rings can also form a condensed ring together with a benzene ring or a hetero ring. Practical examples are imidazolyl, pyrazolyl, triazolyl, piperidino, pyrrolidyl, pyrrolyl, morpholino, pyrazolidyl, and thiazolidyl, and pyrrolidyl is preferable.
Of these substituents, those which can further have substituents can be further substituted by substituents enumerated for R1 and R2 described above.
Preferred examples of R3 are a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, and substituted or nonsubstituted cycloalkenyl group.
R4 represents a hydrogen atom or a substituent bonded by a carbon atom. Examples of the substituent bonded by a carbon atom are a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, substituted or nonsubstituted acyl group, substituted or nonsubstituted alkyloxycarbonyl group, substituted or nonsubstituted aryloxycarbonyl group, and substituted or nonsubstituted carbamoyl group.
More specifically, a hydrogen atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, and cycloalkenyl group represented by R4 are a 1- to 32-carbon, straight-chain or branched-chain alkyl group, 7- to 32-carbon aralkyl group, 2- to 32-carbon alkenyl group, 2- to 32-carbon alkynyl group, 3- to 32-carbon cycloalkyl group, and 3- to 32-carbon cycloalkenyl group. Practical examples are methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl, 3-{4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecaneamido}phenyl}propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, and 3-(2,4-di-t-amylphenoxy)propyl). An aryl group represented by R4 is preferably a 6- to 36-carbon aryl group, and a monocyclic group is more preferable. Practical examples are phenyl, 4-t-butylphenyl, 2-methylphenyl, 2,4,6-trimethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,6-dichlorophenyl, 2-chlorophenyl, and 2,4-dichlorophenyl. An acyl group represented by R4 is preferably a 2- to 32-carbon acyl group. Practical examples are acetyl, pivaloyl, octanoyl, and benzoyl. Examples of an alkyloxycarbonyl group, aryloxycarbonyl group, and carbamoyl group are those described above as groups which substitute R1 and R2.
Of these substituents, those which can further have substituents can be further substituted by substituents enumerated as groups which substitute R1 and R2 described above.
Preferred examples of R4 are a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, and substituted or nonsubstituted aryl group.
R3 and R4 can combine to form a 5- or 6-membered ring bonded by a nitrogen atom. Practical examples are imidazolyl, pyrazolyl, triazolyl, piperidyl, piperidino, pyrrolidinyl, pyrrolyl, morpholyl, morpholino, pyrazolidinyl, thiazolidinyl, pyrazolinyl, and piperadinyl. These rings can form a condensed ring together with a benzene ring or a hetero ring.
As R3 and R4, substituents which form a ring structure are preferred to those which do not. Of these substituents, groups forming a 6-membered ring bonded by a nitrogen atom are preferable. Of these groups, morpholino, piperadinyl substituted by an acyl group, piperidino, and piperidino substituted by a carboxyl group are preferable.
Examples of R5 are a halogen atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkyloxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkyloxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkyloxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, and acyl group.
Practical examples of R5 are groups described above as groups which substitute R1 and R2.
Of these substituents, those which can further have substituents can be further substituted by substituents enumerated as groups which substitute R1 and R2 described above.
Preferred examples of R5 are an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, cyano group, nitro group, acylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkyloxycarbonylamino group, sulfonamide group (alkylsulfonylamino group and arylsulfonylamino group), carbamoyl group, sulfamoyl group, sulfonyl group, alkyloxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, and acyl group.
R5 is more preferably a nitro group (particularly useful as intermediate of coupler in a silver halide color photographic lightsensitive material), substituted or nonsubstituted, 2- to 32-carbon acylamino group, substituted or nonsubstituted, 1 to 32-carbon alkylsulfonylamino group, or substituted or nonsubstituted, 6- to 40-carbon arylsulfonylamino group. R5 is most preferably a nitro group or a 6- to 40-carbon arylsulfonylamino group having a substituent. The substituent, which the arylsulfonylamino group has, is preferably a 1- to 32-carbon alkoxy group, 1- to 32-carbon alkyl group, 1- to 32-carbon sulfonylamino group, 1- to 32-carbon acylamino group, or halogen atom.
n is an integer of 0 to 4, preferably 1 or 2, and most preferably, 1.
In a cyan coupler represented by formula (I), a group represented by R1, R2, R3, R4, R5, or X can be a divalent group, and thereby the coupler represented by formula (I) can form a polymer, which is a dimer or a higher-order polymer, or can form a homopolymer or a copolymer by combining with a polymeric chain. In the case of forming a polymer, monomer, that is, the coupler represented by formula (I) can be the same or different. In the case of forming a homopolymer or a copolymer by combining with a polymeric chain, its typical example is a homopolymer or copolymer of an addition polymer ethylene type unsaturated compound having a cyan coupler moiety represented by formula (I). When this is the case, one or more types of cyan color-forming repeating units having a cyan coupler moiety represented by formula (I) can be contained in the polymer. Alternatively, the polymer can be a copolymer containing one or more types of non-color-forming ethylene type monomers as copolymerization components. The number of the cyan color-forming repeating unit having a cyan coupler moiety represented by formula (I) is preferably 3 to 1,000, and more preferably, 10 to 100. The unit is more specifically represented by formula (P) below.
In formula (P), R represents a hydrogen atom, 1- to 4-carbon alkyl group, or chlorine atom, A represents xe2x80x94CONHxe2x80x94, xe2x80x94COOxe2x80x94, or a substituted or non-substituted phenylene group, B represents a substituted or nonsubstituted alkylene group, phenylene group, or aralkylene group, and L represents xe2x80x94CONHxe2x80x94, xe2x80x94NHCONHxe2x80x94, xe2x80x94NHCOOxe2x80x94, xe2x80x94NHCOxe2x80x94, xe2x80x94OCONHxe2x80x94, xe2x80x94NHxe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94OCOxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94NHSO2xe2x80x94, or xe2x80x94SO2NHxe2x80x94. Each of a, b, and c represents 0 or 1. Q represents a cyan coupler moiety in which a hydrogen atom splits off from R1, R2, R3, R4, R11 to R14, or X in a compound represented by formula (III). A polymer is preferably a copolymer of a cyan-forming monomer represented by a coupler unit of formula (III) and a non-color-forming, ethylene-type monomer which does not couple with an oxidation product of an aromatic primary amine developing agent.
Examples of the non-color-forming, ethylene-type monomer which does not couple with an oxidation product of an aromatic primary amine developing agent are acrylic acid, xcex1-chloroacrylic acid, xcex1-alkylacrylic acid (e.g., methacrylic acid), amide or ester derived from these acrylic acids (e.g., acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methylacrylate, ethylacrylate, n-propylacrylate, n-butylacrylate, t-butylacrylate, iso-butylacrylate, 2-ethylhexylacrylate, n-octylacrylate, laurylacrylate, methylmethacrylate, ethylmethacrylate, n-butylmethacrylate, and xcex2-hydroxymethacrylate), vinyl ester (e.g., vinyl acetate, vinyl propionate, and vinyl laurate), acrylonitrile, methacrylonitrile, an aromatic vinyl compound (e.g., styrene and its derivative such as vinyltoluene, divinylbenzene, vinylacetophenone, and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (e.g., vinyl ethyl ether), maleic ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine.
Acrylic ester, methacrylic ester, and maleic ester are particularly preferable. Two or more types of these non-color-forming, ethylene type monomers can be used together. For example, it is possible to use methylacrylate and butylacrylate, butylacrylate and styrene, butylmethacrylate and methacrylic acid, and methylacrylate and diacetoneacrylamide.
As is well known in the field of polymer couplers, an ethylene-based unsaturated monomer to be copolymerized with a vinyl-based monomer corresponding to formula (I) described above can be so selected as to have good effects on the physical properties and/or chemical properties of a copolymer formed, e.g., the solubility, the compatibility with a binder, such as gelatin, of a photographic colloid composition, the flexibility, and the thermal stability.
To make a silver halide photosensitive material, preferably a red-sensitive silver halide emulsion layer to contain a cyan coupler of the present invention, the use of a so-called incorporated coupler is preferable. For this purpose, at least one group of R1, R2, R3, R4, R5, and X is preferably a so-called ballast group (having a total number of carbon atoms of preferably 10 or more). The total number of carbon atoms of the ballast group is more preferably 10 to 50. Particularly preferably, R3, R4, and R5 have a ballast group.
An especially favorable combination as a cyan coupler represented by formula (I) of the present invention is that x is a hydrogen atom, R1 is a cyano group, R2 is a branched 4- to 32-carbon alkyloxycarbonyl group, G1 is a nitrogen atom, R3 and R4 form a ring structure, preferably 6-membered heterocyclic ring, and R5 is a nitro group, substituted or nonsubstituted, 2- to 32-carbon acylamino group, substituted or nonsubstituted, 1- to 32-carbon alkylsulfonylamino group, or substituted or nonsubstituted, 6- to 40-carbon arylsulfonylamino group. n is particularly preferably 1.
The most favorable combination as a cyan coupler represented by formula (I) of the present invention is that X is a hydrogen atom, R1 is a cyano group, R2 is a 6- to 32-carbon cycloalkyloxycarbonyl group, G1 is a nitrogen atom, R3 and R4 form a ring structure, preferably 6-membered heterocyclic ring, and R5 is a nitro group or a substituted or nonsubstituted, 6- to 40-carbon arylsulfonylamino group. n is particularly preferably 1.
Of couplers represented by formula (I), a coupler having a structure represented by formula (III) is preferable.
A cyan coupler represented by formula (III) of the present invention will be described in detail below. In formula (III), X, R1, R2, R3, and R4 have the same meanings as X, R1, R2, R3, and R4 in formula (I) described above, and preferred examples of these X, R1, R2, R3, and R4 are also the same.
Each of R11 to R14 represents a hydrogen atom or a substituent. Examples of the substituent are a halogen atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkyloxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkyloxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkyloxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, and acyl group.
Practical examples of R11 to R14 are groups enumerated above as groups which substitute R1 and R2 in formula (I) described above.
Preferred examples of R11 to R14 are a hydrogen atom, substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, substituted or nonsubstituted heterocyclic group, cyano group, nitro group, substituted or nonsubstituted acylamino group, substituted or nonsubstituted anilino group, substituted or nonsubstituted ureido group, substituted or nonsubstituted sulfamoylamino group, substituted or nonsubstituted alkylthio group, substituted or nonsubstituted arylthio group, substituted or nonsubstituted alkyloxycarbonylamino group, substituted or nonsubstituted sulfonamide group (alkylsulfonylamino group and arylsulfonylamino group), substituted or nonsubstituted carbamoyl group, substituted or nonsubstituted sulfamoyl group, substituted or nonsubstituted sulfonyl group, substituted or nonsubstituted alkyloxycarbonyl group, substituted or nonsubstituted heterocyclic oxy group, substituted or nonsubstituted acyloxy group, substituted or nonsubstituted carbamoyloxy group, substituted or nonsubstituted aryloxycarbonylamino group, substituted or nonsubstituted imide group, substituted or nonsubstituted heterocyclic thio group, substituted or nonsubstituted sulfinyl group, substituted or nonsubstituted phosphonyl group, substituted or nonsubstituted aryloxycarbonyl group, and substituted or nonsubstituted acyl group.
R11 is more preferably a nitro group (particularly useful as intermediate of coupler in a silver halide color photographic lightsensitive material), substituted or nonsubstituted, 2- to 32-carbon acylamino group, substituted or nonsubstituted, 1 to 32-carbon alkylsulfonylamino group, or substituted or nonsubstituted, 6- to 40-carbon arylsulfonylamino group. R11 is most preferably a nitro group or a 6- to 40-carbon arylsulfonylamino group having a substituent. The substituent, which the arylsulfonylamino group has, is preferably a 1- to 32-carbon alkoxy group, 1- to 32-carbon alkyl group, 1- to 32-carbon sulfonylamino group, 1- to 32-carbon acylamino group, or halogen atom.
Each of R12 to R14 is preferably a hydrogen atom or a 6- to 40-carbon arylsulfonylamino group having a substituent, and most preferably, a hydrogen atom.
A particularly favorable combination as a cyan coupler represented by formula (III) of the present invention is that X is a hydrogen atom, R1 is a cyano group, R2 is a branched 4- to 32-carbon alkyloxycarbonyl group, R3 and R4 form a ring structure, preferably 6-membered heterocyclic ring, and R11 is a substituted or nonsubstituted, 2- to 32-carbon acylamino group, substituted or nonsubstituted, 1- to 32-carbon alkylsulfonylamino group, substituted or nonsubstituted, 6- to 40-carbon arylsulfonylamino group, or nitro group. Each of R12 to R14 is a hydrogen atom or a 6- to 32-carbon arylsulfonylamino group having a substituent. The substituent, which the arylsulfonylamino group has, is preferably a 1- to 32-carbon alkoxy group, 1- to 32-carbon alkyl group, 1- to 32-carbon sulfonylamino group, 1- to 32-carbon acylamino group, or halogen atom.
A cyan coupler represented by formula (III) is more preferably a structure represented by formula (V) below.
In formula (V), X, R3, R4, R11, R12, R13, and R14 have the same meanings as X, R3, R4, R11, R12, R13, and R14 in formula (III).
R21, R22, R23, R24, and R25 can be the same or different and each represents a hydrogen atom or a substituent. Preferred examples of the substituent are a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, and substituted or nonsubstituted aryl group. More preferred examples are as follows.
Each of R21 and R22 represents preferably an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or cycloalkenyl group. Examples are a 1- to 36-carbon, straight-chain, branched-chain, or cyclic alkyl group, 7- to 36-carbon aralkyl group, 2- to 36-carbon alkenyl group, 2- to 36-carbon alkynyl group, and 3- to 36-carbon cycloalkenyl group, and more specifically, methyl, ethyl, propyl, isopropyl, t-butyl, t-amyl, t-octyl, tridecyl, cyclopentyl, and cyclohexyl. The upper limit of the number of carbon atoms of an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, and cycloalkenyl group is more preferably 12. Each of R21 and R22 is further preferably a nonsubstituted 1- to 8-carbon alkyl group. Each of R23, R24, and R25 represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or cycloalkenyl group. Examples of the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, and cycloalkenyl group are groups previously enumerated as R21 and R22. Each of R23, R24, and R25 is particularly preferably a hydrogen atom.
Z represents a non-metallic atomic group required to form a 5- to 8-membered ring. This ring can be substituted, can be a saturated ring, or can have an unsaturated bond. A non-metallic atom is preferably a nitrogen atom, oxygen atom, sulfur atom, or carbon atom, and more preferably, a carbon atom.
Examples of a ring formed by Z are a cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, piperazine ring, oxane ring, and thiane ring. These rings can be substituted by the substituents described above.
A ring formed by Z is preferably a cyclohexane ring which can be substituted, and particularly preferably, a cyclohexane ring whose 4-position is substituted by a 1- to 24-carbon alkyl group (which can be substituted by the aforementioned substituents).
A cyan coupler represented by formula (V) used in the present invention has an oil-soluble group in its molecules and hence is readily soluble in a high-boiling organic solvent. Preferably, this coupler itself and a dye formed by oxidation coupling of the coupler with a color formation reducing agent (developing agent) are nondiffusible in a hydrophilic colloid layer.
A particularly favorable combination as a cyan coupler represented by formula (V) of the present invention is that X is a hydrogen atom, each of R21 and R22 is t-butyl, each of R23, R24, and R25 is a hydrogen atom, Z forms a cyclohexane ring, the 4-position of this cyclohexane ring is substituted by a 1- to 8-carbon alkyl group, R3 and R4 form a ring structure (preferably a group which forms a 6-membered ring bonded by a nitrogen atom, e.g., morpholino, piperadinyl substituted by an acyl group, or piperidino substituted by a carboxyl group), R11 is a substituted or nonsubstituted, 1- to 32-carbon alkylsulfonylamino group, substituted or nonsubstituted, 6- to 30-carbon arylsulfonylamino group, or nitro group, and each of R12 to R14 is a hydrogen atom or a 6- to 30-carbon arylsulfonylamino group having a substituent. The substituent, which the arylsulfonylamino group has, is preferably a 1- to 32-carbon alkoxy group, 1- to 32-carbon alkyl group, 1- to 32-carbon sulfonylamino group, 1- to 32-carbon acylamino group, or halogen atom.
A pyrrolotriazole compound represented by formula (I), (III), and (IV) of the present invention will be described in detail below. Note that compounds represented by formulas (I), (III), and (IV) have conventionally unknown novel structures, are useful as synthetic intermediates of couplers in silver halide color photographic lightsensitive material, and can be used as useful intermediates of chemical, medicinal or agrichemical organic compounds.
Each substituent of formula (I) of the pyrrolotriazole compound represented by formula (I) has the same meaning as that of a cyan coupler represented by formula (I) for use in the silver halide color photographic lightsensitive material mentioned above, with the exception of the definition of X. Also, each substituent of formula (III) of the pyrrolotriazole compound represented by formula (III) has the same meaning as that of a cyan coupler represented by formula (III) for use in the silver halide color photographic lightsensitive material mentioned above, with the exception of the definition of X. Specifically, in the pyrrolotriazole compound represented by formula (I) and (III), X represents a hydrogen atom, halogen atom, 1- to 32-carbon alkyloxy group, 6- to 32-carbon aryloxy group, 1- to 32-carbon alkylthio group, 6- to 32-carbon arylthio group, 2- to 32-carbon alkyloxycarbonyloxy group, 7- to 32-carbon aryloxycarbonyloxy group, 1- to 32-carbon carbamoyloxy group, 3- to 32-carbon heterocyclic carbonyloxy group, or 2- to 32-carbon, 5- or 6-membered nitrogen-containing heterocyclic group which bonds to a coupling active position by a nitrogen atom.
In the pyrrolotriazole compound represented by formula (I), each preferable substituent of X, R1, R2, G1, G2, R3, R4, R5 and n has the same meaning as each preferable substituent of a cyan coupler represented by formula (I) for use in the silver halide color photographic lightsensitive material mentioned above. Also, in the pyrrolotriazole compound represented by formula (III), each preferable substituent of X, R1, R2, R3, R4, R11, R12, R13, and R14 has the same meaning as each preferable substituent of a cyan coupler represented by formula (III) for use in the silver halide color photographic lightsensitive material mentioned above.
In formula (IV), X, R3, R4, R11, R12, R13, and R14 have the same meanings as X, R3, R4, R11, R12, R13, and R14 in formula (III) described above.
Also, Z, R21, R22, R23, R24, and R25 in formula (IV) have the same meanings as Z, R21, R22, R23, R24, and R25 in formula (V) described above.
A particularly favorable combination as a pyrrolotriazole compound represented by formula (IV) of the present invention is that X is a hydrogen atom, each of R21 and R22 is t-butyl, each of R23, R24, and R25 is a hydrogen atom, Z forms a cyclohexane ring, the 4-position of this cyclohexane ring is substituted by a 1- to 8-carbon alkyl group, R3 and R4 form a ring structure (preferably a group which forms a 6-membered ring bonded by a nitrogen atom, e.g., morpholino, piperadinyl substituted by an acyl group, or piperidino substituted by a carboxyl group), R11 is a substituted or nonsubstituted, 1- to 32-carbon alkylsulfonylamino group, substituted or nonsubstituted, 6- to 30-carbon arylsulfonylamino group, or nitro group, and each of R12 to R14 is a hydrogen atom or a 6- to 30-carbon arylsulfonylamino group having a substituent. The substituent, which the arylsulfonylamino group has, is preferably a 1- to 32-carbon alkoxy group, 1- to 32-carbon alkyl group, 1- to 32-carbon sulfonylamino group, 1- to 32-carbon acylamino group, or halogen atom.
Practical examples of cyan couplers and pyrrolotriazole compounds defined by the present invention will be presented below. However, the present invention is not limited to these examples.
A compound represented by formula (V) can be synthesized by the following method.
Practical synthesis examples of a pyrrolotriazole compound of the present invention will be described below.

Silver halide color photographic lightsensitive material and novel pyrrolotriazole compound