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Optical Information Recording Method And Method Of Utilizing A Dye

Abstract: An optical Information recording medium comprises; a recording layer capable of recording and reproducing information by irradiation with a laser light, and an image recording layer capable of recording a visible image and containing a dye as a major component.

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Patent Information

Application #
Filing Date
21 January 2008
Publication Number
38/2008
Publication Type
INA
Invention Field
ELECTRONICS
Status
Email
patent@depenning.com
Parent Application

Applicants

FUJIFILM CORPORATION
26-30, NISHIAZABU 2-CHOME, MINATO-KU, TOKYO, JAPAN

Inventors

1. MIKOSHIBA, HISASHI
C/O FUJIFILM CORPORATION., 210 NAKANUMA, MINAMI-ASHIGARA-SHI, KANAGAWA, JAPAN
2. SHIBATA, MICHIHIRO
C/O FUJIFILM CORPORATION, 12-1 OGI-CHO 2-CHOME, ODAWARA-SHI, KANAGAWA, JAPAN

Specification

DESCRIPTION OPTICAL INFORMATION RECORDING MEDIUM, IMAGE-RECORDING METHOD AND METHOD OF UTILIZING A DYE Technical Field The present invention relates to an optical image recording medium and, in particular, to an optical information recording medium having an image recording layer capable of recording a visible image in addition to an optical information recording layer (preferably on the opposite side to the optical information recording side), an image recording method of recording an image on the optical information recording medium, and a method of utilizing a dye in the image recording layer. Background Art Optical information recording media (optical disks) capable of recording information for once using a laser light have conventionally been known. The optical disks are also referred to as write-once CDs (so-called CD-Rs) and, in a typical structure thereof, a recording layer containing an organic dye, a reflection layer containing a metal such as gold and a protective layer made of a resin are laminated successively in this order on a transparent disk-shape substrate. Information is recorded onto the CD-R by irradiating the CD-R with a laser light in a near infrared region (usually, a laser light near 780 nm in wavelength). An irradiated portion of the recording layer absorbs the light to locally increase the temperature at the portion, and the optical characteristics of the portion are changed by physical or chemical change (for example, formation of pits) to record the information. On the other hand, readout (reproduction) of information is also performed by the irradiation of the CD-R with a laser light of the same wavelength as used for recording. Information is reproduced by the detection of the difference in the reflectance between the portion where the optical characteristics of the recording layer altered (recorded portion) and the portion where the optical characteristics did not alter (non-recorded portion). In recent years, information recording media of higher recording density are being demanded. To meat such a demand, optical disks called writable digital versatile disks (so-called DVD-Rs) have been proposed. The DVD-R has a structure comprising two disks each comprising a transparent disk-like substrate in which guide grooves (pre-grooves). for tracking of laser light to be irradiated are formed with a narrow width (from 0.74 to 0.8 µm) of one-half or less a groove width of CD-Rs, having provided thereon a recording layer comprising a dye, generally a light-reflecting layer on the recording layer and, if necessary, a protective layer, which two disks are adhered to each other with an adhesive with the recording layers disposed at the inside, or a structure wherein the disk described above and a disk-shaped protective substrate of the same shape as that of the disk are adhered to each other with an adhesive with the recording layer at the inside. The recording and reproduction of information on DVD-R are performed by irradiation with a visible laser light (generally a laser light of from 630 nm to 680 nm in wavelength), and it is believed that recording at higher density than with CD-R is possible. Among the optical disks, there are known those optical disks having a label stuck on the opposite side to the recording side on which musical data or the like are recorded, with the label having printed thereon visible information such as a title of a music composition of music data recorded on the recording side or a tile for discriminating recorded date. Such optical disks are produced by previously printing the tile or the like on a circular label sheet using a printer and sticking the label sheet onto the opposite side of the optical disk to the recording side. However, in the case of producing an optical disk having a desired visible image such as a title recorded on the opposite side to the recording side as described above, a printer is additionally required in addition to an optical disk drive. Thus, there is required a complicated operation wherein recording on a recording side of an optical disk is performed by using an optical disk drive, the optical disk is removed from the optical disk drive, and a label sheet having been printed by means of a separately prepared printer is stuck thereon. Therefore, there has been proposed an optical recording medium which permits display by changing contrast between the surface and the background by using a laser marker on the opposite side to the recording side (see JP-A-11-66617). This method permits recording of a desired image on the opposite side to the recording side without separately preparing a printer. However, this method requires use of a high-power gas laser such as a carbonic acid gas laser due to low sensitivity, and a visible image formed by the laser light as described above has such a low contrast that it has an inferior viewability. On the other hand, if the same laser light source as is employed for recording or reproducing information (digital information) can be used for recording visible information, the visible information can be displayed by using an apparatus a general user uses for recording. Also, in view of saving hardware source of a recording apparatus, it is preferred that a laser light source used for recording or reproducing information (digital information) can commonly be used as a laser light source for recording a visible image. Disclosure of the Invention The present invention has been made in view of the above-mentioned conventional problems, and its subject is to attain the following object. That is, an object of the invention is to provide an optical information recording medium which permits formation of a distinct, highly contrasty visible image in an image recording layer provided in addition to an optical information recording layer (preferably on the opposite side to the recording side) by using a laser light, and an image recording method of recording an image onto an image recording layer of the optical information recording medium, which method can minimize the hardware source for the recording apparatus and enables a general user to record an image with ease using the recording apparatus. Means for solving the above-mentioned subject is as follows. That is: (1) An optical information recording medium comprising: a recording layer capable of recording and reproducing information by irradiation with a laser light; and an image recording layer capable of recording a visible image and containing a dye as a major component. (2) The optical information recording medium as described in (1), wherein the dye is an oxonol dye, (3) The optical information recording medium as described in (1) or (2), wherein the dye is an oxonol dye having a structure represented by the following general formula (11): wherein Za25 and Za26 each independently represents atoms forming an acidic nucleus, Ma , Ma and Ma each independently represents a substituted or unsubstituted methine group, Ka represents an integer of from 0 to 3, Q represents a monovalent cation for neutralizing charge and, when Ka represents a plural number, plural Ma s and Ma s may be the same or different from each other. (4) The optical information recording medium as described in (1) or (2), wherein the dye is an oxonol dye having a structure represented by the following general formula (I): a substituted or unsubstituted methine group, L represents a divalent linking group which does not form a n conjugation system together with the two bonds, Ka and Ka each independently represents an integer of from 0 to 3, Q represents a monovalent cation for neutralizing charge, or 2Q represents a divalent cation and, when Ka^^ and Ka'^^each represents a plural number, plural Ma^^s, Ma^^s, Ma^^s and Ma s may be the same or different from each other. (5) The optical information recording medium as described in (1), wherein the dye is a cyanine dye. (6) The optical information recording medium as described in (1) or (5), wherein the dye is a cyanine dye represented by the general formula (2') wherein Za and Za each independently represents atoms forming a hetero ring, 0 1 00 O ^ Ma , Ma and Ma each independently represents a substituted or unsubstituted methine group, ka2 represents an integer of from 0 to 3, and, when ka2 represents 2 01 00 or more, plural Ma s and Ma s may be the same or different from each other, Q2 represents an ion for neutralizing charge, and y2 represents a number necessary for neutralizing charge. (7) The optical information recording medium as described in (1), (5) or (6), wherein the dye is a cyanine dye represented by the general formula (4'): wherein Za31 and Za32 each independently represents atoms forming a carbon ring or a hetero ring, R1a and R2a each independently represents a substituent, R121 R122, R123, R124 , R125 , R126 and R127 each independently represents a hydrogen atom or a substituent, ka3 represents an integer of from 0 to 3 and, when ka3 represents 2 or more, plural R s and R s may be the same or different from each other, Q3 represents an ion for neutralizing charge, and y3 represents a number necessary for neutralizing charge. (8) The optical information recording medium as described in (1), wherein the dye is an azo dye. (9) The optical information recording medium as described in (1) or (8), wherein the dye is an azo dye represented by the general formula (2"): A-N=N-B (2") wherein A represents a monovalent group derived from a coupler component, and B represents a monovalent group derived from a diazonium salt. (10) The optical information recording medium as described in (1), (8) or (9), wherein the dye is an azo dye represented by the general formula (4"): wherein A and B each independently represents atoms forming a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aromatic hetero ring, and G represent a monovalent group having the ability of coordinating to a metal ion. (11) The optical information recording medium as described in (1), wherein the dye is a phthalocyanine dye. (12) The optical information recording medium as described in (11), wherein the dye is a phthalocyanine dye represented by the general formula (5): wherein Ra1 to Ra8 and Rβ1 to R8 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a formyl group, a carboxyl group, a sulfo group, an alkyl group containing from 1 to 20 carbon atoms, an aryl group containing from 6 to 14 carbon atoms, an aralkyl group containing from 7 to 15 carbon atoms, a hetero ring group containing from 1 to 10 carbon atoms, an alkoxy group containing from 1 to 20 carbon atoms, an aryloxy group containing from 6 to 14 carbon atoms, an acyl group containing from 2 to 21 carbon atoms, an alkylsulfonyl group containing from 1 to 20 carbon atoms, an arylsulfonyl group containing from 6 to 20 carbon atoms, a carbamoyl group containing from 1 to 25 carbon atoms, a sulfamoyl group containing from 0 to 32 carbon atoms, an alkoxycarbonyl group containing from 2 to 21 carbon atoms, an aryloxycarbonyl group containing from 7 to 15 carbon atoms, an acylamino group containing from 2 to 21 carbon atoms, a sulfonylamino group containing from 1 to 20 carbon atoms or an amino group containing from 0 to 36 carbon atoms, M represents two hydrogen atoms, a metal, a metal oxide or a metal having a ligand. (13) The optical information recording medium as described in (1), wherein the dye is a pyrromethene dye. (14) The optical information recording medium as described in (1) or (13), wherein the dye is a pyrromethine dye represented by the general formula (P): may be connected to each other to form an aromatic ring or a hetero ting, the ring may have a substituent and, further, the ring may be condensed with an aromatic ring or a hetero ring. (15) An image recording method of recording an image in an image recording layer of the optical information recording medium described in any one of (1) to (14), wherein the same laser light as that used for recording optical information in the recording layer is used for recording a visible image in the image recording layer. (16) A method of utilizing the dye described in any one of (1) to (14) in an image recording layer of an optical information recording medium. The image recording layer according to the present invention (in some cases, referred to as a visual information recording layer) is preferably a visual information recording layer in which a substantially same track is irradiated with laser light several times to record visual information, or may be a visual information recording layer in which laser light swings in the radial direction of an optical disc and a substantially same track is irradiated with the laser light several times to record visual information. The visual information recording layer of the optical recording medium according to the invention requires properties different from those required in typical digital data recording in the following respects: That is, in digital data recording, a pit is formed by one laser light irradiation. Therefore, a typical optical recording medium used in digital data recording and the optical recording medium of the invention require different properties. Typically, when a pit is formed in a dye recording layer, it is important to form a pit that provides sufficient reflectance and a sufficient degree of modulation so that a drive can recognize the pit. Therefore, those skilled in the art will not envision to use the system in which a substantially same track is irradiated with laser light several times, or the system in which laser light swings in the radial direction of an optical disc and a substantially same track is irradiated with the laser light several times. Also, for a typical optical disc, since the position where a pit is formed in the radial direction will be specified, the laser light will never be controlled to swing in the radial direction of the optical disc, or those skilled in the art will never envision to swing the laser light in the radial direction of the optical disc to form a pit. In such a system totally different from the related-art drive systems, the optical recording medium of the invention enables high contrast, high definition visual information recording (such as images) with excellent light resistance of recorded visual information. Brief Description of the Drawings Fig. 1 is a schematic view of a layered structure of a preferred optical recording medium of the invention; Fig. 2 is a block diagram showing the constitution of an optical disk recording apparatus in accordance with one embodiment of the invention; Fig. 3 is a view showing the structure of an optical pickup which is a constituent of the optical disk recording apparatus; Fig. 4 is a view for illustrating the contents of image data to be used for forming a visible image in a visible image-recording layer of the optical disk by the optical disk recording apparatus; Fig. 5 is a view for illustrating the contents of controlling irradiation with a laser light for expressing high or low density of the image upon formation of the visible image in the visible image-recording layer of the optical disk by the optical disk recording apparatus; Fig. 6 is a view for illustrating the method of controlling a laser light upon formation of a visible image in the visible image-recording layer of the optical disk by the optical disk recording apparatus; Fig. 7 is a view for illustrating the contents of laser power control by a laser power control circuit which is a constituent of the optical disk recording apparatus; Fig. 8 is a view showing a return light of a laser light emitted to the visible image-recording layer of the optical disk from an optical pickup of the optical disk recording apparatus; Fig. 9 is a view showing FG pulses generated by a frequency generator 21 which is a constituent of the optical disk recording apparatus in accordance with the amount of rotation of a spindle motor and a clock signal generated based on the FG pulses; Fig. 10 is a flow chart for illustrating operation of the optical disk recording apparatus; Fig. 11 is a flow chart for illustrating operation of the optical disk recording apparatus; Fig. 12 is a view showing a disk ID recorded in the visible image-recording layer of the optical disk; Fig. 13 is a view showing the shape of a return light of a laser light received by a light-receiving element in the optical pickup of the optical disk recording apparatus; Fig. 14 is a view for illustrating the size of a beam spot diameter of a laser light emitted from the optical pickup of the optical disk recording apparatus to the visible image-recording layer of the optical disk; Fig. 15 is a view for illustrating the method of detecting that the laser light irradiation position of the optical disk recording apparatus has passed the standard position of the optical disk; Fig. 16 is a view for illustrating the method of detecting that the laser light irradiation position of the optical disk recording apparatus has passed the standard position of the optical disk; Fig. 17 is a timing chart for illustrating operation of the optical disk recording apparatus upon formation of a visible image by irradiating the visible image-recording layer of the optical disk with a laser light; Fig. 18 is a view showing a visible image-recording layer of the optical disk having been irradiated with a laser light by the optical disk recording apparatus; Fig. 19 is a view for illustrating the method of expressing high or low density of a visible image formed in the optical image-recording layer of the optical disk by the optical disk recording apparatus; Fig. 20 is a view for illustrating the method of expressing high or low density of a visible image formed in the optical image-recording layer of the optical disk by the optical disk recording apparatus; Fig. 21 is a view for illustrating the method of expressing high or low density of a visible image formed in the optical image-recording layer of the optical disk by the optical disk recording apparatus; Fig. 22 is a view for illustrating the method of expressing high or low density of a visible image formed in the optical image-recording layer of the optical disk by the optical disk recording apparatus; Fig. 23 is a view for illustrating the method of expressing high or low density of a visible image formed in the optical image-recording layer of the optical disk by the optical disk recording apparatus; Fig. 24 is a view for illustrating the method of moving the laser light irradiation position in the diameter direction of the optical disk upon formation of a visible image in the visible image-recording layer of the optical disk by the optical disk recording apparatus; Fig. 25 is a view for illustrating the contents of laser power control performed by the optical disk recording apparatus; Fig. 26 is a view showing the positional relation between the optical disk and the optical pickup in the case where the optical disk is set so that the visible image-recording layer faces the optical pickup and in the case where the optical disk is set so that the opposite side of the optical disk to the visible image-recording layer side faces the optical pickup; Fig. 27 is a perspective view showing an adapter for adjusting the positional relation between the optical disk and the optical pickup; Fig. 28 is a view showing outline constitution of the optical disk recording apparatus equipped with the function of adjusting positional relation between the optical disk and the optical pickup; Fig. 29 is a view for illustrating the method of enlarging the beam spot diameter of a laser light emitted to the visible image-recording layer of the optical disk; Fig. 30 is a view for illustrating the method of performing formation of the visible image by moving the laser light irradiation position along the pre-groove formed on the opposite side of the optical disk to the visible image-recording layer side; Fig. 31 is a view for illustrating a prohibition region of the optical disk where irradiation with laser light for forming a visible image by the optical disk recording apparatus is prohibited; Fig. 32 is a block diagram showing the constitution of a modified example of the optical disk recording apparatus; and Fig. 33 is a view showing absorbance change of the image-recording layers of the optical disks 1-1 to 1-7. 10 denotes an optical pickup; 11 denotes a spindle motor (rotationally driving means); 12 denotes a KF amplifier; 13 denotes a servo circuit; 16 denotes a controlling unit; 17 denotes an encoder; 18 denotes a strategy circuit; 19 denotes a laser driver; 20 denotes a laser power controlling circuit; 21 denotes a frequency generator; 30 denotes a stepping motor; 31 denotes a motor driver; 32 denotes a motor controller; 33 denotes a PLL circuit; 34 denotes a FIFO memory; 35 denotes a driving pulse generating section; 36 denotes a buffer memory; 53 denotes a laser diode; 53a denotes a front monitor diode; 56 denotes a light-receiving element; 64 denotes a focus actuator; 65 denotes a tracking actuator; 100 denotes a optical disk recording apparatus; 212 denotes a substrate; 214 denotes a recording layer; 216 denotes a first reflection layer; 222 denotes a substrate (dummy); 224 denotes a image-recording layer; 226 denotes a second reflection layer; 230 denotes an adhesive layer; 270 denotes a chucking portion; 271 denotes an adaptor; 280 denotes a driving mechanism; 320 denotes an encoder; D denotes an optical disk; a denotes a curve showing absorbance change of the optical disk 1-1 of the invention; b denotes a curve showing absorbance change of the optical disk 1-2 of the invention; c denotes a curve showing absorbance change of the optical disk 1-3 of the invention; d denotes a curve showing absorbance change of the optical disk 1-4 of the invention; e denotes a curve showing absorbance change of the optical disk 1-5 of the invention; f denotes a curve showing absorbance change of the optical disk 1-6 of the invention; and g denotes a curve showing absorbance change of the optical disk 1-7 of the invention. Best Mode for Carrying Out the Invention The optical information recording medium of the invention is an optical information recording medium having a recording layer which permits recording and reproduction of information by irradiation with a laser light. It has an image recording layer capable of recording a visible image in addition to the aforementioned recording layer (preferably on the opposite side), with the image recording layer containing a dye as a major component. The dye has an absorbance of preferably 0.05 or more for a laser light. The dyes may be used independently or in combination of two or more thereof. The optical information recording medium and the image recording method of the invention will be described below. As to kind of the optical information recording medium of the invention, any of read-only type, writable type and re-writable type may be employed, with writable type being preferred. Recording type is not particularly limited, and any of phase change type, optomagnetic type and dye type may be employed, with dye type being preferred. As to the stratum structure of the optical information recording medium of the invention, there are illustrated, for example, the following structures. (1) A first structure comprises a substrate having provided thereon a recording layer, a reflection layer and an adhesive layer in this order, with an image recording layer and a dummy substrate being provided on the adhesive layer. (2) A second structure comprises a substrate having provided thereon a recording layer, a reflection layer, a protective layer and an adhesive layer in this order, with an image recording layer and a dummy substrate being provided on the adhesive layer. (3) A third structure comprises a substrate having provided thereon a recording layer, a reflection layer, a protective layer, an adhesive layer and a protective layer in this order, with an image recording layer and a dummy substrate being provided on the protective layer. (4) A fourth structure comprises a substrate having provided thereon a recording layer, a reflection layer, a protective layer, an adhesive layer, a protective layer and a reflection layer in this order, with an image recording layer and a dummy substrate being provided on the antireflection layer. (5) A fifth structure comprises a substrate having provided thereon a recording layer, a reflection layer, an adhesive layer and a reflection layer in this order, with an image recording layer and a dummy substrate being provided on the antireflection layer. Fig. 1 shows an example of the stratum structure. Additionally, the stratum structures of (1) to (5) described above are merely illustrative, and the orders of the layers in the stratum structure are not limited only to the above-described orders, and one or more of the layers may be exchanged or omitted. Further, each layer may be constituted by a single layer or a plurality of layers. The substrate and each of the layers will be described below. [Image recording layer] As has been described hereinbefore, the optical information recording medium of the invention has an image recording layer containing a dye as a major component in addition to the recording layer (preferably on the opposite side. Here, the phrase "containing a dye as a major component" means that the content of the dye based on the weight of the total solid components in the image recording layer amounts to 50% or more (preferably 80% or more). In the image recording layer is recorded a visible image (visible information) a user desires, such as a letter, a figure or a picture pattern. Examples of the visible image include disk title, information on the content, thumbnail of the content, pattern related to the content, designing pattern, information on copyright, the recording date and time, recording method and recording format. It suffices for the image recording layer to visibly record information such as a letter, an image or a picture pattern. In the invention, use of a dye having a maximum absorption within a light wavelength range of 400 to 850 nm and having an absorbance of 0.05 or more (preferably 0.1 or more and 1.0 or less) for a laser light to be used is preferred. Specific examples of the dye include cyanine dyes, imidazoquinoxaline series dyes, pyrylium series or thiopyrylium series dyes, azulenium series dyes, squarylium series dyes, azo dyes, metal (Ni or Cr) complex salt series dyes (phthalocyanine dyes, azo metal chelate dyes and pyrromethene metal chelate dyes), naphthoquinone series dyes, anthraquinone series dyes, indophenol series dyes, indoaniline series dyes, triphenylmethane series dyes, merocyanine series dyes, oxonol series dyes, aminium series dyes and UV ray absorbents. Of these, cyanine series dyes, phthalocyanine series dyes, azo dyes (including metal chelate dyes), merocyanine series dyes, oxonol series dyes and UV ray absorbents are preferably used. A dye adapted for a laser light of a wavelength used for recording can be obtained by, for example, changing the length of the dye conjugation system. That is, in the case of recording with a laser light of 750 to 850 nm in wavelength, methine chain length of, for example, a cyanine dye or a merocyanine dye is preferably from 5 to 7 and, with an oxonol series dye, methine chain length is preferably from 7 to 9. Also, in the case of recording with a laser light of from 600 to 700 nm in wavelength, mehine chain length of, for example, a cyanine dye or a merocyanine dye is preferably from 3 to 5 and, with an oxonol series dye, methine chain length is preferably from 5 to 7. Further, in the case of recording with a laser light of from 350 to 450 nm in wavelength, it is possible to use a UV ray absorbent or a near-ultraviolet ray absorbent. However, the above-mentioned dyes having a side absorption in this laser wavelength region are preferably used. Cyanine dyes whose methine chain length is 1 and oxonol dyes whose methine chain length is 1 are preferred. As a combination of dyes, there can preferably be illustrated a combination of an oxonol dye and a cyanine dye; a combination of an oxonol dye and an azo dye; a combination of one oxonol dye and another oxonol dye; a combination of an oxonol dye and a phthalocyanine dye; a combination of an oxonol dye and a pyrromethene dye; a combination of one cyanine dye and another cyanine dye; a combination of a cyanine dye and an azo dye, a combination of a cyanine dye and a phthalocyanine dye; a combination of a cyanine dye and a pyrromethene dye; a combination of an azo dye and a phthalocyanine dye; a combination of an azo dye and a pyrromethene dye; and a combination of a phthalocyanine dye and a pyrromethene dye. In the case of combining the dyes, the content ratio (by weight) of the dyes is preferably from 99:1 to 1:99, more preferably from 95:5 to 30:70, still more preferably from 90:10 to 40:60. Oxonol dyes are described below. The oxonol dyes are compounds represented by the following general formula (A) and preferably dyes having chained acidic nuclei or cyclic acidic nuclei with a methane number of from 1 to 7. In the formula, n preferably represents an integer of from 1 to 4. Rs may form a ring. Oxonol dyes represented by the foregoing general formula (II) are more preferred, dyes represented by the general formula (I) are still more preferred, and dyes represented by the general formula (III) are yet more preferred. Also, dyes represented by the general formulae (IV), (V), (VI), (VE), (IF) or (1) may be used. In the general formula (1), R11 R12, R13 and R14 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted hetero ring group, R21 R22 and R3 represent any one of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted hetero ring group, a halogen atom, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a cyano group, a substituted or unsubstituted acyl group, a substituted or unsubstituted carbamoyl group, an amino group, a substituted amino group, a sulfo group, a hydroxyl group, a nitro group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted carbamoylamino group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group and a substituted or unsubstituted sulfamoyl group, m represents an integer of 0 or more and, when m represents an integer of 2 or more, plural R s may be the same or different from each other, Zx+ represents a cation, and x represents an integer of 1 or more. R11 R12, R13 and R14 in the general formula (1) each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted hetero ring group. As the substituted or unsubstituted alkyl group represented by R11 R12, R13 and R14, there are illustrated an alkyl group containing from 1 to 20 carbon atoms (e.g., methyl, ethyl, propyl, butyl, i-butyl, t-butyl, i-amyl, cyclopropyl, cyclohexyl, benzyl or phenethyl). Also, in the case where R11 R12, R13 and R14 each represents an alkyl group, they may be connected to each other to form a carbon ring (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, cycloheptyl or cyclooctyl) or a hetero ring (e.g., piperidyl, chromanyl or morpholyl). The alkyl group represented by R11 R12, R13 or R14 is preferably a chain alkyl group or a cyclic alkyl group containing from 1 to 8 carbon atoms. Most preferably, the alkyl group is a chain (straight or branched) alkyl group containing from 1 to 5 carbon atoms, two of the alkyl groups of R^^ and R^^, or R^^ and R^^, are connected to each other to form a cyclic alkyl ring containing from 1 to 8 carbon atoms (preferably a cyclohexyl ring), or the alkyl group is a substituted alkyl group containing from 1 to 20 carbon atoms (e.g., benzyl or phenethyl). As the substituted or unsubstituted aryl group represented by R11 R12, R13 and R14, there are illustrated an aryl group containing from 6 to 20 carbon atoms (e.g., phenyl or naphthyl). The substituted or unsubstituted aryl group represented by R11 R12, R13 and R14 is preferably an aryl group containing from 6 to 10 carbon atoms. The substituted or unsubstituted hetero ring group represented by R11 R12, R13 and R14 is a 5- to 6-membered saturated or unsaturated hetero ring constituted by carbon atom, nitrogen atom, oxygen atom or sulfur atom, and examples thereof include a pyridyl group, a pyrimydyl group, a pyridazyl group, a piperidyl group, a triazyl group, a pyrrolyl group, an imidazolyl group, a triazolyl group, a furanyl group, a thiophenyl group, a thiazolyl group, an oxazolyl group, an isothiazolyl group and an isoxazolyl group. The hetero ring group may be a benzo-condensed derivative thereof (e.g., a quinolyl group, a benzimidazolyl group, a benzothiazolyl group or a benzoxazolyl group). The substituted or unsubstituted hetero ring group represented by R11 R12, R13 and R14 is preferably a substituted or unsubstituted hetero ring group containing from 6 to 10 carbon atoms. As substituents for the substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group and substituted or unsubstituted hetero ring group represented by R11 R12, R13 and R14, there are illustrated a group of substituents S to be described hereinafter. Examples of substituents belonging to group S include an alkyl group containing from 1 to 20 carbon atoms (e.g., methyl, ethyl, propyl, carboxymethyl or ethoxycarbonylmethyl), an aralkyl group containing from 7 to 20 carbon atoms (e.g., benzyl or phenethyl), an alkoxy group containing from 1 to 8 carbon atoms (e.g., methoxy or ethoxy), an aryl group containing from 6 to 20 carbon atoms (e.g., phenyl or naphthyl), an aryloxy group containing from 6 to 20 carbon atoms (e.g., phenoxy or naphthoxy), a hetero ring (e.g., pyridyl, pyrimidyl, pyridazyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, 2-pyrrolidinon-l-yl, 2-piperidon-l-yI, 2,4-dihydroxyimidazolidin-3-yl, 2,4-dihydroxyoxazolidin-3-yl, succinimido, phthahmido or maleimido), a halogen atom (e.g., fluorine, chlorine, bromine or iodine), a carboxyl group, an alkoxycarbonyl group containing from 2 to 10 carbon atoms (e.g., methoxycarbonyl or ethoxycarbonyl), a cyano group, an acyl group containing from 2 to 10 carbon atoms (e.g., acetyl or pivaloyl), a carbamoyl group contining from 1 to 10 carbon atoms (e.g., carbamoyl, methylcarbamoyl or morpholinocarbamoyi), an amino group, a substituted amino group containing from 1 to 20 carbon atoms (e.g., dimethylamino, diethylamino, bis(methylsulfonylethyl)amino, N-ethyl-N'-sulfoethylamino), a sulfo group, a hydroxyl group, a nitro group, an alkylsulfonylamino group containing from 1 to 10 carbon atoms (e.g., methylsulfonylamino), a carbamoylamino group containing from 1 to 10 carbon atoms (e.g., carbamoylamino or methylcarbamoylamino), a sulfonyl group containing from 1 to 10 carbon atoms (e.g., methanesulfonyl or ethanesulfonyl), a sulfinyl group containing from 1 to 10 carbon atoms (e.g., methanesulfinyl) and a sulfamoyl group containing from 0 to 10 carbon atoms (e.g., sulfamoyl or methanesulfamoyl). The carboxyl group and the sulfo group may be in a salt form thereof. R , R and R in the general formula (1) each independently represents any one of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted hetero ring group, a halogen atom, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a cyano group, a substituted or unsubstituted acyl group, a substituted or unsubstituted carbamoyl group, an amino group, a substituted amino group, a sulfo group, a hydroxyl group, a nitro group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted carbamoylamino group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted sulfinyl group and a substituted or unsubstituted sulfamoyl group. Preferably, R , R and R are any of a hydrogen atom, a substituted or unsubstituted alkyl group containing from 1 to 20 carbon atoms, a substituted or unsubstituted hetero ring group containing from 2 to 20 carbon atoms, a substituted or unsubstituted alkoxy group containing from 1 to 20 carbon atoms, a substituted or unsubstituted aryl group containing from 6 to 20 carbon atoms and a halogen atom, more preferably, any of a hydrogen atom, a substituted or unsubstituted alkyl group containing from 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group containing from 1 to 10 carbon atoms, a substituted or unsubstituted hetero ring group containing from 2 to 10 carbon atoms and a halogen atom and, most preferably, any of a hydrogen atom, an unsubstituted alkyl group containing from 1 to 5 carbon atoms, an unsubstituted alkoxy group containing from 1 to 5 carbon atoms, a substituted or unsubstituted hetero ring group containing from 2 to 6 carbon atoms and a halogen atom. R , R and R may further have a substituent. As examples of the substituent, there are illustrated those which are included in the aforesaid substituent group S. It is preferred that m is 0 and that both R and R are a hydrogen atom. It is also preferred that m is 1 and that R21, R22 and R3 are all a hydrogen atom. m in the general formula (1) represents an integer of 0 or more, preferably an integer of from 0 to 5 inclusive, more preferably an integer of from 0 to 3, particularly preferably an integer of from 0 to 2. In the general formula (1), when m represents an integer of 2 or more, plural R3s may be the same or different from each other, and each independently represents a hydrogen atom or the aforesaid substituent. In the general formula (1), Zx+ represents a cation, and x represents an integer of 1 or more. The cation represented by 2x+ is preferably a quaternary ammonium ion, more preferably a 4,4'-bipyridinium cation represented by the general formula (1-4) in JP-A-2000-52658 or a 4,4'-bipyridinium cation disclosed in JP-A-2002-59652. In the general formula (1), x is preferably 1 or 2. Preferred specific examples of the compound represented by the foregoing general formula (1) are shown below which, however, do not limit the invention in any way. and the specific examples thereof are also the same as examples of that which Za^\ Za22, Za23' and Za24 form. The acidic nucleus which Za or Za26 forms is preferably indandione, pyrazolone, pyrazolinedione or benzothiophenone dioxide, with pyrazolone being most preferred. Ma , Ma and Ma each independently represents a substituted or unsubstituted methine group and are the same as defined with respect to Ma^^ Ma^^, Ma , Ma , Ma and Ma in the general formula (I), with examples thereof being also the same, Ma27, Ma28 and Ma29 are preferably an unsubstituted methine group. Ka represents an integer of from 0 to 3 and is the same as defined with respect to Ka and Ka in the general formula (I). Ka is preferably 2. Q represents a monovalent cation which neutralizes charge. In the case where Ka23 represents a plural number, plural Ma27 s. Ma28 s and Ma s may be the same or different from each other. As dyes of the structure represented by the general formula (II), those dyes are preferred which are represented by the general formula (IV), (V), (VI) or (VTI). represented as "R") each independently represents a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, a substituted or unsubstituted alkyl group (including a cycloalkyl group and a bicycloalkyl group), a substituted or unsubstituted alkenyl group (including a cycloalkenyl group and a bicycloaikenyl group), a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted hetero ring group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted silyloxy group, a substituted or unsubstituted hetero ring oxy group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted carbamoyloxy group, a substituted or unsubstituted alkoxycarbonyloxy group, a substituted or unsubstituted aryloxycarbonyloxy group, a substituted or unsubstituted amino group (including an anilino group), a substituted or unsubstituted acylamino group, a substituted or unsubstituted aminocarbonylamino group, a substituted or unsubstituted alkoxycarbonylamino group, a substituted or unsubstituted aryloxycarbonylamino group, a substituted or unsubstituted sulfamoylamino group, a substituted or unsubstituted alkyl or arylsulfonylamino group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted hetero ring thio group, a substituted or unsubstituted sulfamoyl group, a sulfo group, a substituted or unsubstituted alkyl or arylsulfinyl group, a substituted or unsubstituted alkyl or arylsulfonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted aryl or hetero ring azo group, a substituted or unsubstituted imido group, a substituted or unsubstituted phosphino group, a substituted or unsubstituted phosphinyl group, a substituted or unsubstituted phosphinyloxy group, a substituted or unsubstituted phosphinylamino group and a substituted or unsubstituted silyl group. More particularly, R represents a halogen atom (e.g., a chlorine atom, a bromine atom or an iodine atom), an alkyl group [a straight, branched or cyclic, substituted or unsubstituted alkyl group including an alkyl group (preferably an alkyl group containing from 1 to 30 carbon atoms, e.g., methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl or 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group containing from 3 to 30 carbon atoms, e.g., cyclohexyl, cyclopentyl or 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group containing from 5 to 30 carbon atoms, i.e., a monovalent group formed by removing one hydrogen atom from a bicycloalkane containing from 5 to 30 carbon atoms; e.g., bicyclo[l,2,2]heptan-2-yl or bicyclo[2,2,2]octan-3-yl) and, further, a tricycle structure having more ring systems; the term "an alkyl group" as used in substituents in the following descriptions (for example, an alkyl group in an alkylthio group) also representing an alkyl group of such concept], an alkenyl group [a straight, branched or cyclic, substituted or unsubstituted alkenyl group including an alkenyl group (preferably an alkenyl group containing from 2 to 30 carbon atoms, e.g., vinyl, allyl. prenyl, geranyl or oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group containing from 3 to 30 carbon atoms, i.e., a monovalent group formed by removing one hydrogen atom from a cycloalkene containing from 3 to 30 carbon atoms; e.g., 2-cyclopenten-l-yl or 2-cyciohexen-l-yI), and a bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group containing from 5 to 30 carbon atoms, i.e., a monovalent group formed by removing one hydrogen atom from a bicycloalkene having one double bond; e.g., bicycIo[2,2,l]hept-2-en-l-yl or bicyclo[2,2,2]oct-2-en-4-yl)], an alkynyl group (preferably a substituted or unsubstituted alkynyl group containing from 2 to 30 carbon atoms, e.g., ethynyl, propargyl or trimethylsilylethynyl), an aryl group (preferably a substituted or unsubstituted aryl group containing from 6 to 30 carbon atoms, e.g., phenyl, p-tolyl, naphthyl, m-chlorophenyl or o-hexadecanoylaminophenyl), a hetero ring group (preferably a monovalent group formed by removing one hydrogen atom from a 5- or 6-membered, substituted or unsubstituted, aromatic or non-aromatic hetero ring compound, more preferably a 5- or 6-membered aromatic hetero ring group containing from 3 to 30 carbon atoms, e.g., 2-furyl, 2-thienyl, 2-pyrimidinyl or 2- benzothiazolyl), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group containing from 1 to 30 carbon atoms, e.g., methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy or 2- methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group containing from 6 to 30 carbon atoms, e.g., phenoxy, 2-methylphenoxy, 4-t- butylphenoxy, 3-nitrophenoxy or 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group containing from 3 to 20 carbon atoms, e.g., trimethylsilyloxy or t-butyldimethylsilyloxy), a hetero ring oxy group (preferably a substituted or unsubstituted hetero ring oxy group containing from 2 to 30 carbon atoms, e.g., l-phenyltetrazol-5-oxy or 2-tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group containing from 2 to 30 carbon atoms or a substituted or unsubstituted arylcarbonyloxy group containing from 6 to 30 carbon atoms, e.g., formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy or p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group containing from 1 to 30 carbon atoms, e.g., N,N-dimethylcarbamoyloxy, N,N- diethylcarbamoyloxy, morpholinocarbonyloxy, N,N-di-n-octylaminocarbonyloxy or N-n-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group containing from 2 to 30 carbon atoms, e.g., methoxy carbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy or n- octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group contining from 7 to 30 carbon atoms, e.g., phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy or p-n- hexadecyloxyphenoxycarbonyloxy), an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group containing from 1 to 30 carbon atoms or a substituted or unsubstituted arylamino group containing from 6 to 30 carbon atoms, e.g., amino, methylamino, dimethylamino, aniline, N-methyl-anilino or diphenylamino), an acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group containing from I to 30 carbon atoms or a substituted or unsubstituted arylcasrbonylamino group containing from 6 to 30 carbon atoms, e.g., formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino or 3,4,5-tri-n-octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group containing from 1 to 30 carbon atoms, e.g., carbamoylamino, N,N"dimethylaminocarbonylamino, N,N- diethylaminocarbonylamino or morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group containing from 2 to 30 carbon atoms, e.g., methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino or N- methyl-methoxycarbonylamino), an aryloxycarbonylamino group (preferably a substituted sor unsubstituted aryloxycarbonylamino group containing from 7 to 30 carbon atoms, e.g., phenoxycarbonylamino, p-chlorophenoxycarbonylamino or m-n- octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group containing from 0 to 30 carbon atoms, e.g., sulfamoylamino, N,N-dimethylaminosulfonylamino or N-n-octylaminosulfonylamino), an alkyl or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group containing from 1 to 30 carbon atoms or a substituted or unsubstituted arylsulfonylamino group containing from 6 to 30 carbon atoms, e.g., methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5- trichlorophenylsulfonylamino or p-methylphenylsulfonylamino), a mercapto group, an alkylthio group (preferably a substituted or unsubstituted alkylthio group containing from 1 to 30 carbon atoms, e.g., methylthio, ethylthio or n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group containing from 6 to 30 carbon atoms, e.g., phenylthio, p-chlorophenylthio or m-methoxyphenylthio), a hetero ring thio group (preferably a substituted or unsubstituted hetero ring thio group containing from 2 to 30 carbon atoms, e.g., 2-benzothiazolylthio or l-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group contining from 0 to 30 carbon atoms, e.g., N-ethylsulfamoyl, N-(3-dodecyloxypropyl)sulfamoyl, N,N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl or N-(N'-phenylcarbamoyl)sulfamoyl), a sulfo group, an alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group containing from 1 to 30 carbon atoms or a substituted or unsubstituted arylsulfinyl group contining from 6 to 30 carbon atoms, e.g., methylsulfinyl, ethylsulfinyl, phenylsulfinyl or p-methylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group containing from 1 to 30 carbon atoms or a substituted or unsubstituted arylsulfonyl group containing from 6 to 30 carbon atoms, e.g., methylsulfonyl, ethylsulfonyl, phenylsulfonyl or p-methylphenylsulfonyl), an acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group containing from 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group containing from 7 to 30 carbon atoms or a hetero ring carbonyl group containing from 4 to 30 carbon atoms and being connected to a carbonyl group through a carbon atom, e.g., acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, p-n-octyloxyphenylcarbonyl, 2-pyridylcarbonyl or 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group containing from 7 to 30 carbon atoms, e.g., phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl or p-t-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group containing from 2 to 30 carbon atoms, e.g., methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl or n-octadecyloxycarbonyl), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl group containing from 1 to 30 carbon atoms, e.g., carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl, N,N-di-n-octylcarbamoyl or N-(methylsulfonyl)carbamoyl), an aryl or hetero ring azo group (preferably a substituted or unsubstituted arylazo group containing from 6 to 30 carbon atoms or a substituted or unsubstituted hetero ring azo group containing from 3 to 30 carbon atoms, e.g., phenylazo, p-chlorophenylazo or 5-ethylthio-l,3,4-thiadiazol-2-ylazo), an imido group (preferably N-succinimido or N-phthalimido), a phosphino group (preferably a substituted or unsubstituted phosphino group containing from 2 to 30 carbon atoms, e.g., dimethylphosphino, diphenylphosphino or methylphenyloxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group containing from 2 to 30 carbon atoms, e.g., phosphinyl, dioctyloxyphosphinyl or diethoxyphosphinyl), a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group containing from 2 to 30 carbon atoms, e.g., diphenoxyphosphinyloxy or dioctyloxyphosphinyloxy), a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group containing from 2 to 30 carbon atoms, e.g., dimethoxyphosphinylamino or dimethylaminophosphinylamino) or a silyl group (preferably a substituted or unsubstituted silyl group containing from 3 to 30 carbon atoms, e.g., trimethylsilyl, t-butvldimethvlsilvl or phenvldimethvlsilvl). Most preferably, R26 , R27 and R28 each represents a hydrogen atom. As substituents of R31 R34 R41 R42 R43 and R44 there may be illustrated the same ones as defined with respect to R, with a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group being preferred. Among them, a substituted or unsubstituted aryl group is more preferred. Ma , Ma and Ma each independently represents a substituted or unsubstituted methine group and are the same as defined with respect to Ma27, Ma28 and Ma29 in the general formula (II), with specific examples and preferred ones thereof being also the same as described there. Ka s each independently represents an integer of from 0 to 3. Ka is preferably 2. Q represents a monovalent cation which neutralizes the charge. In the case where Ka is the plural number, plural Ma s and Ma s may be the same or different from each other. Of the dyes of the structure represented by the general formula (II), dyes of the structure represented by the following general formula (VIII) are preferred. unsubstituted alkoxycarbonyl group is preferred, with an unsubstituted alkoxycarbonyl group being most preferred. R''62, R63, R64, R65 and R66 each independently represents a hydrogen atom, s substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acylamino group or a substituted or unsubstituted hetero ring group. Preferably, all of R ^, R , R'' and R ' are a hydrogen atom. R*"^ is preferably a hydrogen atom or a substituted or unsubstituted aryl group. (JO and R each independently represents a hydrogen atom or a substituent. As the substituent, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a hydroxyl group or a substituted or unsubstituted acylamino group is preferred. Preferably, all of R71 R75 R76 R77 and R82 are a hydrogen atom. R73 and R78 ' each preferably represents a hydroxyl group. R74 and R79 each preferably represents a phenyl group. Preferably, all of R81 R82 R83 R84 R85 R86, R87 and R88 are a hydrogen atom. The dyes of the structure represented by the general formula (I) will be described in detail below. In the general formula (I), Za , Za , Za " and Za each independently represents atoms forming an acidic nucleus. Examples thereof are described in James; The Theory of the Photographic Process, 4th ed., published by McMillan Co., 1977, p.198. Specifically, there are illustrated nuclei such as pyrazol- 5-one, pyrazolidine'3,5-dione, imida2olin-5-one, hydantoin, 2- or 4-thiohydantoin, 2- iminooxa2olidin-4-one, 2-oxazoIin-5-one, 2-thioxazoline-2,4-dione, isorhodanine, rhodanine, thiophen-3-one, thiophen-3-one-l ,1 -dioxide, 3,3-dioxo[l ,3]oxathiolan-5- one, indolin-2-one, indolin-3-one, 2-oxoindazolium, 5,7-dioxo-6,7- dihydrothiazoIo[3,2a]pyrimidine, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6- dione (e.g., merdramic acid), barbituric acid, 2-thiobarbituric acid, coumarin-2,4- dione, indazolin-2-one, pyrido[l ,2-a]pyrimidine-l ,3-dione, pyrazolo[l,5- b]quinazolone, pyrazolopyridone and 5- or 6-membered hydrocarbon ring (e.g., hexane-l ,3-dione, pentane-l,3-dione or indane-l,3-dione), with pyrazol-5-one, pyrazolidine-3,5-dione, barbituric acid, 2-thiobarbituric acid, 1,3-dioxane-4,6-dione or 3,3-dioxo[l,3]oxathiolan-5-one being preferred. Most preferably, Za , Za , Za "' and Za each represents a 1,3-dioxane-4,6-dione which may be substituted. Examples of the substituent for the acidic nucleus include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkeny] group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a hetero ring group, a cyano group, a hydroxy) group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, a silyloxy group, a hetero rmg oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group (including an anilino group), an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl or arylsulfonylamino group, a mercpato group, an alkylthio group, an arylthio group, a hetero ring thio group, a sulfamoyl group, a sulfo group, an alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or hetero ring azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group or a silyl group. Among them, a substituted or unsubstituted alkyl group containing from 1 to 20 carbon atoms and a substituted or unsubstituted aryl group containing from 6 to 20 carbon atoms are preferred. As the acidic nucleus, unsubstituted acidic nuclei, acidic nuclei substituted by a substituted or unsubstituted alkyl group containing from 1 to 20 carbon atoms and acidic nuclei substituted by a substituted or unsubstituted aryl group are preferred. As the acidic nucleus formed by Za , Za , Za or Za , indanedione, pyrazolone, pyrazolinedione and benzothiophenedioxide are preferred, with pyrazolone being most preferred. Ma21 Ma22, Ma23, Ma24, Ma25 and Ma26 each independently represents a substituted or unsubstituted methine group. Preferred examples of the substituent include an alkyl group containing from 1 to 20 carbon atoms (e.g., methyl, ethyl or propyl), a halogen atom (e.g., chlorine, bromine, iodine or fluorine), an alkoxy group containing from 1 to 20 carbon atoms (e.g., methoxy, ethoxy or isopropoxy), an aryl group containing from 6 to 26 carbon atoms (e.g., phenyl or 2-naphthyl), a hetero ring group containing from 0 to 20 carbon atoms (e.g., 2-pyridyl or 3-pyridyl), an aryloxy group containing from 6 to 20 carbon atoms (e.g., phenoxy, 1-naphthoxy or 2-naphthoxy), an acylamino group containing from 1 to 20 carbon atoms (e.g., acetylamino or benzoylamino), a carbamoyl group containing from 1 to 20 carbon atoms (e.g., N,N-dimethylcarbamoyl), a sulfo group, a hydroxyl group, a carboxyl group, an alkylthio group containing from 1 to 20 carbon atoms (e.g., methylthio) and a cyano group. Also, they may be connected to other methine group to form a ring structure or may be connected to atoms represented by Za to Za to form a ring structure. Preferably, Ma21 Ma22 Ma23 Ma24, Ma25 and Ma26 each independently represents an unsubstituted methine group or a methine group substituted by an ethyl group, a methyl group or a phenyl group, with an unsubstituted methine group being most preferred. L is a divalent linking group not forming a n conjugation system with the two bonds. The divalent linking group is not particularly limited except for not forming a n conjugation system with a chromophore to which it is connected, and preferably represents a linking group containing from 0 to 100, preferably from 1 to 20, carbon atoms and being constituted by one of, or a combination of, an alkylene group (containing from 1 to 20 carbon atoms, e.g., methylene, ethylene, propylene, butylenes or pentylene), an arylene group (containing from 6 to 26 carbon atoms, e.g., phenylene or naphthylene), an alkenylene group (containing from 2 to 20 carbon atoms, e.g., ethenylene or propenylene), an alkynylene group (containing from 2 to 20 independently represents any of a hydrogen atom, a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group. Also, one or more of the linking groups may exist between two chromophres which they link to each other, and two or more (preferably two) of the linking groups may be connected to each other to form a ring. As L, a linking group wherein two alkylene groups (preferably ethylene) are respectively connected to form a ring is preferred. Of them, a linking group wherein a 5- or 6-membered ring (preferably a cyclohexyl ring) is formed is more preferred. In the general formula (I), Ka and Ka each independently represents an integer of from 0 to 3. In the case where Ka21 and Ka22 are the plural number, plural be the same or different from each other. Ka21 and Ka22 both preferably represent 2. Q represents a monovalent cation which neutralizes the charge. Therefore, 2Q represents a divalent cation. The ion represented by Q is not particularly limited, and may be an ion comprising an inorganic compound or an ion comprising an organic compound. Examples of the cation represented by Q include a metal ion such as sodium ion or potassium ion and an onium ion such as a quaternary ammonium ion, an oxonium ion, a sulfonium ion, a phosphonium ion, a selenonium ion or an iodonium ion. As the cation represented by Q, an onium ion is preferred, with a quaternary ammonium ion being more preferred. Of the quaternary ammonium ions, 4,4'-bipyridinium cations represented by the general formula (1-4) in JP-A-2000-52658 and 4,4'-bipyridinium cations disclosed in JP-A-2002-59652 are particularly preferred. With dication compounds such as 4,4'-bipyridinium cation, Q corresponds to 1/2 (dication compound). Of the dyes represented by the general formula (I), those dyes are preferred wherein acidic nuclei which Za , Za , Za and Za form each independently represents pyrazoI-5-one, pyrazoIine-3,5-dione, barbituric acid, 2-thiobarbituric acid, l,3-dioxane-4,6-dione or 33,3-dioxo[l,3]oxathiolan-5-one, which is unsubstituted or substituted by a substituted or unsubstituted alkyl group containing from 1 to 20 carbon atoms or by s substituted or unsubstituted aryl group containing from 6 to 20 carbon atoms. Ma22 , Ma23 , Ma24 , Ma25 and Ma26 each independently represents an unsubstituted methine group or a methine group substituted by an ethyl group, a methyl group or a phenyl group, L represents a linking group wherein two alkylene groups (preferably ethylene) are connected to form a 5- or 6-membered ring, Ka21 and Ka22 both represent 2, and the cation represented by 2Q represents a 4,4'-bipyridinium cation represented by the general formula (1-4) in JP-A-2000-52658 or a 4,4'-bipyridinium cation disclosed in JP-A-2002-59652. Of the dyes represented by the general formula (I), dyes represented by the general formula (III) are preferred. In formula (III), R1 and R2 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R3, R4 and R5 each independently represents a hydrogen atom or a substituent. R1 and R2 may be connected to each other to form a ring structure. R6s each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. L1 represents a divalent linking group. Two R6s may be connected to each other to form a divalent linking group, n and m each independently represents an integer of from 0 to 2. Q represents a monovalent cation which neutralizes the charge. In the case where n and m represent the plural number, plural R3s and R4s may be the same or different from each other. Formula (III) will be described in detail below. R and R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R and R may be connected to each other to form a ring structure. Preferably, R and R each independently represents a substituted or unsubstituted alkyl group. More preferably, R and R respectively represent unsubstituted alkyl groups containing from 1 to 6 carbon atoms and being different from each other in number of carbon atoms. R3 R4 and R5 each independently represents a hydrogen atom or a substituent. R3, R4 and R5 each preferably represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted hetero ring group, with a hydrogen atom, an ethyl group, a methyl group or a phenyl group being more preferred. Most preferably, all of R3 R4 and R5 represent a hydrogen atom. R6 represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Particularly preferably, two R6s are connected to each other to form a divalent linking group. L1 represents a divalent linking group. Preferably, L1 represents a substituted or unsubstituted alkylene group. Most preferably, L1 and two R s are connected to each other to form a ring structure. In such case, the ring structure is preferably a 5- or 6-membered ring (more preferably a 6-membered ring), n and m each independently represents an integer of from 0 to 2. Preferably, both n and m represent 2. Q represents a monovalent cation which neutralizes the charge. Accordingly, 2Q represents a divalent cation. In the case where n and m each represents the plural number, plural R3s and R4s may be the same or different from each other. Preferred examples of the compounds of the invention represented by the general formula (I), (II) or (III) will be illustrated below which, however, are not to be construed as limitting the invention in any way. General oxonol dyes can be synthesized by condensation reaction between a corresponding active methylene compound and a methine source (a compound to be used for introducing a methine group into a methine dye). As to detailed descriptions on this kind of compounds, reference may be made to JP-B-39-22069, JP-B-43-3504, JP-B-52-38056, JP-B-54-38129, JP-B-55-10059, JP-B-58-35544, JP-A-49-99620, JP-A-52-92716, JP-A-59-16834, JP-A-63-3 16853, JP-A-64-40827, BP No. 1,133,986, US Patent Nos. 3,247,127, 4,042,397, 4,181,225, 5,213,956 and 5,260,179. Descriptions thereon are also given in JP-A-63-209995, JP-A-1 0-309871 and JP-A-2002-249674. A process for synthesizing the bis type oxonol dyes is disclosed in EP No. 1,424,691A2. Next, embodiments of an optical information recording medium wherein the dye in the recording layer is a cyanine dye will be described below. Dyes represented by the general formula (2') will be described below. Ma , Ma and Ma in the general formula (2') are the same as defined with respect to Ma11 Ma12 and Ma13 in the general formula (T), and preferred examples thereof are also the same as described there. R101 and R12 each independently represents a substituent, preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted hetero ring group. These substituents may further be substituted, and examples of such substituent are the same as described in group S in the general formula (1). Preferably, R101 and R102 each represents a substituted or unsubstituted alkyl group, more preferably a substituted or unsubstituted alkyl group containing from 1 to 8 carbon atoms, still more preferably an unsubstituted alkyl group containing from 1 to 8 carbon atoms. R101 and R102 may be different from each other or may be the same, preferably are the same. ka2 is the same as defined with kal in the general formula (1'), and preferred examples thereof are also the same as described there. Q2 represents an ion which neutralizes the charge, and y2 represents a number necessary for neutralizing the charge. The ion represented by Q2 is an anion in accordance with the charge of the dye molecule. The ion represented by Q2 is not particularly limited, and may be an ion comprising an inorganic compound or an ion comprising an organic compound. The charge of the ion represented by Q2 may be monovalent or polyvalent. Examples of the anion represented by Q2 include a halide anion such as a chloride ion, a bromide ion or a fluoride ion, a heteropolyacid ion such as a sulfate ion, a phosphate ion or a hydrogenphosphate ion, an organic polyvalent anion such as a succinate ion, a maleate ion, a fumarate ion or an aromadic disulfonate ion, a tetrafluoroborate ion and a hexafluorophosphate ion. y2 represents a number necessary for neutralizing the charge and is the same as defined with respect to yl in the general formula (1'). In the case where Q2 represents a divalent anion, entire Q2y2 can be considered as a monovalent anion when y2 is reduced to 1/2. Next, dyes represented by the general formula (4') will be described below. R121 R122 and R123 each represents a hydrogen atom or a substituent. The substituent is the same as defined with respect to the substituent for Ma11 Ma12 and Ma13, and preferred examples thereof are also the same as described there. R , R , R and R127 each represents a hydrogen atom or a substituent. The substituent is the same as defined with respect to R1a and R2a to be described hereinafter, and preferred examples thereof are also the same as described there. R1a and R2a are the same as defined with respect to R101 and R102 in the general formula (2') and preferred examples thereof are also the same as described there. ka3 is the same as defined with ka2 in the general formula (2'), and preferred examples thereof are also the same as described there. Q3 represents an ion which neutralizes the charge, and y3 represents a number necessary for neutralizing the charge. The ion represented by Q3 is an anion in accordance with the charge of the dye molecule. The ion represented by Q3 is not particularly limited, and may be an ion comprising an inorganic compound or an ion comprising an organic compound. The charge of the ion represented by Q3 may be monovalent or polyvalent. Examples of the anion represented by Q3 include a halide anion such as a chloride ion, a bromide ion or a fluoride ion, a heteropolyacid ion such as a sulfate ion, a phosphate ion or a hydrogenphosphate ion, an organic polyvalent anion such as a succinate ion, a maleate ion, a fumarate ion or an aromatic disulfonate ion, a tetrafluoroborate ion and a hexafluorophosphate ion. y3 represents a number necessary for neutralizing the charge and is the same as defined with respect to y2 in the general formula (2'). In the case where Q3 represents a divalent anion, entire Q3γ3 can be considered as a monovalent anion when y3is reduced to 1/2. With the cyanine dye to be used in the invention represented by the above general formula (2') or (4'), Ma , Ma and Ma each preferably represents an unsubstituted methine group, R101 and R102 each independently represents preferably an unsubstituted alkyl group containing from 1 to 8 carbon atoms, R124, R125, R126 and R127 each independently represents preferably a substituted or unsubstituted alkyl group, ka3 preferably represents 1 or 2, Q3 preferably represents an inorganic or organic anion, and y3 preferably represents 1. Most preferred dyes are those which satisfy all of the above-mentioned preferred embodiments. Specific examples of the cyanine compound to be used in the invention having a structure represented by the general formula (2') are illustrated below which, however, are not to be construed as limiting the invention in any way. refractive index (real part: refractive index) at the wavelength of a recording laser light and k (imaginary part: extinction coefficient) are preferably 1.50 < 3.0 and 0.9 < k < 3.00, more preferably 1.50 < n < 2.00 and 0.90 < k < 2.00, most preferably 1.60 < n < 1.90 and 1.20 < k < 1.50 in view of optical characteristic properties of the amorphous film. The dye has a thermal decomposition temperature of preferably from 100°C to 350°C, more preferably from 150°C to 300°C, still more preferably from 200°C to 300°C. The optical information recording medium of the invention is used preferably as a high-speed recording medium permitting 8-fold speed or faster recording, more preferably as a high-speed recording medium permitting 10-fold speed or faster recording, still more preferably as a high-speed recording medium permitting 12-fold speed or faster recording, most preferably as a high-speed recording medium permitting 16-fold speed or faster recording. The data-transporting speed is preferably 80 Mbps or more, more preferably 110 Mbps or more, still more preferably 130 Mbps or more, most preferably 170 Mbps or more. The azo dyes to be used in the invention will be described in detail below. The azo dyes are dyes synthesized by reacting an aryl or heteroaryl diazonium salt (diazo component) with a compound (coupler component) capable of undergoing azo coupling reaction with the diazonium salt and having an acidic hydrogen atom. The azo dyes to be used in the invention are preferably dyes of the structure represented by the general formula (2"). The dyes of the structure represented by the general formula (2") or (4") will be described below. The dyes of the structure represented by the general formula (2") are preferably the dyes represented by the general formula (4"). A in the general formula (2") represents a residue of a compound (coupler component) capable of undergoing azo coupling reaction with the diazonium salt to generate a dye and having an acidic hydrogen atom, i.e., a monovalent groupO derived from the coupler component. A preferably represents a substituted or unsubstituted aryl group, a 5-membered hetero ring group containing a nitrogen atom and 1 to 20 carbon atoms, or a 6-membered hetero ring group containing a nitrogen atom and 2 to 20 carbon atoms. With dyes of the structure represented by the general formula (4"), the ring formed by A1 is preferably an aromatic hydrocarbon ring having a substituent (preferably a benzene ring having a substituent), a 5-membered hetero ring containing a nitrogen atom and 1 to 20 carbon atoms, or a 6-membered hetero ring containing a nitrogen atom and 2 to 20 carebon atoms, with an aromatic hydrocarbon ring having a substituent (preferably a benzene ring having a substituent) being preferred. formulae (IV), (V) and (VI) are preferred. In the above general formulae, R11 and R13 each preferably represents a substituted or unsubstituted alkyl group containing from 1 to 20 carbon atoms, a substituted or unsubstituted aryl group containing from 6 to 20 carbon atoms, a cyano group, a substituted or unsubstituted alkoxycarbonyl group containing from 1 to 20 carbon atoms, or a substituted or unsubstituted aminocarbonyl group containing from 2 to 20 carbon atoms. R14 preferably represents a cyano group, s substituted or unsubstituted alkoxycarbonyl group containing from 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group containing from 6 to 20 carbon atoms, or a substituted or unsubstituted aminocarbonyl group containing from 2 to 20 carbon atoms. R15 represents a substituted or unsubstituted alkyl group containing from 1 to 20 carbon atoms, an aryl group containing from 6 to 20 carbon atoms, or a substituted or unsubstituted aminocarbonylamino group containing from 1 to 20 carbon atoms. Particularly preferably, R13 represents a cyano group, R14 represents an alkoxycarbonyl group containing from 1 to 20 carbon atoms, and R15 represents a substituted or unsubstituted alkyl group containing from 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group containing from 6 to 20 carbon atoms. B represents a monovalent group derived from a diazonium salt, preferably a substituted or unsubstituted aryl group, or a substituted or unsubstituted hetero ring group. That is, B is a diazo component. The diazo component means a partial structure which can be introduced by converting a hetero ring compound or benzene derivative having an amino group as a substituent to a diazo compound (diazonium salt) and conducting diazo coupling reaction with a coupler, and is a concept popularly employed in the field of azo dyes. In other words, the diazo component means a monovalent substituent which is formed by removing the amino group of an amino-substituted hetero ring compound or benzene derivative capable of undergoing the diazo reaction. B is preferably formed by B . B represents atoms forming a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aromatic hetero ring. As the ring formed by B , an aromatic hydrocarbon ring having a substituent (preferably a benzene ring having a substituent), a nitrogen atom-containing 5-membered hetero ring containing from 1 to 20 carbon atoms and a nitrogen-containing 6-membered hetero ring containing from 2 to 20 carbon atoms are preferred, with a nitrogen atom-containing 5-membered hetero ring containing from 1 to 20 carbon atoms and a nitrogen-containing 6-membered hetero ring containing from 2 to 20 carbon atoms are preferred being more preferred. A nitrogen atom-containing 5-membered hetero ring containing from 1 to 20 carbon atoms is still more preferred. As examples of the monovalent hetero ring group represented by A or B, there can be illustrated (AB-1) to (AB-25) shown below. group S in the general formula (I). b and c each represents an integer of from 0 to 6. a, p, q and r each represents an integer of from 0 to 4. d, e, f, g, t and u each represents an integer of from 0 to 3. h, I, j, k, 1 and o each represents an integer of from 0 to 2. In the case where a to u each represents an integer of 2 or more, two or more substituent are the same as described in group S in the general formula (1). G represents a monovalent group capable of coordinating to a metal ion. Examples of G include a hydroxyl group, a carboxyl group, an amino group (including an alkylamino group), an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl- or aryl-sulfonylamino group, a mercapto group, a sulfamoyl group, a sulfo group, an alkyl- or aryl-sulfinyl group, a carbamoyl group, an aryl or hetero ring azo group, a phosphino group and a phosphinyl group. G preferably represents an alkylsulfonylamino group. As the azo dye compound in accordance with the invention, those wherein the azo dye coordinates to a metal ion to form an azo metal chelate dye are also preferred. In particular, the chelate dyes have a better light resistance, thus being preferred. As a metal to be used for the metal chelate dye, Ni, Cu, Zn, Al, Ti, Fe, B, Cr and Co are preferred, with Ni, Co and Al being more preferred. In the case where the dye forms the chelate structure and ligands are insufficient with respect to the central metal to form a stable complex, it is also preferred to add other molecule than the dye of the general formula (2") to form a stable chelate dye. As the ligand to be separately added, compounds containing nitrogen, oxygen or sulfur atom are preferred. Among them, an amine compound (including aniline) and a hetero ring compound containing at least one nitrogen atom are preferred. A 5- or 6-membered amine compound containing from 3 to 20 carbon atoms is the most preferred. Specific examples of the azo dyes to be used in the invention are shown below which, however, are not to be construed as limiting the invention. Processes for synthesizing the azo dyes are described in JP-A-3-268994, JP-A-3-61088, JP-A-7-161069, JP-A-7-251567,JP-A-10.204070, JP-A-ll-12483, JP-A-l 1-166125, JP-A-2001-199169,JP-A-2001-152040 and JP-A-2002-114922. With the dye compounds in accordance with the invention shown by the general formula (1'), the coefficient n of complex refractive index (real part: refractive index) at the wavelength of a recording laser light and k (imaginary part: extinction coefficient) are preferably 2.0 < 3.0 and 0.00 < k < 0.20, more preferably 2.1

Documents

Application Documents

# Name Date
1 314-chenp-2008-abstract.pdf 2011-09-02
1 314-chenp-2008-pct.pdf 2011-09-02
2 314-chenp-2008-claims.pdf 2011-09-02
2 314-chenp-2008-form 5.pdf 2011-09-02
3 314-chenp-2008-correspondnece-others.pdf 2011-09-02
3 314-chenp-2008-form 3.pdf 2011-09-02
4 314-chenp-2008-form 1.pdf 2011-09-02
5 314-chenp-2008-drawings.pdf 2011-09-02
6 314-chenp-2008-form 1.pdf 2011-09-02
7 314-chenp-2008-correspondnece-others.pdf 2011-09-02
7 314-chenp-2008-form 3.pdf 2011-09-02
8 314-chenp-2008-claims.pdf 2011-09-02
8 314-chenp-2008-form 5.pdf 2011-09-02
9 314-chenp-2008-abstract.pdf 2011-09-02
9 314-chenp-2008-pct.pdf 2011-09-02