JP2007095274A - Optical disk - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical disk capable of recording visible images of excellent visibility on an image recording layer in the optical disk provided with the image recording layer capable of recording the visible images by using a laser beam. <P>SOLUTION: The optical disk is provided with the image recording layer capable of recording the visible images by irradiation with a laser beam on a substrate in the order. When measuring reflectivity from the substrate side, the integrated value A of the reflectivity in the area of a wavelength 500 to 600 nm of the image recording layer before recording the visible images on the image recording layer and the integrated value B of the reflectivity in the area of the wavelength 500 to 600 nm of the image recording layer after recording the visible images satisfy the relation of an expression (M1):A<B. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an optical disc, and more particularly to an optical disc having an image recording layer capable of recording a visible image.

  Conventionally, an optical recording medium (optical disc) capable of recording information only once with a laser beam is known. This optical disk is also referred to as a recordable CD (so-called CD-R), and its typical structure is a recording layer made of an organic dye on a transparent disk-shaped substrate, a light reflecting layer made of a metal such as gold, and a resin. A protective layer made of a metal is provided in this order in a laminated state. Information recording on this CD-R is performed by irradiating the CD-R with a near-infrared laser beam (usually a laser beam having a wavelength of around 780 nm), and the irradiated portion of the recording layer emits the light. Information is recorded by absorbing and locally raising the temperature, causing a physical or chemical change (eg, pit generation) and changing its optical properties. On the other hand, information reading (reproduction) is also performed by irradiating a laser beam having the same wavelength as the recording laser beam, and the portion where the optical characteristics of the recording layer have changed (recorded portion) and the portion that has not changed (unrecorded) Information is reproduced by detecting the difference in reflectance from (part).

  In recent years, an optical recording medium having a higher recording density has been demanded. In response to such a demand, an optical disc called a recordable digital vasatile disc (so-called DVD-R) has been proposed. This DVD-R is a transparent disk-shaped substrate in which guide grooves (pre-grooves) for tracking of the irradiated laser beam are narrowly formed to be less than half (0.74 to 0.8 μm) compared to CD-R. On top of that, a recording layer made of a dye, and usually two light reflecting layers on the recording layer, and further a protective layer if necessary, or a disk-shaped protective substrate having the same shape as the disk The recording layer has a structure in which the recording layer is bonded inside with an adhesive. Information recording / reproduction on a DVD-R is performed by irradiating visible laser light (usually laser light having a wavelength in the range of 630 nm to 680 nm), and recording at a higher density than CD-R is possible. Has been.

  By the way, visible information such as a title of music data recorded on the recording surface and a title for identifying the recorded data is recorded on the optical disc on the side opposite to the recording surface on which the music data is recorded. One with a printed label is known. Such an optical disc is manufactured by printing a title or the like on a circular label sheet in advance by a printer or the like, and sticking the label sheet on a surface opposite to the recording surface of the optical disc.

  However, when producing an optical disc in which a desired visible image such as a title is recorded on the label surface as described above, a printer is required separately from the optical disc drive. Therefore, after performing recording on the recording surface of an optical disk using an optical disk drive, it is necessary to perform a complicated operation such as taking out the optical disk from the optical disk drive and attaching a label sheet printed by a separately prepared printer. There is.

  In view of this, an optical recording medium has been proposed in which a laser marker is used on the surface opposite to the recording surface to change the contrast between the surface and the background (for example, see Patent Document 1). By adopting such a method, a desired image can be recorded on the label surface of the optical disk by the optical disk drive without separately preparing a printer or the like. However, with this method, the sensitivity is low and a high-power gas laser such as a carbon dioxide laser must be used, and the visible image formed by the laser light as described above has low contrast and poor visibility.

  As another example, an optical recording medium having a color-developing layer that develops different colors when irradiated with laser beams having different characteristics has been proposed (see, for example, Patent Document 2). However, this optical recording medium has a problem that the layer structure and recording apparatus are complicated and fine gradation cannot be applied.

  On the other hand, a visible information recording layer that uses the same laser light as that used for reproducing (recording) main information and can record visible information by contrast caused by the difference in reflectance between the irradiated portion and the non-irradiated portion of the laser beam Has been proposed (for example, see Patent Document 3). However, in the past, there has been no pursuit for improving the visibility of visible information, leaving room for improvement.

JP-A-11-66617 JP 2003-272240 A JP 2004-103180 A

  The present invention has been made in view of the above-described conventional problems. In an optical disc having an image recording layer capable of recording a visible image using a laser beam, the image recording layer has good visibility. An object is to provide an optical disc capable of recording an image.

  As a result of intensive studies, the present inventors have found that sufficient visibility can be obtained by setting the light reflectance in the region of 500 to 600 nm to a specific range, and have completed the present invention.

<1> The optical disc according to the present invention is an optical disc including a laminate having, in this order, at least an image recording layer capable of recording a visible image by irradiation with a laser beam on a substrate, and having a reflectance from the substrate side. When measured, the integrated value A of the reflectance in the wavelength region of 500 to 600 nm of the image recording layer before recording the visible image on the image recording layer, and the image recording layer after recording the visible image The integrated value B of the reflectance in the region of the wavelength of 500 to 600 nm satisfies the relationship of the following formula (M1).
A <B Formula (M1)

<2> The optical disc according to <1>, wherein the laminate and another laminate having at least the information recording layer and the reflective layer in this order are bonded to another substrate.

<3> The optical disc according to <1> or <2>, wherein the image recording layer contains a dye compound.

<4> The optical disk according to <3>, wherein the image recording layer is formed using a coating liquid containing a dye compound.

<5> The optical disc according to any one of <1> to <4>, wherein the substrate on which the image recording layer is formed is a substrate having no groove.

  ADVANTAGE OF THE INVENTION According to this invention, the optical disk which can record a visible image with favorable visibility on an image recording layer in the optical disk which has an image recording layer which can record a visible image using a laser beam can be provided. .

The optical disc of the present invention is an optical disc comprising a laminate having, in this order, at least an image recording layer capable of recording a visible image by laser light irradiation and a reflective layer on the substrate, and the reflectance from the substrate side. When the visible image is recorded on the image recording layer, the integrated value A of the reflectance in the region of wavelength 500 to 600 nm of the image recording layer and the image recording after recording the visible image. The integral value B of the reflectance in the wavelength region of 500 to 600 nm of the layer satisfies the relationship of the following formula (M1).
A <B Formula (M1)
Hereinafter, the optical disk according to the present embodiment will be described.

  The type of the optical disk according to the present embodiment may be any of a read-only type, a write-once type, a rewritable type, etc., but is preferably a write-once type. The recording format is not particularly limited, such as phase change type, magneto-optical type, and dye type, but is preferably a dye type.

Examples of the layer configuration of the optical disc according to the present embodiment include the following configurations.
(1) Substrate, information recording layer, reflective layer, adhesive layer, image recording layer, substrate (2) Substrate, information recording layer, reflective layer, protective layer, adhesive layer, image recording layer, substrate (3) substrate, information recording Layer, reflective layer, protective layer, adhesive layer, protective layer, image recording layer, substrate (4) substrate, information recording layer, reflective layer, protective layer, adhesive layer, protective layer, reflective layer, image recording layer, substrate (5 ) Substrate, information recording layer, reflective layer, adhesive layer, reflective layer, image recording layer, substrate (6) Cover layer, adhesive layer, information recording layer, reflective layer, substrate, reflective layer, image recording layer, protective layer (7 ) Cover layer, information recording layer, reflective layer, substrate, reflective layer, image recording layer, protective layer (8) Cover layer, adhesive layer, information recording layer, reflective layer, substrate, reflective layer, image recording layer, dielectric layer , Protective layer (9) cover layer, information recording layer, reflective layer, substrate, reflective layer, image recording layer, dielectric layer, protective layer (10) substrate, information recording , Reflective layer, protective layer, reflective layer, the image recording layer, a protective layer (11) substrate, the information recording layer, reflective layer, protective layer, reflective layer, the image recording layer, dielectric layer, protective layer

  Note that the layer configurations (1) to (11) are merely examples, and the layer configuration is not limited to the order described above, and a part of the layer configuration may be replaced. A part may be omitted. Furthermore, each layer may be composed of one layer or a plurality of layers.

  In addition, the configurations of (1) to (5) described above include a laminate having at least an image recording layer in this order on a substrate, and another laminate having at least an information recording layer and a reflective layer in this order on another substrate. It is an optical disc that is bonded to the body.

  Hereinafter, the substrate and each layer will be described.

[Information recording layer]
The information recording layer is a layer on which code information (coded information) such as digital information is recorded, and examples thereof include a dye type, a write-once type, a phase change type, and a magneto-optical type. It is preferable that

  Specific examples of the dye contained in the dye-type information recording layer include a cyanine dye, an oxonol dye, a metal complex dye, an azo dye, and a phthalocyanine dye.

  JP-A-4-74690, JP-A-8-127174, 11-53758, 11-334204, 11-334205, 11-334206, 11-334207 No. 2000-43423, 2000-108513, 2000-158818, and the like are preferably used.

  Furthermore, the recording material is not limited to a dye, but a triazole compound, triazine compound, cyanine compound, merocyanine compound, aminobutadiene compound, phthalocyanine compound, cinnamic acid compound, viologen compound, azo compound, oxonol compound, benzoxazole compound, benzotriazole Organic compounds such as compounds are also preferably used. Among these compounds, cyanine compounds, aminobutadiene compounds, oxonol compounds, benzotriazole compounds, and phthalocyanine compounds are particularly preferable.

  As the dye for the recording layer, it is preferable to use a dye or a combination of dyes used in the image recording layer described later.

  The information recording layer is prepared by dissolving a recording substance such as a dye in a suitable solvent together with a binder and the like, and then coating the coating liquid on a substrate to form a coating film, followed by drying. It is formed by. The concentration of the recording substance in the coating solution is generally in the range of 0.01 to 15% by mass, preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 5% by mass, and most preferably. Is in the range of 0.5-3 mass%.

  The information recording layer can be formed by a method such as vapor deposition, sputtering, CVD, or solvent coating, but solvent coating is preferred.

  Examples of the solvent for the coating solution include esters such as butyl acetate, ethyl lactate and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chloroform; dimethylformamide and the like Amide; Hydrocarbon such as methylcyclohexane; Ether such as dibutyl ether, diethyl ether, tetrahydrofuran, dioxane; Alcohol such as ethanol, n-propanol, isopropanol, n-butanol, diacetone alcohol; 2,2,3,3-tetra Fluorinated solvents such as fluoropropanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether And the like can be given.

  The above solvents can be used alone or in combination of two or more in consideration of the solubility of the dye used. Various additives such as antioxidants, UV absorbers, plasticizers, lubricants and the like may be further added to the coating solution depending on the purpose.

  When a binder is used, examples of the binder include natural organic polymer materials such as gelatin, cellulose derivatives, dextran, rosin and rubber; and hydrocarbon resins such as polyethylene, polypropylene, polystyrene and polyisobutylene; Vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride / polyvinyl acetate copolymer; acrylic resins such as polymethyl acrylate and polymethyl methacrylate; polyvinyl alcohol, chlorinated polyethylene, epoxy resin, butyral resin, Examples include synthetic organic polymers such as rubber derivatives and initial condensates of thermosetting resins such as phenol / formaldehyde resins.

  When a binder is used in combination as a material for the information recording layer, the amount of the binder used is generally in the range of 0.01 to 50 times the mass of the dye, preferably 0.1 to 5 times the amount. It is in the range.

  Examples of the solvent application method include a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, and a screen printing method. The information recording layer may be a single layer or a multilayer. The thickness of the information recording layer is generally in the range of 10 to 500 nm, preferably in the range of 15 to 300 nm, and more preferably in the range of 20 to 150 nm.

  The information recording layer can contain various anti-fading agents in order to improve the light resistance of the information recording layer. As the anti-fading agent, a singlet oxygen quencher is generally used. As the singlet oxygen quencher, those described in publications such as known patent specifications can be used. Specific examples thereof include JP-A Nos. 58-175893, 59-31194, 60-18387, 60-19586, 60-19587, 60-35054, 60-36190, 60-36191, 60-44554, 60-44555, 60-44389, 60-44390, 60-54892, 60-47069, 68-209995, JP No. 4-25492, JP-B-1-38680, and JP-B-6-26028, etc., German Patent No. 350399, and Japanese Chemical Society Journal October 1992, page 1141, etc. be able to.

  The amount of the anti-fading agent such as the singlet oxygen quencher used is usually in the range of 0.1 to 50% by mass, preferably in the range of 0.5 to 45% by mass, more preferably , In the range of 3 to 40% by mass, particularly preferably in the range of 5 to 25% by mass.

  Specific examples of materials constituting the phase change type information recording layer include Sb—Te alloy, Ge—Sb—Te alloy, Pd—Ge—Sb—Te alloy, Nb—Ge—Sb—Te alloy, and Pd—Nb. -Ge-Sb-Te alloy, Pt-Ge-Sb-Te alloy, Co-Ge-Sb-Te alloy, In-Sb-Te alloy, Ag-In-Sb-Te alloy, Ag-V-In-Sb- Te alloy, Ag-Ge-In-Sb-Te alloy, etc. are mentioned. Among these, Ge—Sb—Te alloy and Ag—In—Sb—Te alloy are preferable because they can be rewritten many times.

  The layer thickness of the phase change information recording layer is preferably 10 to 50 nm, more preferably 15 to 30 nm.

  The above-described phase change type information recording layer can be formed by a vapor phase thin film deposition method such as a sputtering method or a vacuum evaporation method.

[substrate]
The substrate of the optical disk of the present invention can be arbitrarily selected from various materials used as a substrate of a conventional optical disk, on either side of the information recording layer and the image recording layer.

  Examples of substrate materials include acrylic resins such as glass, polycarbonate, and polymethyl methacrylate, vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers, epoxy resins, cellulose triacetate (TAC), amorphous polyolefin, and polyester. These may be used together if desired.

  These materials can be used as a film or as a rigid substrate. Among the above materials, polycarbonate is preferable from the viewpoints of moisture resistance, dimensional stability, price, and the like.

  The thickness of the substrate is preferably 5 to 1200 μm, and more preferably 10 to 600 μm. The substrate on the side on which the information recording layer is provided has a track pitch of 700 to 800 nm, a groove depth of 100 to 200 nm, and a groove width of 250 to 250 when laser light having a wavelength of about 660 nm is used for information recording or reproduction. It is preferable that they are 400 nm and a groove inclination angle: 30 to 70 degrees. When laser light having a wavelength of about 405 nm is used for information recording or reproduction, the track pitch is 300 to 400 nm, the groove depth is 20 to 100 nm, the groove width is 100 to 200 nm, and the groove inclination angle is 30 to 70 degrees. Preferably there is. When laser light having a wavelength of around 780 nm is used for information recording or reproduction, track pitch: 1.5 to 1.7 μm, groove depth: 100 to 220 nm, groove width: 400 to 800 nm, groove inclination angle: 30 It is preferable that it is -70 degree | times.

  An undercoat layer is provided on the surface of the substrate on which the information recording layer is provided (the surface on which the groove is formed) for the purpose of improving flatness, improving adhesion, and preventing deterioration of the information recording layer. Also good.

  Examples of the material for the undercoat layer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleic anhydride copolymer, polyvinyl alcohol, N-methylol acrylamide, styrene / vinyl toluene copolymer, chlorosulfonated. High molecular substances such as polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate, and silane coupling agents And the like. The undercoat layer is formed by dissolving or dispersing the above substances in a suitable solvent to prepare a coating solution, and then applying this coating solution to the substrate surface by a coating method such as spin coating, dip coating, or extrusion coating. can do.

  The thickness of the undercoat layer is generally in the range of 0.005 to 20 μm, preferably in the range of 0.01 to 10 μm.

  In order to record a high-definition image on the image recording layer, a tracking groove (groove) may be provided on the substrate on the side where the image recording layer is provided. In this case, in the first aspect, when a laser beam having a wavelength of around 660 nm is used, the track pitch of the groove is preferably in the range of 0.7 to 200 μm, and is preferably in the range of 1 to 100 μm. More preferably, it is more preferable to set it as the range of 1.5-50 micrometers. Further, the depth of the groove is preferably 50 to 300 nm, preferably 80 to 250 nm when tracking is performed during image recording and the thickness of the substrate on the laser beam incident side is 0.6 mm. Is more preferable, and it is more preferable to set it as 100-200 nm. The width of the groove is preferably 100 to 500 nm, more preferably 200 to 400 nm, and further preferably 250 to 350 nm. The inclination angle of the groove is preferably 30 to 70 degrees.

  On the other hand, when a laser beam having a wavelength of around 780 nm is used, the groove track pitch is preferably in the range of 1 to 200 μm, more preferably in the range of 1.6 to 100 μm, and 3 to 50 μm. More preferably, it is within the range. In addition, the depth of the groove is preferably 100 to 300 nm, preferably 130 to 250 nm when tracking is performed during image recording and the thickness of the substrate on the laser light incident side is 0.6 mm. Is more preferable, and it is further more preferable to set it as 150-200 nm. The width of the groove is preferably 100 to 1000 nm, more preferably 200 to 700 nm, and still more preferably 300 to 600 nm. The inclination angle of the groove is preferably 30 to 70 degrees.

  Note that the optimum range of the groove shape may differ depending on the wavelength of the laser light, NA, substrate thickness, and the like.

[Reflective layer]
A reflective layer may be provided adjacent to the information recording layer for the purpose of improving the reflectance during information reproduction. The light-reflective substance that is the material of the reflective layer is a substance having a high reflectivity with respect to laser light. Examples thereof include Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W. , Mn, Re, Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi And metals such as semi-metals and stainless steel. These substances may be used alone or in combination of two or more or as an alloy. Among these, Cr, Ni, Pt, Cu, Ag, Au, Al, and stainless steel are preferable. Particularly preferred are Au metal, Ag metal, Al metal or alloys thereof, and most preferred are Ag metal, Al metal or alloys thereof. The reflective layer can be formed on the substrate or the information recording layer, for example, by vapor deposition, sputtering or ion plating of the light reflective material. The thickness of the reflective layer is generally in the range of 10 to 300 nm, and preferably in the range of 50 to 200 nm.

[Adhesive layer]
The adhesive layer is an arbitrary layer formed to improve the adhesion between the reflective layer or protective layer on the information recording layer side and the substrate or protective layer on the image recording layer side.

  As a material constituting the adhesive layer, a photo-curing resin is preferable, and in particular, a material having a small curing shrinkage rate is preferable in order to prevent the disk from warping. Examples of such a photocurable resin include UV curable resins (UV curable adhesive) such as “SD-640” and “SD-347” manufactured by Dainippon Ink and Chemicals, Inc. it can. The thickness of the adhesive layer is preferably in the range of 1 to 1000 μm, more preferably in the range of 5 to 500 μm, and particularly preferably in the range of 10 to 100 μm in order to give elasticity.

[Image recording layer]
In the image recording layer, visible images (visible information) desired by the user, such as characters, graphics, and patterns, are recorded. Examples of visible images include disc titles, content information, content thumbnails, related patterns, design patterns, copyright information, recording date, recording method, recording format, barcodes, and the like.

  The visible image recorded in the image recording layer means a visually recognizable image, and includes all visually recognizable information such as characters (rows), designs, and figures. Also, as character information, usable person designation information, use period designation information, usable number designation information, rental information, resolution designation information, layer designation information, user designation information, copyright holder information, copyright number information, manufacturing Information, manufacturer date information, sale date information, dealer or seller information, use set number information, region designation information, language designation information, application designation information, product user information, use number information, and the like.

  The image recording layer only needs to be able to record image information such as characters, images, and patterns by laser light irradiation, and as the constituent material, the dye described in the information recording layer described above is preferably used. it can.

In the present invention, as described above, when the reflectance is measured from the substrate side, the image recording layer has a wavelength of 500 to 600 nm of the image recording layer before recording the visible image on the image recording layer. The integral value A of the reflectance of the region and the integral value B of the reflectance of the region having a wavelength of 500 to 600 nm of the image recording layer after recording the visible image satisfy the relationship of the following formula (M1).
A <B Formula (M1)

  By satisfy | filling said Formula (M1), the image recording layer with favorable visibility of the recorded visible image is obtained. The reason why the above effect is obtained is not clear, but humans are highly sensitive to light in the region of 500 to 600 nm, and sufficient visibility is obtained when the reflectance increases at that position. In the present invention, it is considered that a sufficient color change has occurred due to the above configuration.

  In the formula (M1), 1.2 × A <B is preferable, and 1.5 × A <B is more preferable.

  As described above, setting an image recording layer satisfying the above formula (M1) before and after image recording can be realized by appropriately selecting a dye used for the image recording layer, for example. Then, these dyes are dissolved in a suitable solvent together with a binder and the like to prepare a coating solution. Next, the coating solution is applied onto a substrate to form a coating film, and then dried to form an image recording layer. It is formed. The concentration of the recording substance in the coating solution is generally in the range of 0.01 to 15% by mass, preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 5% by mass, and most preferably. Is in the range of 0.5-3 mass%.

  Specific examples of the dye include cyanine dyes, imidazoquinoxaline dyes, pyrylium / thiopyrylium dyes, azurenium dyes, squarylium dyes, azo dyes, metal complex dyes such as Ni and Cr (phthalocyanine dyes, azo metal chelate dyes) , Pyromethene metal chelate dyes), naphthoquinone dyes, anthraquinone dyes, indophenol dyes, indoaniline dyes, triphenylmethane dyes, merocyanine dyes, oxonol dyes, aminium dyes, ultraviolet absorbers, Among these, cyanine dyes, phthalocyanine dyes, azo dyes (including metal chelate dyes), merocyanine dyes, oxonol dyes, and ultraviolet absorbers are particularly preferably used.

  Oxonol dye and cyanine dye; Oxonol dye and azo dye; Oxonol dye and another oxonol dye; Oxonol dye and phthalocyanine dye; Oxonol dye and pyromethene dye; Cyanine dye and another cyanine dye; Preferred examples include cyanine dyes and phthalocyanine dyes; cyanine dyes and pyromethene dyes; azo dyes and phthalocyanine dyes; azo dyes and pyromethene dyes; phthalocyanine dyes and pyromethene dyes.

  Among the dyes described above, a cyanine dye or a phthalocyanine dye is preferable, and a combination of both is preferable. In particular, when a cyanine dye and a phthalocyanine dye are mixed and used, an optical disk that satisfies the requirements of the first aspect of the present invention can be obtained.

  The image recording layer can also be an information recording layer by appropriately selecting the type of dye.

  In the case of a combination of dyes, the content ratio (mass ratio) between the dyes is preferably 99: 1 to 1:99, more preferably 80:20 to 20:80, and still more preferably 70:30 to 30:70.

  Regarding the above dyes, the cyanine, phthalocyanine and oxonol dyes will be described in detail.

-Cyanine dye-
For general cyanine dyes, the cyanine dyes and related compounds (Cyanine Dies and Related Compounds. John Wwley & Sons.on Y. or N. 64) from the Chemistry of Heterocyclic Compound series. It is described in.

  In the present invention, the cyanine dye is preferably a cyanine dye represented by the following general formula (1).

In the general formula (1), Za ²¹ and Za ²² each independently represent an atomic group forming a heterocycle. Ma ²¹ , Ma ²² and Ma ²³ each independently represents a substituted or unsubstituted methine group. ka2 represents an integer from 0 to 3, and when ka2 is 2 or more, a plurality of Ma ²¹ and Ma ²² may be the same or different. R ¹⁰¹ and R ¹⁰² each independently represents a substituent. Q2 represents an ion for neutralizing the electric charge, and y2 represents a number necessary for neutralizing the electric charge.

In the general formula (1), Ma ²¹ , Ma ²² and Ma ²³ each independently represents a substituted or unsubstituted methine group. In the case of having a substituent, the substituent includes 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 bicycloalkenyl group). ), Substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted Substituted aryloxy group, substituted or unsubstituted silyloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted carbamoyloxy group, substituted or unsubstituted alkoxycarbonyloxy group Substituted or unsubstituted arylo Sicarbonyloxy, substituted or unsubstituted amino group (including anilino group), substituted or unsubstituted acylamino group, substituted or unsubstituted aminocarbonylamino group, substituted or unsubstituted alkoxycarbonylamino group, substituted or unsubstituted Aryloxycarbonylamino group, substituted or unsubstituted sulfamoylamino group, substituted or unsubstituted alkyl and arylsulfonylamino group, substituted or unsubstituted mercapto group, substituted or unsubstituted alkylthio group, substituted or unsubstituted Arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted sulfamoyl group, sulfo group, substituted or unsubstituted alkyl and arylsulfinyl group, substituted or unsubstituted alkyl and arylsulfonyl group, substituted or Substituted acyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted aryl and heterocyclic azo group, substituted or unsubstituted imide Examples are a 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, or a substituted or unsubstituted silyl group. As mentioned.

  More specifically, the substituent represents a halogen atom (for example, chlorine atom, bromine atom, iodine atom), an alkyl group [straight chain, branched, cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), tricyclo structures with more ring structures, etc. It is intended to embrace. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or unsubstituted 3 to 30 carbon atoms or An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [ It is intended to encompass 2,2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group), an aryl group (preferably a substituted or unsubstituted aryl having 6 to 30 carbon atoms) Groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocycles A monovalent group obtained by removing one hydrogen atom from a compound, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group ( Preferably, it is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably carbon A substituted or unsubstituted aryloxy group of formula 6 to 30, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably, A silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazole -5-oxy, 2-tetrahydropyranyloxy) Acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy , Stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy, N, N -Diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably having 2 to 30 carbon atoms) Or an unsubstituted alkoxycarbonyloxy group, for example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted group having 7 to 30 carbon atoms) Aryloxycarbonyloxy group of, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably amino group, substituted or non-substituted with 1 to 30 carbon atoms) Substituted alkylamino group, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino group (Preferably, a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, Lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, such as carbamoylamino N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, For example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms substituted or unsubstituted A substituted aryloxycarbonylamino group such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted group having 0 to 30 carbon atoms) Substituted sulfamoylamino groups such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably Or substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3, 5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), arylthio group (Preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), heterocyclic thio group (preferably substituted or unsubstituted having 2 to 30 carbon atoms) Hete A ring thio group such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl) N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, Alkyl and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p- Methylphenylsulfinyl) Alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p- Methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, substitution having 4 to 30 carbon atoms Or a heterocyclic carbonyl group bonded to a carbonyl group with an unsubstituted carbon atom, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2- Furylcarbonyl), ally An oxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxy A carbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably having 1 to 1 carbon atoms) 30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl) Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5 -Ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N-succinimide, N-phthalimide), phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms) Dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, eg phosphinyl, dioctyloxyphosphinyl, diethoxyphosphine Finyl), a phosphinyloxy group (preferably A substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferably a substitution having 2 to 30 carbon atoms) Or an unsubstituted phosphinylamino group such as dimethoxyphosphinylamino or dimethylaminophosphinylamino), a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).

The substituent when M ²¹ , M ²² and M ²³ are substituted is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. As the substituted or unsubstituted alkyl group, an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl, butyl, i-butyl, t-butyl, i-amyl, cyclopropyl, cyclohexyl, benzyl) And phenethyl). In the case of representing an alkyl group, they are connected to each other to form a carbocyclic ring (for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, cycloheptyl, cyclooctyl, etc.) or a heterocyclic ring (for example, piperidyl). , Chromanyl, morpholyl, etc.). When the substituent is an alkyl group, it is preferably a chain alkyl group or a cyclic alkyl group having 1 to 8 carbon atoms, and most preferably a chain (straight chain or branched chain) alkyl group having 1 to 5 carbon atoms. A cyclic alkyl group having 1 to 8 carbon atoms (preferably a cyclohexyl ring) in which the alkyl group is bonded to each other to form a ring, or a substituted alkyl group having 1 to 20 carbon atoms (for example, benzyl, phenethyl) It is.

Ma ²¹ , Ma ²² and Ma ²³ are preferably unsubstituted rather than substituted.

In general formula (1), R ¹⁰¹ and R ¹⁰² each independently represent a substituent, but are substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted alkenyl groups, substituted or An unsubstituted alkynyl group or a substituted or unsubstituted heterocyclic group is preferred. These groups may be further substituted, and examples of the substituent to be substituted include the substituents in the case where the above-mentioned Ma ²¹ , Ma ²² and Ma ²³ are substituted.

R ¹⁰¹ and R ¹⁰² are preferably a substituted or unsubstituted alkyl group, further a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and further an unsubstituted group having 1 to 8 carbon atoms. It is an alkyl group. R ¹⁰¹ and R ¹⁰² may be the same or different, but are preferably the same.

  Q2 represents an ion for neutralizing the electric charge, and y2 represents a number necessary for neutralizing the electric charge. The ion represented by Q2 represents an anion depending on the charge of the dye molecule to which it is associated, and there is no particular limitation on the ion represented by Q2, and even an ion composed of an inorganic compound is an ion composed of an organic compound. It does not matter. Further, the charge of the ions represented as Q2 may be monovalent or multivalent. Examples of the anion represented as Q2 include halogen anions such as chloride ion, bromide ion and fluoride ion, heteropoly acid ions such as sulfate ion, phosphate ion and hydrogen phosphate ion, oxalate ion and maleate. Examples thereof include organic polyvalent anions such as acid ions, fumarate ions and aromatic disulfonate ions, tetrafluoroborate ions, and hexafluorophosphate ions.

In general formula (1), y2 represents a number necessary for neutralization of electric charge. When Q2 is a divalent anion, if y2 is 1/2, Q2y2 is considered as a monovalent anion as a whole. ka2 represents an integer from 0 to 3, and when ka2 is 2 or more, a plurality of Ma ²¹ and Ma ²² may be the same or different.

  Among the cyanine dyes represented by the general formula (1), cyanine dyes represented by the following general formula (2) are preferable.

In the general formula (2), Za ³¹ and Za ³² each independently represent an atomic group forming a carbocycle or a heterocycle. R ^1a and R ^2a each independently represent a substituent. R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ and R ¹²⁷ each independently represents a hydrogen atom or a substituent. ka3 represents an integer from 0 to 3, and when ka3 is 2 or more, a plurality of R ¹²¹ and R ¹²² may be the same or different. Q3 represents an ion for neutralizing the electric charge, and y3 represents a number necessary for neutralizing the electric charge.

In the general formula (2), R ¹²¹ , R ¹²² and R ¹²³ are a hydrogen atom or a substituent, and the substituent is synonymous with the substituent for substituting Ma ²¹ , Ma ²² and Ma ²³ in the general formula (1). The preferred examples are also the same. R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , and R ¹²⁷ are a hydrogen atom or a substituent, and the substituent is synonymous with the above-described substituent when M ²¹ , M ²² , and M ²³ are substituted, and is preferable. The example is similar. R ^1a and R ^2a have the same ^{meanings as} R ¹⁰¹ and R ¹⁰² in formula (1), and preferred examples are also the same. ka3 is synonymous with ka2 of General formula (1), and its preferable example is also the same.

  In general formula (2), Q3 represents an ion that neutralizes charge, and y3 represents a number necessary for charge neutralization. The ion represented by Q3 represents an anion depending on the charge of the dye molecule to which it corresponds, and there is no particular limitation on the ion represented by Q3. Even an ion composed of an inorganic compound is an ion composed of an organic compound. It does not matter. Further, the charge of the ion represented as Q3 may be monovalent or multivalent. Examples of the anion represented as Q3 include halogen anions such as chloride ion, bromide ion and fluoride ion, heteropoly acid ions such as sulfate ion, phosphate ion and hydrogen phosphate ion, oxalate ion and maleate. Examples thereof include organic polyvalent anions such as acid ions, fumarate ions and aromatic disulfonate ions, tetrafluoroborate ions, and hexafluorophosphate ions.

  y3 represents a number necessary for charge neutralization. When Q3 is a divalent anion, if y3 is ½, Q3y3 is considered as a monovalent anion.

In the cyanine dye represented by the general formula (1) used in the present embodiment, Ma ²¹ , Ma ²² and Ma ²³ are preferably unsubstituted methine groups, and R ¹⁰¹ and R ¹⁰² are each independently It is preferably an unsubstituted alkyl group having 1 to 8 carbon atoms, and Za ²¹ and Za ²² each independently preferably form an indolenine ring, Ka2 is 1 or 2, and Q2 is 1 Y2 is 1.

In the cyanine dye represented by the general formula (2), R ¹²⁴ , R ¹²⁵ , R ¹²⁶ and R ¹²⁷ are each independently a substituted or unsubstituted alkyl group, and R ¹²¹ , R ¹²² and R ¹²³ are hydrogen. An atom is preferable, and Za ³¹ and Za ³² each independently preferably form a benzene ring or a naphthalene ring. Ka3 is preferably 1 or 2, Q3 is preferably an inorganic or organic anion, and y3 is preferably 1.

  Specific examples of the cyanine compound having the structure represented by the general formula (1) are given below. The present invention is not limited by this specific example.

  The cyanine dye according to the present embodiment (preferably the dye compound represented by the general formula (2)) has a complex refractive index coefficient n (real part: refractive index) at the recording laser wavelength due to the optical characteristics of the amorphous film. , K (imaginary part: extinction coefficient) are preferably 1.50 ≦ n ≦ 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. What has a thermal decomposition temperature in the range of 100 to 350 degreeC is preferable. Furthermore, what is in the range of 150 to 300 degreeC is preferable. Furthermore, the thing in the range of 200 to 300 degreeC is preferable.

-Phthalocyanine dye-
Next, the phthalocyanine dye will be described. The phthalocyanine dye is preferably a phthalocyanine dye represented by the following general formula (3).

In the general formula (3), Rα ^{1 to} Rα ⁸ and Rβ ^{1 to} Rβ ⁸ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a formyl group, a carboxyl group, a sulfo group, or 1 to 20 carbon atoms. An alkyl group having 6 to 14 carbon atoms, a heterocyclic group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, and 2 carbon atoms. An acyl group having 1 to 21 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, a carbamoyl group having 1 to 25 carbon atoms, a sulfamoyl group having 0 to 32 carbon atoms, and 2 carbon atoms. 1 to 21 alkoxycarbonyl groups, 7 to 15 aryloxycarbonyl groups, 2 to 21 acylamino groups, 1 to carbon atoms 0 sulfonylamino group, an amino group having a carbon number of 0 to 36, M represents a metal having two hydrogen atoms, a metal, a metal oxide or a ligand.

In the general formula (3), Rα ^{1 to} Rα ⁸ and Rβ ^{1 to} Rβ ⁸ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a formyl group, a carboxyl group, a sulfo group, or 1 to 20 carbon atoms. An alkyl group having 6 to 14 carbon atoms, a heterocyclic group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, and 2 carbon atoms. An acyl group having 1 to 21 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, a carbamoyl group having 1 to 25 carbon atoms, a sulfamoyl group having 0 to 32 carbon atoms, and 2 carbon atoms. 1 to 21 alkoxycarbonyl groups, 7 to 15 aryloxycarbonyl groups, 2 to 21 acylamino groups, 1 to carbon atoms 0 sulfonylamino group, an amino group having a carbon number of 0 to 36, M represents a metal having two hydrogen atoms, a metal, a metal oxide or a ligand.

In the general formula (3), it is preferable that all of Rα ^{1 to} Rα ⁸ are not hydrogen atoms at the same time. Furthermore, ^one of Rα ¹ and Rα ² , one of Rα ³ and Rα ⁴ , Rα ⁵ and Rα It is preferable that any one of ⁶ and any one of Rα ⁷ and Rα ⁸ are not hydrogen atoms at the same time. Particularly, at this time, it is preferable that all of Rβ ^{1 to} Rβ ⁸ are hydrogen atoms at the same time. preferable.

In the general formula (3), preferred examples of Rα ^{1 to} Rα ⁸ and Rβ ^{1 to} Rβ ⁸ include a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 16 carbon atoms, and 6 to 6 carbon atoms. 10 aryl groups, alkoxy groups having 1 to 16 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, alkylsulfonyl groups having 1 to 16 carbon atoms, arylsulfonyl groups having 6 to 16 carbon atoms, carbon atoms A sulfamoyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 17 carbon atoms, an aryloxycarbonyl group having 7 to 11 carbon atoms, an acylamino group having 2 to 18 carbon atoms, and a sulfonylamino group having 1 to 18 carbon atoms Group, but more preferable are a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a carbon atom. An alkoxy group having 1 to 16 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an alkylsulfonyl group having 1 to 14 carbon atoms, an arylsulfonyl group having 6 to 14 carbon atoms, a sulfamoyl group having 2 to 16 carbon atoms, An alkoxycarbonyl group having 2 to 13 carbon atoms, an acylamino group having 2 to 14 carbon atoms, and a sulfonylamino group having 1 to 14 carbon atoms, and more preferably, Rα ^{1 to} Rα ⁸ are a hydrogen atom, a halogen atom, Sulfo group, alkoxy group having 8 to 16 carbon atoms, sulfonyl group having 1 to 12 carbon atoms, sulfamoyl group having 1 to 12 carbon atoms, acylamino group having 2 to 12 carbon atoms, 1 to 12 carbon atoms sulfonylamino group, Rβ ¹ ~Rβ ⁸ is a hydrogen atom or a halogen atom, particularly preferably, less of Rα ¹ ~Rα ⁸ Both one but, an alkylsulfonyl group having 1 to 10 carbon atoms, an arylsulfonyl group having 6 to 14 carbon atoms, a sulfamoyl group of 1 to 10 carbon atoms, Rβ ¹ ~Rβ ⁸ is a hydrogen atom.

In the general formula (3), Rα ^{1 to} Rα ⁸ and Rβ ^{1 to} Rβ ⁸ may further have a substituent, and examples of the substituent include those described below. A linear or cyclic alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, isopropyl group, cyclohexyl group), aryl group having 6 to 18 carbon atoms (for example, phenyl group, chlorophenyl group, 2, 4-di-t-amylphenyl group, 1-naphthyl group), alkenyl group having 2 to 20 carbon atoms (for example, vinyl group, 2-methylvinyl group), alkynyl group having 2 to 20 carbon atoms (for example, Ethynyl group, 2-methylethynyl group, 2-phenylethynyl group), halogen atom (for example, F, Cl, Br, I), cyano group, hydroxyl group, carboxyl group, acyl group having 2 to 20 carbon atoms (for example, Acetyl group, benzoyl group, salicyloyl group, pivaloyl group), alkoxy group having 1 to 20 carbon atoms (for example, methoxy group, butoxy group, cyclohexyl group). Ruoxy group), an aryloxy group having 6 to 20 carbon atoms (eg, phenoxy group, 1-naphthoxy group, toluoyl group), an alkylthio group having 1 to 20 carbon atoms (eg, methylthio group, butylthio group, benzylthio group, 3-methoxypropylthio group), arylthio group having 6 to 20 carbon atoms (for example, phenylthio group, 4-chlorophenylthio group), alkylsulfonyl group having 1 to 20 carbon atoms (for example, methanesulfonyl group, butanesulfonyl group) ), An arylsulfonyl group having 6 to 20 carbon atoms (for example, benzenesulfonyl group, paratoluenesulfonyl group), a carbamoyl group having 1 to 17 carbon atoms (for example, unsubstituted carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group) , N-butylcarbamoyl group, dimethylcarbamoyl ), An amide group having 1 to 16 carbon atoms (for example, an acetamide group or a benzamide group), an acyloxy group having 2 to 10 carbon atoms (for example, an acetoxy group or a benzoyloxy group), or an alkoxycarbonyl having 2 to 10 carbon atoms. Groups (for example, methoxycarbonyl group, ethoxycarbonyl group), 5- or 6-membered heterocyclic groups (for example, aromatic heterocyclic groups such as pyridyl group, thienyl group, furyl group, thiazolyl group, imidazolyl group, pyrazolyl group); A heterocyclic group such as a cyclic group, a piperidine cyclic group, a morpholine cyclic group, a pyran cyclic group, a thiopyran cyclic group, a dioxane cyclic group or a dithiolane cyclic group).

In the general formula (3), a preferable substituent for Rα ^{1 to} Rα ⁸ and Rβ ^{1 to} Rβ ⁸ is a linear or cyclic alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 14 carbon atoms. , An alkoxy group having 1 to 16 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, a halogen atom, an alkoxycarbonyl group having 2 to 17 carbon atoms, a carbamoyl group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms 10 is an amide group, and among them, preferred are linear or cyclic alkyl groups having 1 to 10 carbon atoms, aralkyl groups having 7 to 13 carbon atoms, aryl groups having 6 to 10 carbon atoms, and the number of carbon atoms. An alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a chlorine atom, an alkoxycarbonyl group having 2 to 11 carbon atoms, a carbamoyl group having 1 to 7 carbon atoms, and an aryl group having 1 to 8 carbon atoms. Particularly preferred are linear branched or cyclic alkyl groups having 1 to 8 carbon atoms, aralkyl groups having 7 to 11 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, and 3 carbon atoms. Are an alkoxycarbonyl group having 9 to 9 carbon atoms, a phenyl group and a chlorine atom, more preferably an alkoxy group having 1 to 6 carbon atoms.

  In the general formula (3), M is preferably a metal, among which zinc, magnesium, copper, nickel or palladium is preferable, copper, zinc or magnesium is more preferable, and copper is particularly preferable. The phthalocyanine dye molecule may have a ferrocenyl group which may be substituted.

  Specific examples of the phthalocyanine dye are shown below.

  Examples of the phthalocyanine derivative used in the present embodiment include “Phthalocyanine—Chemistry and Function” (p. 1 to 62) published by K. Shirai and Kobayashi, Inc. C. Leznoff-A. B. P. Lever co-authored, published by VCH, “Phthalogicanes-Properties and Applications” (p. 1-54), etc., can be synthesized by citation or similar methods.

-Oxonol dye-
Next, the oxonol dye will be described. The oxonol dye is a compound represented by the following general formula (A), preferably a dye having a chain acidic nucleus or a cyclic acidic nucleus having a methine number of 1 to 7. In general formula (A), n is preferably an integer of 1 to 4. Rs can form a ring. More preferred are oxonol dyes represented by the general formula (II), more preferred are dyes represented by the general formula (I), and still more preferred are dyes represented by the general formula (III). Moreover, the pigment | dye represented by general formula (IV), (V), (VI), (VII), (II '), (1) is also used.

  The compound represented by the general formula (1) includes a compound example represented by the following general formula (III).

In general formula (1), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. R ²¹ , R ²² and R ³ are each 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 Substituted, unsubstituted heterocyclic group, halogen atom, carboxyl group, substituted or unsubstituted alkoxycarbonyl group, cyano group, substituted or unsubstituted acyl group, substituted or unsubstituted carbamoyl group, amino group, substituted amino group , Sulfo group, hydroxyl group, nitro group, substituted or unsubstituted alkylsulfonylamino group, substituted or unsubstituted arylsulfonylamino group, substituted or unsubstituted carbamoylamino A 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 are represented. m represents an integer of 0 or more, and when m is 2 or more, a plurality of R ³ may be the same or different. Z ^{x +} represents a cation, and x represents an integer of 1 or more.

R ¹¹ , R ¹² , R ¹³ and R ^{14 in the} general formula (1) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. Represents either. Examples of the substituted or unsubstituted alkyl group represented by R ¹¹ , R ¹² , R ¹³ and R ¹⁴ include an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl, butyl, i-butyl, t -Butyl, i-amyl, cyclopropyl, cyclohexyl, benzyl, phenethyl). When R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent an alkyl group, they are connected to each other to form a carbocyclic ring (for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, Cycloheptyl, cyclooctyl, etc.) or a heterocyclic ring (for example, piperidyl, chromanyl, morpholyl, etc.) may be formed. The alkyl group represented by R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is preferably a chain alkyl group or a cyclic alkyl group having 1 to 8 carbon atoms, and most preferably a chain shape having 1 to 5 carbon atoms. (Straight chain or branched chain) alkyl group, R ¹¹ and R ¹² and R ¹³ and R ¹⁴ bonded to each other to form a cyclic alkyl group having 1 to 8 carbon atoms (preferably a cyclohexyl ring), A substituted alkyl group having 1 to 20 carbon atoms (for example, benzyl, phenethyl).

Examples of the substituted or unsubstituted aryl group represented by R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in the general formula (1) include aryl groups having 6 to 20 carbon atoms (for example, phenyl and naphthyl). The aryl group represented by R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ is preferably an aryl group having 6 to 10 carbon atoms.

The substituted or unsubstituted heterocyclic group represented by R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in the general formula (1) is a 5 to 6 member composed of a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom. A ring saturated or unsaturated heterocyclic group such as pyridyl group, pyrimidyl group, pyridazyl group, piperidyl group, triazyl group, pyrrolyl group, imidazolyl group, triazolyl group, furanyl group, thiophenyl group, thiazolyl group, oxazolyl group, An isothiazolyl group, an isoxazolyl group, etc. are mentioned. These may be benzo-fused (for example, quinolyl group, benzimidazolyl group, benzothiazolyl group, benzoxazolyl group, etc.). The substituted or unsubstituted heterocyclic group represented by R ¹¹ , R ¹² , R ¹³ , or R ¹⁴ is preferably a substituted or unsubstituted heterocyclic group having 6 to 10 carbon atoms.

As a substituent of the substituted or unsubstituted alkyl group, the substituted or unsubstituted aryl group, and the substituted or unsubstituted heterocyclic group represented by R ¹¹ , R ¹² , R ¹³ , R ¹⁴ in the general formula (1) Includes the substituent group S described later.

  Examples of the substituent represented by S include an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl, carboxymethyl, ethoxycarbonylmethyl), an aralkyl group having 7 to 20 carbon atoms (for example, benzyl, phenethyl), C1-C8 alkoxy group (for example, methoxy, ethoxy), C6-C20 aryl group (for example, phenyl, naphthyl), C6-C20 aryloxy group (for example, phenoxy, naphthoxy), hetero A cyclic group (for example, pyridyl, pyrimidyl, pyridazyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2 , 4-Dioxyoxazolidine-3-yl, succinimide, phthalimide, male Imide), halogen atoms (eg, fluorine, chlorine, bromine, iodine), carboxyl groups, C2-C10 alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl), cyano groups, C2-C10 acyl groups (For example, acetyl, pivaloyl), carbamoyl having 1 to 10 carbon atoms (for example, carbamoyl, methylcarbamoyl, morpholinocarbamoyl), amino group, substituted amino group having 1 to 20 carbon atoms (for example, dimethylamino, diethylamino, bis (methyl Sulfonylethyl) amino, N-ethyl-N′-sulfoethylamino), sulfo group, hydroxyl group, nitro group, alkylsulfonylamino group having 1 to 10 carbon atoms (for example, methylsulfonylamino), 1 to 10 carbon atoms A carbamoylamino group (eg carbamoylamino) Methylcarbamoylamino), a sulfonyl group having 1 to 10 carbon atoms (for example, methanesulfonyl, ethanesulfonyl), a sulfinyl group having 1 to 10 carbon atoms (for example, methanesulfinyl), and a sulfamoyl group having 0 to 10 carbon atoms (for example, Sulfamoyl, methanesulfamoyl). In the case of a carboxyl group and a sulfo group, they may be in a salt state.

R ²¹ , R ²² and R ^{3 in the} general formula (1) are each independently 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 group. Aryloxy group, substituted or unsubstituted heterocyclic group, halogen atom, carboxyl group, substituted or unsubstituted alkoxycarbonyl group, cyano group, substituted or unsubstituted acyl group, substituted or unsubstituted carbamoyl group, amino group, Substituted amino group, sulfo group, hydroxyl group, nitro group, substituted or unsubstituted alkylsulfonylamino group, substituted or unsubstituted carbamoylamino group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, It represents either a substituted or unsubstituted sulfinyl group and a substituted or unsubstituted sulfamoyl group. R ²¹ , R ²² and R ³ are preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms, a substituted or unsubstituted carbon. An alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a halogen atom, and more preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or An unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 10 carbon atoms, and a halogen atom are preferable, most preferably a hydrogen atom, an unsubstituted alkyl group having 1 to 5 carbon atoms, and It is a substituted alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 6 carbon atoms, and a halogen atom. R ²¹ , R ²² and R ³ may further have a substituent, and examples of the substituent include the substituent group S described above.

It is preferable that m is 0, and R ²¹ and R ²² are both hydrogen atoms. Further, m is preferably 1, and R ²¹ , R ²² and R ³ are all preferably hydrogen atoms.

  M in the general formula (1) represents an integer of 0 or more, preferably an integer of 0 to 5 (0 or more and 5 or less), more preferably an integer of 0 to 3, particularly preferably an integer of 0 to 2. It is.

In the general formula (1), when m is 2 or more, the plurality of R ³ may be the same or different and each independently represents a hydrogen atom or the above-described substituent.

In the general formula (1), Z ^{x +} represents a cation, and x represents an integer of 1 or more.

The cation represented by Z ^{x +} is preferably a quaternary ammonium ion, and more preferably a 4,4′-bipyridinium cation represented by the general formula (I-4) of JP-A No. 2000-52658. Ion and 4,4′-bipyridinium cation disclosed in JP 2002-59652 A. In general formula (1), x is preferably 1 or 2.

  Although the preferable specific example of a compound represented by the said General formula (1) is given to the following, this invention is not limited to these.

  In the case of an oxonol dye, a compound represented by the general formula (II) is preferable.

Next, general formula (II) will be described in detail. In the formula (II), Za ²⁵ and Za ²⁶ are each independently an atomic group forming an acidic nucleus. The acidic nucleus is synonymous with that formed by Za ²¹ , Za ²² , Za ²³ , Za ²⁴ in the general formula (I), and specific examples thereof are also the same. The acidic nucleus formed by Za ²⁵ and Za ²⁶ is preferably indandione, pyrazolone, pyrazolinedione, or benzothiophenone dioxide. Of these, pyrazolone is most preferred.

Ma ²⁷ , Ma ²⁸ , and Ma ²⁹ are each independently a substituted or unsubstituted methine group, and have the same meaning as Ma ²¹ , Ma ²² , Ma ²³ , Ma ²⁴ , Ma ²⁵ , and Ma ^{26 in} formula (I). Yes, the specific examples and preferred examples are also the same. Ma ²⁷ , Ma ²⁸ and Ma ²⁹ are preferably unsubstituted methine groups.

Ka ²³ represents an integer of 0 to 3. It is synonymous with Ka < ²¹ >, Ka < ²² > of general formula (I). Ka ²³ is preferably 2 in both cases. Q represents a monovalent cation that neutralizes the charge.

When there are a plurality of Ka ^{23 s} , a plurality of Ma ²⁷ , Ma ²⁸ and Ma ²⁹ may be the same or different.

  The dye having the structure represented by the general formula (II) is preferably one represented by the general formula (IV), (V), (VI), or (VII).

In the general formulas (IV), (V), (VI) and (VII), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²¹ , R ²² , R ^{23, R 24, R 25,} R 26, to ^{R 27, R 28, R 31} , R 32, R 33, R 34, R 41, R 42, R 43, R 44 are each independently a hydrogen atom or a substituent It is. Ma ²⁷ , Ma ²⁸ , and Ma ²⁹ are each independently a substituted or unsubstituted methine group. Ka ²³ represents an integer of 0 to 3. Q represents a monovalent cation that neutralizes the charge. When there are a plurality of Ka ²¹ and Ka ²² , a plurality of Ma ²⁷ and Ma ²⁸ may be the same or different.

In the general formulas (IV), (V), (VI) and (VII), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³² , R ³³ (the above may be expressed as “R”) each independently represents a hydrogen atom or a substituent. Substituents include halogen atoms, substituted or unsubstituted alkyl groups (including cycloalkyl groups and bicycloalkyl groups), substituted or unsubstituted alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), substituted or unsubstituted groups. Alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted Or an unsubstituted silyloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted carbamoyloxy group, a substituted or unsubstituted alkoxycarbonyloxy group, a substituted or unsubstituted aryl Oxycarbonyloxy, substituted Or an 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 aryloxycarbonyl An amino group, a substituted or unsubstituted sulfamoylamino group, a substituted or unsubstituted alkyl and arylsulfonylamino group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, Substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted sulfamoyl group, sulfo group, substituted or unsubstituted alkyl and arylsulfinyl group, substituted or unsubstituted alkyl and arylsulfonyl group, substituted or unsubstituted acyl group , If replacement Is an unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted aryl and heterocyclic azo group, substituted or unsubstituted imide group, substituted or unsubstituted Examples thereof include a 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 specifically, R represents a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), tricyclo structures with more ring structures, etc. It is intended to embrace. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or unsubstituted 3 to 30 carbon atoms or An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [ It is intended to encompass 2,2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group), an aryl group (preferably a substituted or unsubstituted aryl having 6 to 30 carbon atoms) Groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocycles A monovalent group obtained by removing one hydrogen atom from a compound, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group ( Preferably, it is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably carbon A substituted or unsubstituted aryloxy group of formula 6 to 30, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably, A silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazole -5-oxy, 2-tetrahydropyranyloxy) Acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy , Stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy, N, N -Diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably having 2 to 30 carbon atoms) Or an unsubstituted alkoxycarbonyloxy group, for example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted group having 7 to 30 carbon atoms) Aryloxycarbonyloxy group of, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably amino group, substituted or non-substituted with 1 to 30 carbon atoms) Substituted alkylamino group, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino group Preferably, a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroyl Amino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, eg For example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms substituted or unsubstituted A substituted aryloxycarbonylamino group such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted group having 0 to 30 carbon atoms) Substituted sulfamoylamino groups such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably C1-C30 substituted or unsubstituted alkylsulfonylamino, C6-C30 substituted or unsubstituted arylsulfonylamino, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5- Trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, ethylthio, n-hexadecylthio), arylthio group (preferably Is a substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic ring having 2 to 30 carbon atoms) O group such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl And an arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methyl Phenylsulfinyl), a Kills and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p- Methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, substitution having 4 to 30 carbon atoms Or a heterocyclic carbonyl group bonded to a carbonyl group with an unsubstituted carbon atom, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2- Furylcarbonyl), arylo A sicarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxy A carbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably having 1 to 1 carbon atoms) 30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), a Reel and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5- Ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, For example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphini Phosphinyloxy group (preferably charcoal) A substituted or unsubstituted phosphinyloxy group having a number of 2 to 30 such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy, a phosphinylamino group (preferably a substituted or An unsubstituted phosphinylamino group such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms such as trimethylsilyl, t -Butyldimethylsilyl, phenyldimethylsilyl).

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ are hydrogen Atoms are most preferred.

R ³¹ , R ³⁴ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ may be the same as the above R as the substituent, but may be a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group. Aryl groups are preferred. Among these, a substituted or unsubstituted aryl group is more preferable.
Ma ²⁷ , Ma ²⁸ , and Ma ²⁹ are each independently a substituted or unsubstituted methine group. It is synonymous with Ma < ²⁷ >, Ma < ²⁸ >, Ma < ²⁹ > of general formula (II), The specific example and preferable thing are also the same. Ka ²³ each independently represents an integer of 0 to 3. Ka ²³ is preferably 2. Q represents a monovalent cation that neutralizes the charge. When there are a plurality of Ka ^{23 s} , a plurality of Ma ²⁷ and Ma ²⁸ may be the same or different.

  The dye having the structure represented by the general formula (II) is preferably a dye having a structure represented by the following general formula (VIII).

  The dye represented by formula (VIII) will be described in detail.

In the general formula (VIII), R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ and R ⁶⁰ each independently represent a hydrogen atom or a substituent. . In the case of a substituent, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a halogen atom, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted acylamino group is preferable. Among them, all of which are hydrogen atoms, and R ⁵¹ , R ⁵³ , R ⁵⁵ , R ⁵⁶ , R ⁵⁸ , R ⁶⁰ are substituted with halogen atoms, and R ⁵² , R ⁵⁴ , R ⁵⁷ , R ⁵⁹ are What is a hydrogen atom is preferable. R ⁶¹ and R ⁶⁷ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a cyano group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group It represents an alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted acylamino group. Of these, a substituted or unsubstituted alkoxycarbonyl group is preferred, and an unsubstituted alkoxycarbonyl group is most preferred.

R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acylamino group, or substituted or An unsubstituted heterocyclic group is represented. R ⁶² , R ⁶³ , R ⁶⁵ and R ⁶⁶ are all preferably hydrogen atoms. R ⁶⁴ is preferably a hydrogen atom or a substituted or unsubstituted aryl group.

^R71 , ^R72 , ^R73 , ^R74 , ^R75 , ^R76 , ^R77 , ^R78 , ^R79 , ^R80 , ^R81 , ^R82 , ^R83 , ^R84 , ^R85 , ^R86 , ^R87 , R ⁸⁸ each independently represents a hydrogen atom or a substituent. When it is a substituent, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a hydroxyl group, or a substituted or unsubstituted acylamino group is preferable. R ⁷¹ , R ⁷² , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ and R ⁸⁰ are all preferably hydrogen atoms. R ⁷³ and R ⁷⁸ are each preferably a hydroxyl group. R ⁷⁴ and R ⁷⁹ are each preferably a phenyl group.

R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ are all preferably hydrogen atoms.

The dye having the structure represented by the general formula (I) will be described in detail. In the formula (I), Za ²¹ , Za ²² , Za ²³ , and Za ²⁴ are each independently an atomic group that forms an acidic nucleus, and examples thereof include James ed., The Theory of the Photographic Process, 4th. Edition, McMillan, 1977, p. 198. Specifically, each optionally substituted pyrazol-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4- ON, 2-oxazolin-5-one, 2-thiooxazoline-2,4-dione, isorhodanine, rhodanine, thiophen-3-one, thiophen-3-one-1,1-dioxide, 3,3-dioxo [1 , 3] oxathiolane-5-one, indoline-2-one, indoline-3-one, 2-oxoindazolium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione (for example, Meldrum acid), barbituric acid, 2-thio Barbituric acid, coumarin-2,4-dione, indazolin-2-one, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazolone, pyrazolopyridone, 5 or 6 membered And nuclei such as carbocycle (eg, hexane-1,3-dione, pentane-1,3-dione, indan-1,3-dione), and the like, preferably pyrazol-5-one, pyrazolidine-3,5 -Dione, barbituric acid, 2-thiobarbituric acid, 1,3-dioxane-4,6-dione, or 3,3-dioxo [1,3] oxathiolane-5-one.

Za ²¹ , Za ²² , Za ²³ and Za ²⁴ are most preferably 1,3-dioxane-4,6-dione, which may be substituted.

  Substituents for substituting the acidic nucleus are halogen atoms, alkyl groups (including cycloalkyl groups and bicycloalkyl groups), alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups, Cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (anilino group) ), Acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, Borocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group Examples thereof include a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group. Among these, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms is preferable.

  The acidic nucleus is preferably unsubstituted, substituted with a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or substituted with a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

The acidic nucleus formed by Za ²¹ , Za ²² , Za ²³ and Za ²⁴ is preferably indandione, pyrazolone, pyrazolinedione or benzothiophenone dioxide. Of these, pyrazolone is most preferred.

Ma ²¹ , Ma ²² , Ma ²³ , Ma ²⁴ , Ma ²⁵ , and Ma ²⁶ are each independently a substituted or unsubstituted methine group. As the substituent, an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, isopropyl), a halogen atom (for example, chlorine, bromine, iodine, fluorine), an alkoxy group having 1 to 20 carbon atoms (for example, methoxy) , Ethoxy, isopropoxy), aryl groups having 6 to 26 carbon atoms (for example, phenyl, 2-naphthyl), heterocyclic groups having 0 to 20 carbon atoms (for example, 2-pyridyl, 3-pyridyl), from 6 carbon atoms 20 aryloxy groups (for example, phenoxy, 1-naphthoxy, 2-naphthoxy), C1-C20 acylamino groups (for example, acetylamino, benzoylamino), C1-C20 carbamoyl groups (for example, N, N- Dimethylcarbamoyl), sulfo group, hydroxy group, carboxy group, alkylthio group having 1 to 20 carbon atoms (for example, Chiruchio), and a cyano group. Moreover, it may combine with another methine group to form a ring structure, or may combine with an atomic group represented by Za ²¹ to Za ²⁴ to form a ring structure.

Ma ²¹ , Ma ²² , Ma ²³ , Ma ²⁴ , Ma ²⁵ , and Ma ²⁶ are each independently any of a methine group that is preferably unsubstituted, substituted with an ethyl group, a methyl group, or a phenyl group. Most preferred is an unsubstituted methine group.

L is a divalent linking group that does not form a π-conjugated system with two bonds. The divalent linking group is not particularly limited except that it does not form a π-conjugated system between chromophores to which they are bonded, but preferably an alkylene group (having 1 to 20 carbon atoms such as methylene, ethylene, propylene, butylene, pentylene). ), Arylene groups (having 6 to 26 carbon atoms such as phenylene and naphthylene), alkenylene groups (having 2 to 20 carbon atoms such as ethenylene and propenylene), alkynylene groups (having 2 to 20 carbon atoms such as ethynylene and propynylene), -CO- N (R ¹⁰¹ ) —, —CO—O—, —SO ₂ —N (R ¹⁰² ) —, —SO ₂ —O—, —N (R ¹⁰³ ) —CO—N (R ¹⁰⁴ ) —, —SO ₂ -, - SO -, - S -, - O -, - CO -, - N (R 105) -, from heterylene group (C 1 -C 26, for example 6-chloro-1,3,5-triazyl -2, 4 Diyl group, pyrimidine-2,4-diyl) one or more combination comprised carbon number of 0 or more and 100 or less, preferably a linking group having 1 to 20. R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , and R ¹⁰⁵ each independently represent any of a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group. In addition, one or more linking groups represented by L may exist between two chromophores to which they are linked, and a plurality (preferably two) may be bonded to form a ring. Good.

  L is preferably a group in which two alkylene groups (preferably ethylene) are combined to form a ring. Among them, the case where a 5- or 6-membered ring (preferably a cyclohexyl ring) is formed is more preferable.

In the general formula (I), Ka ²¹ and Ka ²² each independently represents an integer of 0 to 3.

When there are a plurality of Ka ²¹ and Ka ²² , a plurality of Ma ²¹ , Ma ²² , Ma ²⁵ and Ma ²⁶ may be the same or different.

Ka ²¹ and Ka ²² are preferably both 2.

  Q represents a monovalent cation that neutralizes the charge. Therefore, 2Q represents a divalent cation. The ion represented by Q is not particularly limited, and may be an ion made of an inorganic compound or an ion made of an organic compound. Examples of the cation represented by Q include metal ions such as sodium ion and potassium ion, quaternary ammonium ion, oxonium ion, sulfonium ion, phosphonium ion, selenonium ion, and onium ion such as iodonium ion. .

  The cation represented by Q is preferably an onium ion, and more preferably a quaternary ammonium ion. Particularly preferred among the quaternary ammonium ions are 4,4′-bipyridinium cation represented by general formula (I-4) in JP-A-2000-52658 and JP-A-2002-59652. 4,4′-bipyridinium cation. In the case of a dicationic compound such as 4,4'-bipyridinium cation, Q corresponds to 1/2 (a dicationic compound).

In the general formula (I), preferably, the acidic nuclei formed by Za ²¹ , Za ²² , Za ²³ and Za ²⁴ are each independently unsubstituted or substituted with a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Or pyrazol-5-one, pyrazolidine-3,5-dione, barbituric acid, 2-thiobarbituric acid, 1,3 substituted with substituted or unsubstituted aryl groups having 6 to 20 carbon atoms -Dioxane-4,6-dione, 3,3-dioxo [1,3] oxathiolane-5-one, and Ma ²¹ , Ma ²² , Ma ²³ , Ma ²⁴ , Ma ²⁵ , Ma ²⁶ are each independently Either unsubstituted or a methine group substituted with an ethyl group, a methyl group, or a phenyl group, and L is a 5- or 6-membered ring formed by bonding two alkylene groups (preferably ethylene) Ka ²¹ , Ka ^{2 2} is both 2, and the cation represented by 2Q is a 4,4′-bipyridinium cation represented by the general formula (I-4) of JP-A No. 2000-52658 and JP-A No. 2002-2002. This is the case of the 4,4′-bipyridinium cation disclosed in Japanese Patent No. 59652. Among the dyes represented by the general formula (I), the dye represented by the general formula (III) is preferable.

In formula (III), R ¹ and R ² each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or a substituent. R ¹ and R ² may be bonded to each other to form a ring structure. Each R ⁶ is independently a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. L ¹ is a divalent linking group. Two R ⁶ may combine to form a divalent linking group. n and m each independently represents an integer of 0 to 2. Q represents a monovalent cation that neutralizes the charge. When n and m are plural, a plurality of R ³ and R ⁴ may be the same or different.

Formula (III) will be described in detail. R ¹ and R ² each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ¹ and R ² may be bonded to each other to form a ring structure. R ¹ and R ² are preferably each independently or a substituted or unsubstituted alkyl group. More preferably, R ¹ and R ² are different unsubstituted alkyl groups having 1 to 6 carbon atoms. R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or a substituent. R ³ , R ⁴ and R ⁵ are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. More preferably, they are a hydrogen atom, an ethyl group, a methyl group, or a phenyl group. Most preferably, R ³ , R ⁴ and R ⁵ are all hydrogen atoms. R ⁶ is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Among them, those in which two R ⁶ are bonded to form a divalent linking group are preferable. L ¹ is a divalent linking group. Preferably, L ¹ is a substituted or unsubstituted alkylene group. L ¹ and R ⁶ are most preferably those in which L ¹ and two R ⁶ form a ring structure. In this 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 0 to 2. n and m are both preferably 2. Q represents a monovalent cation that neutralizes the charge. Therefore, 2Q represents a divalent cation. When n and m are plural, a plurality of R ³ and R ⁴ may be the same or different.

  Although the preferable specific example of the compound represented by general formula (I), (II) or (III) of this invention is given to the following, this invention is not limited to these.

  A general oxonol dye can be synthesized by a condensation reaction between a corresponding active methylene compound and a methine source (a compound used for introducing a methine group into a methine dye). Details of this type of compound are described in JP-B-39-22069, JP-A-43-3504, JP-A-52-38056, JP-A-54-38129, JP-A-55-10059, JP-A-58-35544, JP-A-49-49. -99620, 52-92716, 59-16834, 63-316853, 64-40827, and British Patent Nos. 1339986, U.S. Pat. Nos. 3,247,127, 4042397, and 4181225. Nos. 5213956 and 5260179 can be referred to. Also described in JP-A-63-209995, JP-A-10-309871 and JP-A-2002-249674.

  A method for synthesizing bis-type oxonol dyes is disclosed in European Patent EP1424691A2.

  A leuco dye can also be used. Specifically, crystal violet lactone; 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl 2- Phthalide compounds such as methylindol-3-yl) -4-azaphthalide; 3-cyclohexylmethylamino-6-methyl-7-anilinofluorane, 2- (2-chloroanilino) -6-dibutylaminofluorane, 3- Diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-xylidinofluorane, 2- (2-chloroanilino) -6-diethylaminofluorane, 2-anilino-3-methyl- 6 (N-ethylisopentylamino) fluorane, 3-diethylamino-6-chloro-7-anilinofluor Down, 3-benzyl-ethyl-6-methyl-7-anilinofluoran, 3-methyl-propylamino-6-methyl-7-anilinofluoran fluoran compounds such Oran; and the like are preferable.

  Further, in the optical disc of the present invention, the information recording layer and the image recording layer may be the same or different from each other, but the information recording layer and the image recording layer may be different from each other. Since the required characteristics differ between the recording layers, it is preferable that the constituent components are different. Specifically, the constituent components of the information recording layer are preferably excellent in recording / reproducing characteristics, and the constituent components of the image recording layer are preferably those in which the contrast of the recorded image is high. In particular, when a dye is used, it is preferable to use a cyanine dye, a phthalocyanine dye, an azo dye, an azo metal complex, or an oxonol dye among the dyes described above from the viewpoint of improving the contrast of a recorded image in the image recording layer. .

  The image recording layer can be formed by preparing a coating solution by dissolving the above-described dye in a solvent and coating the coating solution. As the solvent, the same solvent as that used for preparing the coating solution for the information recording layer described above can be used. Other additives, coating methods and the like are the same as those of the information recording layer described above.

  The thickness of the image recording layer is preferably 0.01 to 200 μm, more preferably 0.05 to 20 μm, and further preferably 0.1 to 5 μm.

  Below, another layer is demonstrated.

(Protective layer)
A protective layer may be provided for the purpose of physically and chemically protecting the reflective layer and the information recording layer.

  In addition, in the case of adopting the same configuration as that for manufacturing a DVD-R type optical disc, that is, a configuration in which two substrates are bonded with the information recording layer and the image recording layer inside, it is not always necessary to provide a protective layer. Absent.

Examples of materials used for the protective layer include inorganic substances such as ZnS, ZnS—SiO ₂ , SiO, SiO ₂ , MgF ₂ , SnO ₂ , and Si ₃ N ₄ , thermoplastic resins, thermosetting resins, and UV curable materials. Organic substances such as resins can be mentioned. The protective layer can be formed, for example, by laminating a film obtained by extrusion of plastic on the reflective layer via an adhesive. Or you may provide by methods, such as vacuum evaporation, sputtering, and application | coating.

  In the case of a thermoplastic resin or a thermosetting resin, it can also be formed by dissolving these in a suitable solvent to prepare a coating solution, and then applying and drying the coating solution. In the case of a UV curable resin, it can also be formed by applying this coating solution and curing it by irradiation with UV light. In these coating liquids, various additives such as an antistatic agent, an antioxidant, and a UV absorber may be added according to the purpose. The thickness of the protective layer is generally in the range of 0.1 μm to 1 mm.

  As another configuration, for example, a reflective layer, an information recording layer, and a cover layer may be sequentially formed on a substrate. The cover layer is preferably formed on the information recording layer via an adhesive layer. In this case, the configuration other than the cover layer is as described above.

(Cover layer)
The cover layer is formed to prevent the inside of the optical disk from impact and the like, and is not particularly limited as long as it is a transparent material, but is preferably polycarbonate, cellulose triacetate, or the like, more preferably moisture absorption at 23 ° C. and 50% RH. Is a material of 5% or less.

  “Transparent” means that the recording light and the reproduction light are so transparent that the light is transmitted (transmittance: 90% or more).

  The cover layer is prepared by dissolving a photocurable resin constituting the adhesive layer in an appropriate solvent to prepare a coating solution, and then coating the coating solution on the information recording layer at a predetermined temperature to form a coating film. For example, a cellulose triacetate film (TAC film) obtained by, for example, plastic extrusion is laminated on the coating film, and light is irradiated from above the laminated TAC film to cure the coating film. The TAC film preferably contains an ultraviolet absorber. The thickness of the cover layer is in the range of 0.01 to 0.2 mm, preferably in the range of 0.03 to 0.1 mm, and more preferably in the range of 0.05 to 0.095 mm.

  Moreover, a polycarbonate sheet etc. can also be used as a cover sheet.

  In addition, a polycarbonate sheet etc. can also be used as a cover layer. When the adhesive is given to the bonding surface of a transparent sheet, the said adhesive agent is unnecessary.

  Moreover, you may form the light transmissive layer which consists of ultraviolet curable resin etc. instead of a cover layer.

  A hard coat layer may be formed on the cover layer. The hard coat layer can be formed by coating or the like on the cover layer after forming a reflective layer, an information recording layer, etc. on the substrate and forming a cover layer thereon. When the cover layer is a transparent sheet, before the transparent sheet is bonded to the information recording layer, a hard coat layer is formed on the transparent sheet so that the hard coat layer is the outermost surface. May be bonded onto the information recording layer to produce an optical disc according to this embodiment.

  Further, as described above, the optical disc according to the present embodiment can be applied to a so-called read-only optical disc having a recording portion (pit) in which information reproducible by laser light is recorded. .

[Image recording method]
Image recording on the image recording layer of the optical disc according to the present embodiment is performed using the optical disc according to the present embodiment and a recording apparatus capable of recording image information on at least the image recording layer of the optical disc.

  First, a recording apparatus used for recording on an optical disk according to the present invention will be described.

(Optical disk recording device)
In the optical disc of the present invention, recording of an image on the image recording layer and recording of optical information on the information recording layer can be performed by, for example, one optical disc drive (recording device) having a recording function on both layers. . When one optical disk drive is used as described above, after recording on one of the image recording layer and the information recording layer, the recording can be reversed and recording can be performed on the other layer.

  The optical disk of the present invention described above can be used particularly suitably for the following apparatuses and methods.

For example, an optical disc recording apparatus in which the above-described optical disc of the present invention is suitably used is
(1) An optical disc recording apparatus that records information by irradiating a recording surface (for example, a dye recording layer (recording layer)) of an optical disc with laser light, and an optical pickup that irradiates the optical disc with laser light Irradiating position adjusting means for adjusting the irradiation position of the laser beam on the optical disc by the optical pickup; and an optical disc in which the recording surface is formed on one surface and the image recording layer is formed on the other surface. Image forming control means for controlling the optical pickup and the irradiation position adjusting means so that a visible image corresponding to image information is formed on the image recording layer of the optical disc when set so as to face the optical pickup. The beam spot diameter of the laser beam irradiated by the optical pickup onto the image recording layer when forming the visible image is information The optical pickup is characterized by comprising a beam spot control means for controlling the optical pickup to be larger than the beam spot diameter of the laser beam to be irradiated to the recording surface when performing the recording.

  According to this configuration, by irradiating the image recording layer of the optical disc with laser light according to the image data, the reflectance changes like an image with the change in absorbance of the image recording layer, and a visible image corresponding to the image data Can be formed. When such a visible image is formed, the laser beam is irradiated to a larger area while the optical disc is rotated once by increasing the beam spot diameter of the laser beam applied to the image recording layer of the optical disc. The time required for forming a visible image can be shortened. In addition, the above-described optical disc of the present invention can record a good visible image by such a method.

Another aspect of the optical disk recording apparatus is:
(2) An optical disk recording apparatus for recording information by irradiating a recording surface of an optical disk with laser light, an optical pickup for irradiating the optical disk with laser light, and a laser beam applied to the optical disk by the optical pickup. When the optical position adjustment means for adjusting the irradiation position and the optical disk having the recording surface on one side and the image recording layer on the other side are set so that the image recording layer faces the optical pickup And a means for controlling the optical pickup and the irradiation position adjusting means so that a visible image corresponding to image information is formed on the image recording layer of the optical disc, wherein the optical pickup is located on the image recording layer. The intensity of the irradiated laser beam is a first intensity at which the image recording layer hardly changes based on the image information, or the first intensity Image forming control means for controlling the image recording layer to have one of the second intensities greater than the intensity of the image recording layer, and detecting information relating to the laser beam irradiated to the optical disc by the optical pickup, Servo means for controlling the optical pickup so that a desired laser beam is irradiated based on a detection result, and the image formation control means is a laser beam irradiated by the optical pickup according to the control based on the image information. The intensity of the laser beam emitted from the optical pick-up for a predetermined time regardless of the contents of the image information when the time when the intensity of the laser beam continuously becomes the second intensity exceeds a certain time. The servo means controls the optical peak based on a detection result of information relating to the laser beam irradiated at the first intensity. It is characterized by controlling the up.

  According to this configuration, by irradiating the image recording layer of the optical disc with laser light according to the image data, the reflectance changes like an image with the change in absorbance of the image recording layer, and a visible image corresponding to the image data Can be formed. When such a visible image is formed, even if the intensity of the laser beam corresponding to the image data lasts for a long time, which is the second intensity for changing the image recording layer, the laser beam is used regardless of the image data. Since the first intensity laser beam that hardly changes the image recording layer is irradiated for the control, the laser beam control based on the irradiation result can be performed. In addition, the above-described optical disc of the present invention can record a good visible image by such a method.

Another aspect of the optical disk recording apparatus is:
(3) An optical disk recording apparatus for recording information by irradiating a recording surface of an optical disk with laser light, an optical pickup that irradiates the optical disk with laser light, and a laser beam applied to the optical disk by the optical pickup. When the optical position adjustment means for adjusting the irradiation position and the optical disk having the recording surface on one side and the image recording layer on the other side are set so that the image recording layer faces the optical pickup In addition, image forming control means for controlling the optical pickup and the irradiation position adjusting means so that a visible image corresponding to image information is formed on the image recording layer of the optical disk, and the optical disk are set in the optical disk recording apparatus. The surface of the optical disc facing the optical pickup is the image recording layer or the recording In either the based is, is characterized by comprising a relative position adjusting means for adjusting the relative positional relationship between the optical pickup and the optical pickup facing the surface of the optical disc.

  According to this configuration, by irradiating the image recording layer of the optical disc with laser light according to the image data, the reflectance changes like an image with the change in absorbance of the image recording layer, and a visible image corresponding to the image data Can be formed. When the optical disc is set, the positional relationship between the optical pickup and the surface facing the optical pickup is adjusted depending on whether the image recording layer or the recording surface is set to face the optical pickup. Can do. Therefore, when the recording surface is set to face the optical pickup, and when the image recording layer is set to face the optical pickup, the distance between the optical pickup and the surface facing the optical pickup is different. However, it is possible to suppress the problem that various controls such as focus control cannot be performed due to the difference in distance. In addition, the above-described optical disc of the present invention can record a good visible image by such a method.

Another aspect of the optical disk recording apparatus is:
(4) An optical disk recording apparatus for recording information by irradiating a recording surface of an optical disk with laser light, an optical pickup for irradiating the optical disk with laser light, and a laser beam applied to the optical disk by the optical pickup. An irradiation position adjusting means for adjusting an irradiation position, and an optical disc in which the recording surface is formed on one surface and an image recording layer is formed on the other surface, and an optical disc in which a guide groove is spirally formed on the recording surface When the image recording layer is set so as to face the optical pickup, the laser light is irradiated along the guide groove based on the reflected light from the optical disk of the laser light irradiated by the optical pickup. Servo means for controlling the irradiation position adjusting means, and the laser light irradiation position is moved along the guide groove by the servo means. And an image formation control means for controlling laser light emitted from the optical pickup so that a visible image corresponding to image information is formed on the image recording layer of the optical disc. Yes. In addition, the above-described optical disc of the present invention can record a good visible image by such a method.

  According to this configuration, by irradiating the image recording layer of the optical disc with laser light according to the image data, the reflectance changes like an image with the change in absorbance of the image recording layer, and a visible image corresponding to the image data Can be formed. At this time, the guide groove formed on the recording surface is detected, and the laser beam irradiation is more complicated than when recording is performed on the recording surface by moving the laser beam irradiation position along the detected guide groove. Visible image formation can be performed without performing position control.

Another aspect of the optical disk recording apparatus is:
(5) An optical disc recording apparatus for recording information by irradiating a recording surface of an optical disc with laser light, an optical pickup for irradiating the optical disc with laser light, and a rotation driving means for rotating the optical disc, The clock signal output means for outputting a clock signal having a frequency corresponding to the rotational speed of the optical disk by the rotation driving means, and the optical disk in which the recording surface is formed on one surface and the image recording layer is formed on the other surface, Means for controlling the optical pickup so that a visible image corresponding to image information is formed on the image recording layer of the optical disc when the recording layer is set so as to face the optical pickup; The output means controls the laser light emitted from the optical pickup based on the image information for each period of the clock signal. Image forming control means; rotation detecting means for detecting that the optical disk has been rotated once from a predetermined reference position by the rotation driving means; and forming the visible image on the image recording layer of the optical disk. When the rotation detecting unit detects that the optical disk has been rotated once from the predetermined reference position while being irradiated with laser light by the optical pickup, the irradiation position of the laser light by the optical pickup is determined by the optical disk. And an irradiation position adjusting means for moving a predetermined amount in a predetermined radial direction of the optical disc set in the recording apparatus.

  According to this configuration, by irradiating the image recording layer of the optical disc with laser light according to the image data, the reflectance changes like an image with the change in absorbance of the image recording layer, and a visible image corresponding to the image data Can be formed. When this visible image is formed, laser light irradiation control for visible image formation is performed every period of the clock signal having a frequency corresponding to the rotation speed of the optical disk, that is, every time the optical disk rotates by a certain angle. A visible image having contents (for example, density) corresponding to the image data can be formed at a position for each fixed angle. In addition, the above-described optical disc of the present invention can record a good visible image by such a method.

Another aspect of the optical disk recording apparatus is:
(6) An optical disk recording apparatus for recording information by irradiating a recording surface of an optical disk with laser light, an optical pickup for irradiating the optical disk with laser light, and a rotation driving means for rotating the optical disk; A rotation detecting means for detecting that the optical disk has been rotated once from a predetermined reference position by the rotation driving means; and an optical disk in which the recording surface is formed on one surface and an image recording layer is formed on the other surface. Image formation control means for controlling the optical pickup so that a visible image corresponding to image information is formed on the image recording layer of the optical disc when the image recording layer is set to face the optical pickup; In order to form the visible image on the image recording layer of the optical disk, the laser beam is irradiated by the optical pickup before the visible image is formed. When the rotation detecting unit detects that the optical disk has been rotated once from the predetermined reference position, the irradiation position of the laser beam by the optical pickup is set to a predetermined diameter of the optical disk set in the optical disk recording apparatus. Irradiation position adjusting means for moving the image in the direction by a predetermined amount, and the image formation control means moves the visible image from the predetermined reference position of the image recording layer of the optical disk rotated by the rotation driving means. While the optical pickup is irradiated with laser light to form, the laser light irradiation position from the position ahead of the predetermined reference position of the optical disc by a predetermined amount from the predetermined reference position of the optical disc The optical pickup is controlled so that the laser beam for forming the visible image is not irradiated onto the area. It is characterized in.

  According to this configuration, by irradiating the image recording layer of the optical disc with laser light according to the image data, the reflectance changes like an image with the change in absorbance of the image recording layer, and a visible image corresponding to the image data Can be formed. When such a visible image is formed, a visible image is formed by irradiating a laser beam from the reference position of the optical disc while rotating the optical disc, and the region immediately before the laser beam irradiation position returns to the reference position. The laser beam irradiation for forming a visible image is not performed. Therefore, the laser beam irradiation position control is disturbed for some reason such as unstable rotation of the optical disk, the laser beam is continuously irradiated from the reference position, the optical disk is rotated once, and the irradiation position passes through the reference position again. In other words, even if the laser beam irradiation position moves to a position that overlaps the position where the laser beam has already been irradiated later, the laser beam for forming a visible image is prevented from being irradiated to that position. As a result, the quality of the visible image formed can be prevented from deteriorating.

Another aspect of the optical disk recording apparatus is:
(7) An optical disc recording apparatus for recording information by irradiating a recording surface of an optical disc with laser light, an optical pickup for irradiating the optical disc with laser light, and laser light on the optical disc by the optical pickup. An irradiation position adjusting means for adjusting the irradiation position; a disk identification means for obtaining disk identification information for identifying the type of the optical disk set in the optical disk recording apparatus; and the recording surface on one surface. When the optical disc on which the image recording layer is formed is set so that the image recording layer faces the optical pickup, the visible image corresponding to the image information is formed on the image recording layer of the optical disc. A means for controlling the optical pickup and the irradiation position adjusting means, which is identified by the disc identifying means; Depending on the type of the optical disk is characterized by comprising an image forming control means for controlling the optical pickup and the irradiation position adjusting means.

  According to this configuration, by irradiating the image recording layer of the optical disc with laser light according to the image data, the reflectance changes like an image with the change in absorbance of the image recording layer, and a visible image corresponding to the image data Can be formed. When such a visible image is formed, control for forming a visible image can be performed according to the type of the set disc.

Another aspect of the optical disk recording apparatus is:
(8) An optical pickup that irradiates the optical disk with laser light, a modulation means that modulates information supplied from the outside, and a laser light that is emitted from the optical pickup in accordance with information supplied from the modulation means. In an optical disk recording apparatus comprising a laser beam control means for controlling, when a visible image is formed on the image recording layer of an optical disk in which the recording surface is formed on one surface and the image recording layer is formed on the other surface Suppose that the modulation means prohibits the modulation of the image information supplied from the outside and the modulation means when the image recording layer of the optical disc is set to face the optical pickup. The laser beam control means is arranged so that a visible image corresponding to unmodulated image information is formed on the image recording layer of the optical disc. Gosuru is characterized by comprising an image forming control unit.

  According to this configuration, by irradiating the image recording layer of the optical disc with laser light according to the image data, the reflectance changes like an image with the change in absorbance of the image recording layer, and a visible image corresponding to the image data Can be formed. When such a visible image is formed, the image data is not modulated because the modulation by the modulation means for modulating the record data is prohibited when information is recorded on the recording surface. Accordingly, a data transfer configuration for recording information on the recording surface can be used in combination without providing a special data transfer configuration for forming a visible image corresponding to the image data.

Another aspect of the optical disk recording apparatus is:
(9) An optical disk recording apparatus for recording information by irradiating a recording surface of an optical disk with laser light, an optical pickup that irradiates the optical disk with laser light, and a laser beam applied to the optical disk by the optical pickup. When the optical position adjustment means for adjusting the irradiation position and the optical disk having the recording surface on one side and the image recording layer on the other side are set so that the image recording layer faces the optical pickup And an image formation control means for controlling the optical pickup and the irradiation position adjusting means so that a visible image corresponding to the image information is formed on the image recording layer of the optical disc. Controls the laser light emitted from the optical pickup in accordance with the gradation level indicated in the image information. There.

  According to this configuration, by irradiating the image recording layer of the optical disc with laser light according to the image data, the reflectance changes like an image with the change in absorbance of the image recording layer, and a visible image corresponding to the image data Can be formed. When such a visible image is formed, laser light control can be performed according to the gradation of each position (coordinate) on the image recording layer indicated in the image data, and a visible image with gradation expression is formed. can do.

Another aspect of the optical disk recording apparatus is:
(10) An optical disk recording apparatus for recording information by irradiating a recording surface of an optical disk with laser light, the rotating means for rotating the optical disk, and the optical disk rotated by the rotating means from the one surface An optical pickup that irradiates laser light and is movable in a substantially radial direction of the optical disc, and means for adjusting the level of laser light emitted from the optical pickup when forming a visible image on an image recording layer. The first intensity that hardly changes the recording layer and the image recording layer of the optical disc based on the image data representing the visible image to be formed, or the color of the image recording layer while hardly changing the recording layer The level of the laser beam emitted from the optical pickup is set to be one of the second intensities that change And having a laser light level control means for settling.

  According to this apparatus, information can be recorded on the optical disc of the present invention by irradiating the recording layer with laser light in the same manner as before, and a visible image can be formed on the image recording layer. Can do. Furthermore, since information recording and visible image formation can be performed by irradiating laser light from the same surface of the optical disk, the user needs to perform troublesome operations such as turning the optical disk over and resetting it. There is no.

  The image forming method on the image recording layer of the optical disc of the present invention uses an optical disc recording apparatus having an optical pickup that records information by irradiating the recording surface of the optical disc with a laser beam, A method of forming a visible image on an image recording layer formed on an opposite surface, wherein the laser beam irradiation position by the optical pickup is set to a predetermined spiral or concentric circumferential path on the image recording layer. The optical pickup irradiates the optical pickup so that a visible image corresponding to image information is formed on the image recording layer of the optical disc while moving along the optical information. An area including a predetermined number (a plurality) of adjacent paths belonging to each of the divided fan-shaped portions is defined as a unit area, and the unit in the visible image Shades of frequency is characterized by controlling the irradiation timing of the laser light irradiated on each of the paths belonging to the unit region as represented.

  According to this method, by irradiating the image recording layer of the optical disc with laser light according to the image data, the reflectance changes like an image with the change in absorbance of the image recording layer, and a visible image corresponding to the image data is obtained. Can be formed. When such a visible image is formed, the laser beam irradiation timing control can be performed according to the gradation level of each position (coordinate) on the image recording layer indicated in the image data, and the visible image in which gradation expression is made Can be formed.

A. Specific Configuration of the Optical Disc Recording Device The optical disc recording device is an optical disc recording device that records information by irradiating a recording surface of an optical disc with a laser beam. It has a function of forming a visible image corresponding to image data by irradiating the image recording layer of the optical disc having the image recording layer formed on the surface opposite to the surface with laser light. In such an apparatus, a visible image can be recorded not only on an image recording layer but also on a recording layer for recording normal digital data on an optical disk using a predetermined dye.

-Configuration of optical disc recording device-
FIG. 1 is a block diagram showing a configuration of the optical disc recording apparatus 100. As shown in the figure, this optical disk recording apparatus 100 is connected to a host personal computer (PC) 110, and includes an optical pickup 10, a spindle motor 11, an RF (Radio Frequency) amplifier 12, and a servo circuit 13. The decoder 15, the control unit 16, the encoder 17, the strategy circuit 18, the laser driver 19, the laser power control circuit 20, the frequency generator 21, the stepping motor 30, the motor driver 31, and the motor controller 32. A PLL (Phase Locked Loop) circuit 33, a FIFO (First In First Out) memory 34, a drive pulse generator 35, and a buffer memory 36.

  The spindle motor 11 is a motor that rotationally drives an optical disk D that is a target of data recording, and the number of rotations is controlled by a servo circuit 13. In the optical disk recording apparatus 100 according to the present embodiment, recording or the like is performed by the CAV (Constant Angular Velocity) method, and therefore the spindle motor 11 is set at a constant angular velocity set by an instruction from the control unit 16 or the like. It is designed to rotate.

  The optical pickup 10 is a unit that irradiates the optical disk D rotated by the spindle motor 11 with a laser beam, and its configuration is shown in FIG. As shown in FIG. 2, the optical pickup 10 includes a laser diode 53 that emits a laser beam B, a diffraction grating 58, an optical system 55 that focuses the laser beam B on the surface of the optical disc D, and a light receiving device that receives reflected light. An element 56 is provided.

  In the optical pickup 10, the laser diode 53 emits a laser beam B having an intensity corresponding to the drive current when supplied with the drive current from the laser driver 19 (see FIG. 1). The optical pickup 10 separates the laser beam B emitted from the laser diode 53 into a main beam, a preceding beam, and a succeeding beam by a diffraction grating 58, and these three laser beams are polarized beam splitter 59, collimator lens 60, 1 / The light is condensed on the surface of the optical disc D through the four-wavelength plate 61 and the objective lens 62. Then, the three laser beams reflected on the surface of the optical disk D are transmitted again through the objective lens 62, the quarter wavelength plate 61, and the collimator lens 60, reflected by the polarization beam splitter 59, and passed through the cylindrical lens 63. The light is incident on the light receiving element 56. The light receiving element 56 outputs a received signal to the RF amplifier 12 (see FIG. 1), and the received light signal is supplied to the control unit 16 and the servo circuit 13 via the RF amplifier 12.

  The objective lens 62 is held by a focus actuator 64 and a tracking actuator 65 and can move in the optical axis direction of the laser beam B and the radial direction of the optical disc D. Each of the focus actuator 64 and the tracking actuator 65 moves the objective lens 62 in the optical axis direction and the radial direction according to the focus error signal and the tracking error signal supplied from the servo circuit 13 (see FIG. 1). The servo circuit 13 generates a focus error signal and a tracking error signal based on the light reception signal supplied via the light receiving element 56 and the RF amplifier 12, and moves the objective lens 62 as described above to perform focus control. And tracking control.

  Further, the optical pickup 10 has a front monitor diode (not shown). When the laser diode 53 emits laser light, a current is generated in the front monitor diode that receives the emitted light, and the current is 1 is supplied from the optical pickup 10 to the laser power control circuit 20 shown in FIG.

  The RF amplifier 12 amplifies the EFM (Eight to Four Modulation) modulated RF signal supplied from the optical pickup 10, and outputs the amplified RF signal to the servo circuit 13 and the decoder 15. The decoder 15 performs EFM demodulation on the EFM-modulated RF signal supplied from the RF amplifier 12 during reproduction to generate reproduction data.

  The servo circuit 13 is supplied with an instruction signal from the control unit 16, an FG pulse signal having a frequency corresponding to the rotation speed of the spindle motor 11 supplied from the frequency generator 21, and an RF signal from the RF amplifier 12. The servo circuit 13 performs rotation control of the spindle motor 11 and focus control and tracking control of the optical pickup 10 based on these supplied signals. As a driving method of the spindle motor 11 when information is recorded on the recording surface of the optical disc D or when a visible image is formed on the image recording layer of the optical disc D, the optical disc D is driven at a constant angular velocity (CAV: Constant Angular). (Velocity) or a system (CLV: Constant Linear Velocity) for rotationally driving the optical disc D so as to have a constant recording linear velocity may be used. In the optical disc recording apparatus 100 described in FIG. The servo circuit 13 rotates the spindle motor 11 at a constant angular velocity instructed by the control unit 16.

  The buffer memory 36 is supplied from the host PC 110 and is information (hereinafter referred to as recording data) to be recorded on the recording surface of the optical disc D and information corresponding to a visible image to be formed on the image recording layer of the optical disc D (hereinafter referred to as image). Data). The recording data stored in the buffer memory 36 is output to the encoder 17, and the image data is output to the control unit 16.

  The encoder 17 performs EFM modulation on the recording data supplied from the buffer memory 36 and outputs it to the strategy circuit 18. The strategy circuit 18 performs time axis correction processing on the EFM signal supplied from the encoder 17 and outputs the result to the laser driver 19.

  The laser driver 19 drives a laser diode 53 (see FIG. 2) of the optical pickup 10 according to a signal modulated according to the recording data supplied from the strategy circuit 18 and the control of the laser power control circuit 20.

  The laser power control circuit 20 controls the laser power emitted from the laser diode 53 (see FIG. 2) of the optical pickup 10. Specifically, the laser power control circuit 20 controls the laser driver 19 so that a laser beam having a value that matches the target value of the optimum laser power indicated by the control unit 16 is emitted from the optical pickup 10. The laser power control by the laser power control circuit 20 performed here is controlled so that laser light having a target intensity is emitted from the optical pickup 10 using the current value supplied from the front monitor diode of the optical pickup 10. Feedback control.

  In the FIFO memory 34, the image data supplied from the host PC 110 and stored in the buffer memory 36 is supplied via the control unit 16 and sequentially stored. Here, the image data stored in the FIFO memory 34, that is, the image data supplied from the host PC 110 to the optical disc recording apparatus 100 includes the following information. This image data is data for forming a visible image on the surface of the disk-shaped optical disk D. As shown in FIG. 3, each of n pieces of data on a large number of concentric circles centered on the center O of the optical disk D is used. Information indicating the degree of gradation (shading) is described for each coordinate (indicated by a black dot in the figure). The image data includes coordinate points P11, P12,... P1n, in which information indicating the gradation of each coordinate belongs to the innermost circle, coordinates P21, P22,. ..P2n is data in which information indicating the degree of gradation of each coordinate point up to the coordinate Pmn of the outermost circle in the order of the coordinates belonging to the circle on the outer circumference side is described in the FIFO memory 34. Information indicating the gradation of each coordinate on the polar coordinates is supplied in the above order. FIG. 3 is a diagram schematically illustrating the positional relationship between the coordinates, and actual coordinates are arranged more densely than illustrated. When the host PC 110 creates image data to be formed on the photosensitive surface of the optical disc D in a commonly used bitmap format or the like, the bitmap data is converted into the polar coordinate format data as described above. Then, the converted image data may be transmitted from the host PC 110 to the optical disc recording apparatus 100.

  When a visible image is formed on the image recording layer of the optical disc D based on the image data supplied as described above, a clock signal for image recording is supplied from the PLL circuit 33 to the FIFO memory 34. It has become. Each time the clock pulse of the image recording clock signal is supplied, the FIFO memory 34 outputs information indicating the gradation degree of one coordinate accumulated first to the drive pulse generator 35. Yes.

  The drive pulse generator 35 generates a drive pulse for controlling the irradiation timing of the laser light emitted from the optical pickup 10. Here, the drive pulse generation unit 35 generates a drive pulse having a pulse width corresponding to information indicating the degree of gradation for each coordinate supplied from the FIFO memory 34. For example, when the gradation of a certain coordinate is relatively large (when the density is large), a drive pulse with a light level (second intensity) pulse width increased is generated as shown in the upper part of FIG. For coordinates with a relatively small degree of furnishing, as shown in the lower part of FIG. 4, a drive pulse with a reduced write level pulse width is generated. Here, the light level is a power level at which a change occurs in the image recording layer when the image recording layer of the optical disc D is irradiated with the laser power of that level, and the reflectance is clearly changed. When a pulse is supplied to the laser driver 19, a light level laser beam is emitted from the optical pickup 10 for a time corresponding to the pulse width. Accordingly, when the gradation level is large, the laser light of the light level is irradiated for a longer time, and the reflectance changes in a larger area in the unit area of the image recording layer of the optical disc D. As a result, the user or the like It is visually recognized that the region is a region having a high density. In the present embodiment, the gradation shown in the image data is expressed by varying the length of the region whose reflectance is changed per unit region (unit length) in this way. The servo level (first intensity) is a power level at which the image recording layer hardly changes when the image recording layer of the optical disc D is irradiated with the laser power of that level, and it is not necessary to change the reflectance. The region may be irradiated with the laser light of the servo level without irradiating the laser light of the light level.

  The drive pulse generator 35 generates a drive pulse in accordance with the information indicating the gradation for each coordinate as described above, and performs laser power control by the laser power control circuit 20, focus control by the servo circuit 13, and When it is necessary to perform the tracking control, a light level pulse or a servo level pulse for a very short period is inserted regardless of the information indicating the gradation level. For example, as shown in the upper part of FIG. 5, in order to express a visible image according to the gradation of a certain coordinate in the image data, it is necessary to irradiate a laser beam having a light level for a period of time T1. When T1 is longer than a predetermined servo cycle ST for controlling the laser power, a servo off pulse (SSP1) for a very short time t after the servo cycle ST has elapsed from the time when the write level pulse is generated. Insert. On the other hand, as shown in the lower part of FIG. 5, when it is necessary to irradiate a laser beam having a servo level for a period longer than the servo cycle ST in order to represent a visible image according to the gradation of a certain coordinate in the image data, The servo on pulse (SSP2) is inserted after the servo cycle ST has elapsed since the generation of the first pulse.

  As described above, the laser power control by the laser power control circuit 20 is based on the current (intensity of the irradiated laser light) supplied from the front monitor diode that receives the laser light irradiated from the laser diode 53 (see FIG. 2) of the optical pickup 10. (The current having a value corresponding to the current value). More specifically, as shown in FIG. 6, the laser power control circuit 20 samples and holds a value corresponding to the intensity of the irradiated laser beam received by the front monitor diode 53a as described above (S201, S202). . Then, when irradiation is performed with the light level as a target value, that is, when a light level drive pulse (see FIGS. 4 and 5) is generated, the light is supplied from the control unit 16 based on the sample and hold result. Laser power control is performed so that the laser light of the light level target value is irradiated (S203). Further, when irradiation is performed with the servo level as a target value, that is, when a servo level drive pulse (see FIGS. 4 and 5) is generated, it is supplied from the control unit 16 based on the result of sample and hold. Laser power control is performed so that laser light of the target servo level value is irradiated (S204). Therefore, when the write level or servo level pulse is not continuously output for a time longer than the predetermined servo cycle ST (sample cycle), the servo off pulse SSP1 and the servo on pulse are output as described above regardless of the contents of the image data. SSP2 is forcibly inserted so that the laser power can be controlled for each level as described above.

  As described above, the servo off-pulse SSP1 is inserted not only for controlling the laser power but also for performing focus control and tracking control by the servo circuit 13. That is, the tracking control and the focus control are based on the RF signal received by the light receiving element 56 (see FIG. 2) of the optical pickup 10, that is, the return light (reflected light) from the optical disk D of the laser light emitted from the laser diode 53. Done. Here, FIG. 7 shows an example of a signal received by the light receiving element 56 when the laser beam is irradiated. As shown in the figure, the reflected light when the light level laser beam is irradiated includes an element of a peak portion K1 when the laser beam rises and a shoulder portion K2 where the level becomes constant thereafter. The portion shown is considered to be energy used for image formation of the image recording layer. The energy used for image formation of such an image recording layer is not always a stable value, and may vary according to various situations. Therefore, it is conceivable that the shape of the shaded portion in the figure changes each time, that is, the reflected light of the light level laser light is not always stable and has a lot of noise, and if this reflected light is used, There is a risk that accurate focus control and tracking control may be hindered. Therefore, as described above, when the light level laser beam is continuously irradiated for a long time, the reflected light of the servo level laser beam cannot be obtained, and accurate focus control and tracking control cannot be performed. End up.

  Therefore, by inserting the servo off pulse SSP1 as described above, the reflected light of the servo level laser light can be periodically acquired, and focus control and tracking control are executed based on the acquired reflected light. It is. When forming a visible image on the image recording layer of the optical disc D, unlike when recording on the recording surface, it is not necessary to trace along a pre-groove (guide groove) formed in advance. Therefore, in this embodiment, the target value of tracking control is a fixed value (a constant offset voltage is set). Such a control method can be applied not only when image information is formed on the image recording layer but also when image information is formed on the recording surface. That is, if a material that changes not only the reflectance but also the color development when irradiated with laser light is used for the recording surface (recording layer), an image can be formed on the recording surface as well as the image recording layer. When a visible image is formed on the recording surface in this way, the original data recording cannot be performed on the portion where the visible image is formed. Therefore, the data recording area and the visible image forming area are separated in advance. Is preferred.

  As described above, it is preferable that the time for inserting the servo off-pulse SSP1 and the servo off-pulse SSP2 is a minimum time within a range that does not hinder the execution of various servos such as laser power control, tracking control, and focus control. By making the insertion time very short, various servos as described above can be performed with almost no influence on the formed visible image.

  Returning to FIG. 2, the PLL circuit (signal output means) 33 multiplies the FG pulse signal having a frequency corresponding to the rotational speed of the spindle motor 11 supplied from the frequency generator 21, and uses it for the visible image formation described later. Output clock signal. The frequency generator 21 uses the back electromotive current obtained by the motor driver of the spindle motor 11 to output an FG pulse signal having a frequency corresponding to the spindle rotation speed. For example, as shown in the upper part of FIG. 8, when the frequency generator 21 generates eight FG pulses while the spindle motor 11 makes one revolution, that is, the optical disk D makes one revolution, the lower part of FIG. As shown in FIG. 4, the PLL circuit 33 outputs a clock signal (for example, a frequency of 5 times the FG pulse signal and 40 high-level pulses during one rotation of the optical disk D) obtained by multiplying the FG pulse, that is, the spindle motor 11. To output a clock signal having a frequency corresponding to the rotational speed of the optical disk D rotated. A clock signal obtained by multiplying the FG pulse signal in this way is output from the PLL circuit 33 to the FIFO memory 34, and the gradation of one coordinate is added to the clock signal every cycle, that is, every time the disk D rotates by a certain angle. The data shown is output from the FIFO memory 34 to the drive pulse generator 35. As described above, the PLL circuit 33 may be used to generate a clock signal obtained by multiplying the FG pulse. However, when the spindle motor 11 is a motor with sufficiently stable rotational drive capability. In this case, a crystal oscillator may be provided in place of the PLL circuit 33 to generate a clock signal obtained by multiplying the FG pulse as described above, that is, a clock signal having a frequency corresponding to the rotational speed of the optical disc D.

  The stepping motor 30 is a motor for moving the optical pickup 10 in the radial direction of the optical disc D set on the optical disc D. The motor driver 31 rotates the stepping motor 30 by an amount corresponding to the pulse signal supplied from the motor controller 32. The motor controller 32 generates a pulse signal corresponding to the movement amount and the movement direction in accordance with the movement start instruction including the movement direction and movement amount in the radial direction of the optical pickup 10 instructed from the control unit 16, and sends it to the motor driver 31. Output. The stepping motor 30 moves the optical pickup 10 in the radial direction of the optical disc D, and the spindle motor 11 rotates the optical disc D with respect to the optical disc D, whereby the laser light irradiation position of the optical pickup 10 is changed to various positions on the optical disc D. It can be moved, and these components constitute the irradiation position adjusting means.

  The control unit 16 includes a CPU (Central Processing Unit), a ROM (Read Only Memory), a RAM (Random Access Memory), and the like, and controls each unit of the optical disc recording apparatus 100 according to a program stored in the ROM. The recording process on the recording surface of the optical disc D and the image forming process on the image recording layer of the optical disc D are centrally controlled. What has been described above is the configuration of the optical disc recording apparatus 100 according to the present embodiment.

B. Operation of Optical Disc Recording Device Next, the operation of the optical disc recording device 100 configured as described above will be described. As described above, the optical disc recording apparatus 100 can record information such as music data supplied from the host PC 110 on the recording surface of the optical disc D, and can also record information on the image recording layer of the optical disc D. A visible image corresponding to the image data supplied from the PC 110 can be formed. Hereinafter, the operation of the optical disc recording apparatus 100 capable of performing processing such as information recording and visible image formation will be described with reference to FIGS.

  First, when the optical disc D is set in the optical disc recording apparatus 100, the control unit 16 controls the optical pickup 10 and the like, and the surface of the set optical disc D facing the optical pickup 10 is an optical disc of any format. To detect. For example, in the case of DVD-R, the presence or absence of a land pre-pit signal, pre-record signal, or in the case of DVD + R, ADIP (Address in Pregroove) is detected. If such information is not recorded, it is not recognized as an optical disc.

  Here, when a land pre-pit signal or pre-code signal is detected from the set optical disc D, for example, in the case of DVD-R, and ADIP is detected in the case of DVD + R, the recording surface faces the optical pickup 10. Thus, it is determined that the optical disc D is set, and the control unit 16 performs control for recording the recording data supplied from the host PC 110 on the recording surface (step Sa2). Since the control for recording the recording data performed here is the same as that of a conventional optical disk recording apparatus (DVD-R or DVD + R drive apparatus), description thereof is omitted.

  On the other hand, when a pre-pit signal indicating that the optical disk can be drawn is detected from the set optical disk D, it is determined that the optical disk D is set so that the image recording layer faces the optical pickup 10, The control unit 16 determines whether or not the disc ID of the set optical disc D can be acquired (step Sa3). The disc ID of the optical disc D can be mounted in the pre-pit signal. For example, as shown in FIG. 12, a visible image corresponding to information obtained by encoding the disc ID is described along the circumference of the outermost peripheral portion of the optical disc D on the image recording layer side. In FIG. 12, the disk ID is formed on the image recording layer of the optical disk D by forming a reflective area 301a and a non-reflective area 301b having a length corresponding to the code along the circumference of the outermost peripheral portion as shown. It is described. The control unit 16 traces the irradiation position of the laser beam of the optical pickup 10 along the outermost circumference of the optical disc D, and acquires the disc ID from the reflected light.

  Therefore, when the reflective area 301a and the non-reflective area 301b corresponding to the disk ID as described above are not formed on the outermost peripheral portion of the image recording layer, the optical disk D is a general optical disk having no image recording layer. (CD-R, DVD-R, etc.). When the disk ID cannot be acquired in this way, the control unit 16 determines that the optical disk D is incapable of forming a visible image (step Sa4), and performs processing for notifying the user of that fact.

  On the other hand, if the disk ID can be obtained from the optical disk D, the host PC 110 waits until an image formation instruction including image data is received (step Sa5). Performs initialization control for forming a visible image on the image recording layer of the optical disc D (step Sa6). More specifically, the control unit 16 controls the servo circuit 13 so that the spindle motor 11 is rotated at a predetermined angular velocity, or moves the optical pickup 10 to the initial position on the innermost peripheral side in the radial direction of the optical disc D. The instruction for sending is sent to the motor controller 32 to drive the stepping motor 30.

  Further, in the initialization control for image formation, the control unit 16 focuses so that the laser beam having a larger beam spot diameter is irradiated to the image recording layer of the optical disc D than when information is recorded on the recording surface. A control target value can also be instructed to the servo circuit 13.

  The focus control content when the target value as described above is instructed will be described in more detail as follows. As described above, the focus control by the servo circuit 13 is performed based on the signal output from the light receiving element 56 of the optical pickup 10. When recording information on the recording surface of the optical disc D, the servo circuit 13 is focused so that circular return light (A in the figure) is received at the centers of the four areas 56a, 56b, 56c, and 56d of the light receiving element 56 shown in FIG. The actuator 64 (see FIG. 2) is driven. That is, the focus actuator 64 is driven so that (a + c) − (b + d) = 0 when the received light amounts of the areas 56a, 56b, 56c, and 56d are a, b, c, and d.

  On the other hand, when forming a visible image on the image recording layer of the optical disc D, as described above, focus control is performed so that the laser beam having a diameter larger than that when recording information on the recording surface is irradiated to the image recording layer. Is called. When the shape of the return light received by the light receiving element 56 shown in FIG. 12 is an elliptical shape (B or C in the figure), the spot size of the laser light is larger than that in the case of the circle A, so the servo circuit 13 drives the focus actuator 64 so that the elliptical return light is received by the light receiving element 56. That is, the focus actuator 64 is driven so as to satisfy (a + c) − (b + d) = α (α is not 0). Therefore, in the present embodiment, the control unit 16 and the servo circuit 13 constitute beam spot control means.

  As described above, in the initialization control for visible image formation described above, the control unit 16 instructs the servo circuit 13 to set α (not 0), so that a laser having a larger spot diameter than that when recording information on the recording surface. Light can be applied to the image recording layer of the optical disc D. As described above, when a visible image is formed on the image recording layer of the optical disc D, the following effects can be obtained by irradiating laser light having a larger spot diameter than when recording information on the recording surface. That is, in the present embodiment, when forming a visible image, laser light is irradiated while rotating the optical disc D, as in the case of recording information on the recording surface. Therefore, by increasing the beam spot diameter of the laser light, a visible image can be formed on the entire area of the image recording layer of the optical disc D in a shorter time. The reason for this will be described with reference to FIG. As schematically shown in the figure, when comparing the case where the beam spot diameter BS of the laser beam to be irradiated is large and small, the area of the region to be image-formed when the optical disk D is rotated once is the beam. When the spot diameter BS is large, it becomes larger. For this reason, when the beam spot diameter BS is small, the optical disk D has to be rotated more in order to make the entire area the target of image formation (in the example shown in the figure, when the beam spot diameter BS is large, 4 rotations, and when it is small, 6 rotations) ), It takes a lot of time for image formation. For the reasons described above, the optical disc recording apparatus 100 is configured to irradiate a laser beam having a spot diameter larger than that at the time of information recording when forming a visible image.

  Further, in the initialization control for image formation, the control unit 16 sets the target value of each level to the laser power so that the laser light of the write level and the servo level corresponding to the acquired disk ID is emitted from the optical pickup 10. The control circuit 20 is instructed. That is, the ROM of the control unit 16 stores target values to be set as the write level and the servo level for each of a plurality of types of disk IDs. The control unit 16 stores the write level and the write level corresponding to the acquired disk ID. The servo level target values are read out, and these target values are instructed to the laser power control circuit 20.

  The reason why the target power value is set in accordance with the disk ID is based on the following reason. That is, it is conceivable that the characteristics of the dye of the image recording layer differ depending on the type of the optical disc D. If the characteristics are different, the characteristic that the reflectivity changes as a result of irradiation with a laser beam of any power level naturally changes. Become. For this reason, even when the image recording layer of a certain optical disk D is irradiated with laser light of a certain light level, and the reflectance of the irradiated area can be changed sufficiently, the image of the other optical disk D is also displayed. When the recording layer is irradiated with laser light having the same light level, the reflectance of the irradiated region cannot always be changed. Therefore, in the present embodiment, the target values of the write level and the servo level that allow accurate image formation are obtained in advance by experiment for each optical disk corresponding to each of various disk IDs as described above. Then, by storing the obtained target value in the ROM in association with each disk ID, optimum power control can be performed according to the characteristics of the image recording layers of various optical disks D as described above. I am doing so.

  When the initialization control as described above is performed by the control unit 16, a process for actually forming a visible image on the image recording layer of the optical disc D is performed. As shown in FIG. 10, the control unit 16 first transfers the image data supplied from the host PC 110 via the buffer memory 36 to the FIFO memory 34 (step Sa7). Then, the control unit 16 determines from the FG pulse signal supplied from the frequency generator 21 whether the predetermined reference position of the optical disc D rotated by the spindle motor 11 has passed the laser light irradiation position of the optical pickup 10. Is determined (step Sa8).

  Here, a method for detecting whether or not the predetermined reference position and the laser beam irradiation position have passed the position will be described with reference to FIGS. As shown in FIG. 14, the frequency generator 21 outputs a predetermined number (eight in the illustrated example) of FG pulses while the spindle motor 11 rotates once, that is, while the optical disk D rotates once. Therefore, the control unit 16 outputs a reference position detection pulse by synchronizing one of the FG pulses supplied from the frequency generator 21 with the rising timing of the reference pulse, and then makes one rotation from the reference position detection pulse. A reference position detection pulse signal for outputting a reference position detection pulse is generated in synchronization with the rising timing of the minute number (eighth in the illustrated example) pulse. By generating such a reference position detection pulse, it is possible to detect that the time when the pulse is generated is the timing at which the laser light irradiation position of the optical pickup 10 has passed the reference position of the optical disc D. That is, as shown in FIG. 15, the laser beam irradiation position of the optical pickup 10 at the timing when the first reference position detection pulse is generated is indicated by a thick line in the drawing (the optical pickup 10 is movable in the radial direction, so the irradiation position is If the reference position detection pulse generated after one rotation is generated, the laser light irradiation position of the optical pickup 10 is naturally indicated by a thick line in the figure. In position. In this way, the radial line to which the laser beam irradiation position belongs becomes the reference position at the timing at which the reference position detection pulse is first generated, and the control unit 16 is generated each time the optical disk D rotates as described above. It is possible to detect that the irradiation position of the laser beam has passed the reference position of the optical disc D based on the reference position detection pulse signal. In the figure, the alternate long and short dash line shows an example of the movement trajectory of the irradiation position of the laser beam from the generation of a reference position detection pulse to the generation of the next reference position detection pulse.

  After receiving the image formation instruction from the host PC 110, when it is detected that the reference position of the optical disc D has passed the laser light irradiation position by the above-described method, the control unit 16 sets 1 to the variable R indicating the rotation speed. After the increment (step Sa9), it is determined whether or not R is an odd number (step Sa10).

  Here, when it is first detected that the reference position has been passed after receiving the image formation instruction, R = 0 (initial value) + 1 = 1. In this case, R is an odd number in step Sa10. Will be determined. When it is determined that R is an odd number in this way, the control unit 16 performs control for forming a visible image by irradiating the image recording layer of the optical disc D with the laser beam from the optical pickup 10 (step Sa11). More specifically, the control unit 16 controls each unit to sequentially output image data from the FIFO memory 34 in synchronization with the clock signal output from the PLL circuit 33 from the time when the reference position detection pulse is received. Control. By this control, as shown in FIG. 16, every time a clock pulse is supplied from the PLL circuit 33, the FIFO memory 34 outputs information indicating the gradation of one coordinate to the drive pulse generator 35, and the drive pulse The generation unit 35 generates a drive pulse having a pulse width according to the gradation shown in the information and outputs the drive pulse to the laser driver 19. As a result, the optical pickup 10 irradiates the image recording layer of the optical disc D with the laser light at the light level for a time corresponding to the gradation of each coordinate, and the reflectance of the irradiated region changes, as shown in FIG. Such a visible image can be formed.

  As schematically shown in the figure, since the optical disk D is rotated by the spindle motor 11, the irradiation position of the laser beam of the optical pickup 10 is one cycle of the clock signal (the rising edge of the next pulse from the rising edge of the pulse). During the period until the timing), it moves along the circumference by the area indicated by C in the figure. By changing the time during which the laser beam is irradiated at the light level while the laser beam irradiation position passes through the region C according to the gradation level as described above, the gradation level varies depending on the region C as shown in the figure. Accordingly, the reflectance of different areas can be changed. In this way, a visible image corresponding to image data is formed on the image recording layer of the optical disc D by controlling the irradiation time of the light level laser light when passing through each region C according to the gradation of each coordinate. It can be done.

  As described above, when the control for executing the formation of the visible image by the laser light irradiation controlled according to the image data is executed, the process of the control unit 16 returns to Step Sa7, and the image data supplied from the buffer memory 36 Is transferred to the FIFO memory 34. Then, it is detected whether or not the laser light irradiation position of the optical pickup 10 has passed through the reference position of the optical disc D, and when it is detected that the reference position has been passed, 1 is incremented to R. As a result, when R becomes an even number, the control unit 16 controls each unit of the apparatus so as to stop the visible image formation by the laser light irradiation control as described above (step Sa12). More specifically, the FIFO memory 34 is controlled not to output information indicating the gradation of each coordinate to the drive pulse generator 35 in synchronization with the clock signal supplied from the PLL circuit 33. That is, after the control unit 16 forms a visible image by irradiating the image recording layer of the optical disc D with a light level laser beam, the reflectivity of the image recording layer is continued during the next rotation of the optical disc D. Control is performed so as not to irradiate the laser beam for changing.

  When the laser beam irradiation for forming the visible image is stopped in this way, the control unit 16 instructs the motor controller 32 to move the optical pickup 10 to the outer peripheral side in the radial direction by a predetermined amount (step Sa13). In response to the instruction, the motor controller 32 drives the stepping motor 30 via the motor driver 31, thereby moving the optical pickup 10 to the outer peripheral side by a predetermined amount.

  Here, the predetermined amount by which the optical pickup 10 is moved in the radial direction of the optical disc D may be appropriately determined according to the beam spot diameter BS (see FIG. 13) irradiated from the optical pickup 10 as described above. That is, when a visible image is formed on the image recording layer of the disk-shaped optical disk D, the laser beam irradiation position of the optical pickup 10 can be moved on the surface of the optical disk D without any gap, thereby forming a higher quality image. Necessary to realize. Accordingly, if the unit movement amount of the optical pickup 10 in the radial direction as described above is substantially the same as the beam spot diameter BS of the laser beam irradiated to the optical disc D, the laser beam can be emitted onto the surface of the optical disc D with almost no gap. Irradiation is possible, and higher-quality image formation is possible. In some cases, an area larger than the irradiated beam spot diameter may be colored due to various factors such as the property of the image recording layer. In such a case, the width of the colored area is considered, and adjacent colored areas overlap. The unit movement amount may be determined so that it does not occur. In this embodiment, since the beam spot diameter BS is made larger than that for recording on the recording surface (for example, about 20 μm), the control unit 16 holds the optical pickup 10 by the length substantially the same as the beam spot diameter BS. The motor controller 32 is controlled to move in the radial direction, and the stepping motor 30 is driven. The stepping motor 30 in recent years can control the movement amount in units of 10 μm by using the μ step technology, and the optical pickup 10 can be controlled in units of 20 μm using the stepping motor 30 as described above. It is sufficiently feasible to move in the radial direction.

  When the optical pickup 10 is controlled to move by a predetermined amount in the radial direction as described above, the control unit 16 performs the laser beam irradiation at the light level so as to change the light level value of the target laser beam. The changed light level value to be targeted is instructed to the laser power control circuit 20 (step Sa14). In the present embodiment, a CAV method in which laser light is irradiated while rotating the optical disk D while maintaining a constant angular velocity is adopted as a method for forming a visible image. When moved sideways, the linear velocity increases. Therefore, when the optical pickup 10 is moved in the radial direction (outer peripheral side) in this way, the target value of the light level is changed so as to be larger than that at the time as described above, and thereby the linear velocity is changed. Even if this changes, it is possible to irradiate with a laser power having such an intensity that the reflectance of the image recording layer of the optical disk D can be sufficiently changed.

  As described above, when the movement control in the radial direction of the optical pickup 10 and the control to change the target value of the light level are executed, the control unit 16 performs unprocessed image data, that is, the drive pulse generation unit 35 for forming a visible image. It is determined whether or not there is image data not supplied to the image. If there is no image data, the process is terminated.

  On the other hand, if there is unprocessed image data that has not been supplied to the motor controller 32, the process returns to step Sa7 to continue the process for visible image formation. That is, image data is transferred from the control unit 16 to the FIFO memory 34 (step Sa7), and it is determined whether or not the irradiation position of the laser beam has passed the reference position of the optical disc D (step Sa8). When the reference position is passed, the variable R indicating the number of rotations is incremented by 1 (step Sa9), and it is determined whether or not the incremented R is an odd number (step Sa10). Here, when R is an odd number, the control unit 16 controls each part of the apparatus so that the laser beam irradiation for forming a visible image as described above is performed. When R is an even number, the visible image is displayed. Is stopped (irradiated with servo-level laser light), and control such as the above-described movement control of the optical pickup 10 in the radial direction and change of the target value of the light level is performed. That is, when the control unit 16 performs laser light irradiation (including the light level) for image formation on the optical disc D during a certain round, laser light irradiation for image formation is performed during the next round. Is controlled so that the optical pickup 10 is controlled to move in the radial direction during the rotation. Thus, by performing control for moving the optical pickup 10 during the lap when image formation is not performed, control for changing the light level target value, and the like, the irradiation position, the power value of the laser light to be irradiated, and the like are associated with the control. No image is formed while the angle fluctuates, and laser beam irradiation for image formation can be executed after the irradiation position and the intensity of the laser beam are stabilized. Therefore, it is possible to suppress degradation of the quality of the visible image formed due to the radial movement control of the optical pickup 10 as described above.

  What has been described above is the main operation of the optical disc recording apparatus 100. According to the optical disc recording apparatus 100, the light used for recording information on the recording surface without newly installing printing means or the like. Each part of the apparatus such as the pickup 10 is used as much as possible, and a visible image corresponding to the image data can be formed by irradiating the image recording layer of the optical disc D on which the image recording layer is formed with laser light.

  In the present embodiment, the laser beam irradiation timing is based on the clock signal generated using the FG pulse generated according to the rotation of the spindle motor 11, that is, the clock signal generated according to the rotation amount of the optical disc D. Therefore, it is possible to grasp the laser beam irradiation position in the optical disc recording apparatus 100 without acquiring position information or the like from the optical disc D side. Therefore, according to the optical disc recording apparatus 100, there is no restriction that the optical disc D subjected to special processing such as forming a pre-groove (guide groove) in the image recording layer must be used, and pre-groove, position information, etc. A visible image corresponding to image data can be formed even on an image recording layer in which is not formed in advance.

C. Modifications Note that the present invention is not limited to the above-described embodiments, and various modifications as exemplified below are possible.

(Modification 1)
In the embodiment described above, the laser light irradiation time is controlled according to the gradation for each coordinate included in the image data corresponding to the visible image supplied from the host PC 110, so that the image recording layer of the optical disc D is recorded. Although the density of the visible image to be formed is expressed, the light level of the laser power to be irradiated may be changed according to the information indicating the gradation for each coordinate to express the density of the visible image. For example, as shown in FIG. 18, if the image recording layer of the optical disc D has a characteristic in which the degree of change in reflectance changes gradually according to the amount of energy applied, the energy E1, E2, By applying different energy such as E3, the degree of change in reflectance of the image recording layer also changes as D1, D2, and D3. Therefore, for the optical disc D on which the image recording layer having the above characteristics is formed, by changing the light level value of the laser light to be irradiated according to the gradation for each coordinate indicated in the image data. Each coordinate position on the optical disc D can be changed according to the gradation, thereby expressing light and shade.

  In addition to the method of changing the light level value according to the gradation as described above, a plurality of adjacent coordinates as described below are regarded as one unit area for expressing the gradation, and the unit area includes The shade of the visible image formed on the image recording layer of the optical disc D may be expressed by controlling the irradiation time of the laser light with respect to each of a plurality of included coordinates in association with the difference. More specifically, as schematically shown in FIG. 19, in the optical disc recording apparatus 100, the laser light irradiation position of the optical pickup 10 is set to a plurality of circumferences along a circular path TR (shown by a dashed line in the figure). Visible image formation is carried out by making relative movement and appropriately switching the power value of the laser beam irradiated during the movement between the light level and the servo level according to the image data.

  In this modification, a fan-shaped region including a predetermined number (three in the illustrated example) of circumferential paths TR belonging to each of the fan-shaped portions obtained by dividing the optical disk D into a plurality of fan-shaped portions is defined as a unit region TA (thick line in the figure). The irradiation timing of the laser light applied to each of the three circumferential paths TR belonging to the unit area TA is controlled so that the density is expressed for each unit area TA in the visible image.

  For example, when forming an image in which the density of a certain unit area TA is expressed very light (density is not 0), as shown in the upper part of FIG. 20, three circumferential paths TR belonging to the unit area TA are displayed. The irradiation time of the laser beam is controlled so as to change all the reflectances (discolored portions are shown in black in the figure), that is, the drive pulse generator 35 generates a drive pulse as shown in the lower part of FIG. Image data is created, and control is performed such that light level laser light is continuously irradiated during the time that the laser light irradiation position passes through the three circumferential paths TR belonging to the unit area TA.

  On the other hand, when an image expressing the density of the unit area TA is formed, as shown in the upper part of FIG. 21, among the three circumferential paths TR belonging to the unit area TA, the innermost circumferential path. The laser light irradiation time is controlled so as to change only the reflectance of a small portion of TR, that is, as shown in the lower part of FIG. 21, during the time the laser light irradiation position passes through the circumferential path TR on the inner peripheral side. Image data is generated so that the drive pulse generation unit 35 generates a drive pulse that irradiates light level laser light only during a part of the time.

  Further, when the density of the unit area TA is set to an intermediate density, as shown in the upper part of FIG. 22, the innermost circumferential path among the three circumferential paths TR belonging to the unit area TA. The laser light irradiation time is controlled so that the reflectance of all parts of TR changes and half of the intermediate circumferential path TR changes color. That is, as shown in the lower part of FIG. 22, the time during which the laser beam irradiation position passes through the inner circumferential path TR of the circumferential path TR and the laser beam irradiation position passes through the intermediate circumferential path TR. Image data is generated so that the drive pulse generator 35 generates a drive pulse that is irradiated with the laser light at the light level for a part of the current time.

  In the host PC 110, image data that can express gradation for each unit area TA as described above is generated in advance, and the image data is supplied to the optical disc recording apparatus 100, so that the unit area as described above is obtained. A visible image in which gradation representation for each TA is made can be formed on the image recording layer of the optical disc D.

(Modification 2)
In the embodiment described above, when a visible image is formed by irradiating the laser beam while the optical disk D is rotated once from the reference position, the optical pickup 10 is moved by a predetermined amount to the outer peripheral side in the radial direction. By performing the feed control, the laser beam irradiation position is moved so that there is almost no gap on the entire surface of the optical disk D. However, there is a case where the mechanism for driving the optical pickup 10 in the radial direction cannot control the drive amount in units of 20 μm. In an optical disk recording apparatus equipped with such a drive mechanism, the gap area where the laser beam cannot be irradiated on the optical disk D increases, and as a result, the quality of the visible image formed on the image recording layer of the optical disk D decreases. It will be.

  Therefore, when the resolution of the driving means for moving the optical pickup 10 in the radial direction is low, by using both the movement control of the optical pickup 10 in the radial direction by the driving means and the tracking control of the optical pickup 10, The irradiation position in the radial direction of the laser beam may be controlled in a smaller unit, for example, 20 μm. More specifically, as shown in FIG. 23, the optical pickup 10 is first moved to the position A by a radial driving means such as a stepping motor. Then, in a state where the optical pickup 10 is fixed at the position A, tracking control is performed so that the irradiation position in the radial direction of the laser light becomes A1. In this way, a visible image is formed by controlling the laser beam while rotating the optical disk D once with the irradiation position set to A1. When the formation of the visible image in the state where the irradiation position is set to A1, the optical pickup 10 is fixed at the position A, and the irradiation position of the laser light is moved to the outer peripheral side by the distance a by tracking control to position the irradiation position. Set to A2. In this state, a visible image is formed by irradiating a laser beam while rotating the optical disk D once. Similarly, image formation is performed while moving the laser light irradiation position in the order of A3, A4, and A5 by tracking control while the optical pickup 10 is fixed at the position A.

  When the image formation is completed with the laser light irradiation position set to A5, the optical pickup 10 is moved to the outer peripheral side by the distance A by the driving means, and the optical pickup 10 is moved to the position B. Then, by performing tracking control with the optical pickup 10 fixed at the position B, the laser light irradiation position is sequentially moved to the outer peripheral side by a distance a, such as positions B1, B2, B3, B4, and B5. Perform image formation. Thus, by using both the movement control in the radial direction of the optical pickup 10 by the stepping motor and the tracking control in combination, the laser beam can be used even when the resolution of the drive control of the driving means of the optical pickup 10 in the radial direction is low. Can be moved by a finer distance unit.

(Modification 3)
In the optical disc recording apparatus 100 according to the above-described embodiment, the CAV method is employed in which a visible image is formed by irradiating a laser beam while rotating the optical disc D at a constant angular velocity. A constant CLV method may be employed. As described above, when the CAV method is adopted, the light level value of the laser beam irradiated as the irradiation position of the laser beam moves to the outer peripheral side of the optical disc D in order to form a high-quality visible image. Although it is necessary to increase it, in the case of the CLV method, it is not necessary to change the write level value. Therefore, the image quality of the image formed on the image recording layer of the optical disc D does not deteriorate due to the fluctuation of the target laser power value.

(Modification 4)
In the above-described embodiment, the laser power control circuit 20 is configured so that the laser power of the light level target value or the servo level target value is irradiated based on the light reception result of the front monitor diode 53a of the optical pickup 10. Control was to be performed (see FIG. 6). In the above embodiment, in order to control the intensity of the laser light emitted from the laser diode 53 to coincide with the light level target value, the front monitor when the laser diode 53 emits with the light level as a target. The light reception result of the diode 53a is used. In addition, in order to control the intensity of the laser light emitted from the laser diode 53 to coincide with the servo level target value, the light reception result of the front monitor diode 53a when the laser diode 53 emits with the servo level as a target is used. It was.

  In this way, when performing laser power control with each of the write level and servo level as target values, in addition to using the light reception result of the laser beam irradiated with each level as the target value, the servo level is set as the target value. Based on the result of receiving the irradiated laser light, the laser power may be controlled so that not only the servo level but also the light level is a target value. More specifically, the laser power control circuit 20 generates laser light having the intensity of the servo level target value SM as shown in the upper part of FIG. 24 from the light reception result (current value) of the laser light emitted with the servo level as the target value. A current value SI to be supplied to the laser diode 53 for emission from the laser diode 53 is obtained. When the current value SI to be supplied for emitting the laser beam having the servo level target value SM is obtained in this way, the relationship between the current value SI and the supply current value obtained in advance through experiments or the like and the emitted laser power is first-order. As shown in the lower part of FIG. 24, the relationship (primary function) between the supply current value and the emission laser power is derived for the laser diode 53 from the inclination α expressed by the function. Next, the laser power control circuit 20 determines the current to be supplied to the laser diode 53 in order to emit light level laser light from the derived relationship and the light level target value WM set by the control unit 16. The value WI is obtained. When the light level laser beam is irradiated, the laser power control circuit 20 controls the laser driver 19 to supply the laser diode 53 with the current value WI obtained as described above. Control for emitting light level laser light can be performed without using a light reception result of laser light emitted with the light level as a target value in this way.

  In the embodiment and the modification described above, feedback control of the laser power is performed based on the light reception result of the front monitor diode 53a when laser light is irradiated for visible image formation. The feedback control is not performed at the time of visible image formation, and laser light test irradiation is performed before the visible image formation, and a current value is supplied to the laser diode 53 based on the light reception result of the front monitor diode 53a when the test irradiation is performed. Such laser power control may be performed. When the time required for image formation is short, fluctuations in the optical pickup 10 and the surrounding environment (temperature) are small, and a sufficiently accurate laser can be obtained without performing feedback control as described above. In some cases, power control can be performed. Therefore, in an optical disk recording apparatus that can form an image in a short time, it is possible to employ laser power control that does not perform feedback control as described above.

(Modification 5)
In the embodiment described above, the type of the disc set in the optical disc recording apparatus 100 is identified by reading the disc ID recorded on the outermost peripheral portion of the image recording layer of the optical disc D, and the disc type identified. The laser power control or the like corresponding to the optical disc D is performed (see FIG. 11). However, the disc ID recorded on the lead-in on the recording surface of the optical disc D is read, and is read when a visible image is formed on the image recording layer of the optical disc D. Laser power control or the like corresponding to the disc type identified by the disc ID may be performed. In order to obtain the disc ID recorded on the lead-in of the recording surface in this way, the user first sets the optical disc D so that the recording surface faces the optical pickup 10, and the optical disc D on which the optical disc recording apparatus 100 is set. The disk ID is read from the lead-in area. Then, the optical disc recording apparatus 100 prompts the user to turn the disc over and reinsert it, and when the optical disc D is set so that the image recording layer faces the optical pickup 10, the optical disc recording device 100 The visible image may be formed by performing laser power control according to the disk ID read from the lead-in area.

(Modification 6)
As described in the above-described embodiment, the optical disc recording apparatus 100 is formed on the surface opposite to the recording surface by using each part of the apparatus such as the optical pickup 10 for performing information recording on the recording surface. A visible image can be formed on the image recording layer. By the way, in the case of CD-R, the thickness of the protective layer provided on the upper layer of the recording layer is 1.2 mm, whereas the thickness of the protective layer provided on the opposite surface is very small. Therefore, as shown in FIG. 25, the distances d1 and d2 (relative positional relationship) between the position of the layer to be irradiated with the laser light of the optical disk D and the position of the optical pickup 10 are the recording surface and the image recording. Depending on which layer is set to face the optical pickup 10, the optical disk D is set to be different by about 1.2 mm.

  In the focus actuator 64 (see FIG. 2) of the optical pickup 10 designed on the assumption that the distance d1 from the recording surface of the optical disc D is the focal length, the distance between the optical pickup 10 and the irradiation target surface is d2. In some cases, sufficient focus control cannot be performed. Therefore, when the optical disc D is set so that the image recording layer faces the optical pickup 10, the distance between the image recording layer and the optical pickup 10 is about 1.2 mm so that it substantially coincides with d1. A mechanism for holding the optical disc D at a position moved in a direction away from the optical pickup 10 may be provided.

  As such a mechanism, as shown in FIG. 26, an adapter (relative position adjusting means) 271 that can be mounted on the chucking portion 270 at the center of the optical disc D is used, and the image recording layer of the optical disc D is used as described above. When the optical disc D is set in the optical disc recording apparatus 100 so as to face the optical pickup 10, the adapter 271 may be attached to the optical disc D.

  Also, a mechanism that can move between the vicinity of the part where the optical disk D of the optical disk recording apparatus 100 is set and a position away from the part, and a mechanism for changing the holding position of the optical disk D as described above. It is provided in the optical disc recording apparatus 100, and only when the image recording layer of the optical disc D is set so as to face the optical pickup 10, the mechanism is moved to the vicinity of the setting to adjust the holding position of the optical disc D. It may be.

  In addition to moving the holding position of the optical disk D to a position away from the optical pickup 10 by using the adapter 271 and the like as described above, the image recording layer faces the optical pickup 10 as shown in FIG. When the optical disk D is set as described above, a drive mechanism (relative position adjusting means) that moves the position of the optical pickup 10 to a position away from the optical disk D so that the distance between the image recording layer and the optical pickup 10 is d1. 280 may be provided.

(Modification 7)
In the above-described embodiment, focus control is performed according to the return light from the optical disk D received by the light receiving element 56 (see FIG. 2) of the optical pickup 10, and recording is performed on the recording surface in this focus control. The laser beam having a larger spot diameter than that used for the irradiation was applied to the image recording layer of the optical disc D. In the above embodiment, in order to increase the spot diameter, the focus actuator 64 is driven so that the light reception result of the light receiving element 56 becomes the elliptical shapes B and C shown in FIG. In order to irradiate the image recording layer of the optical disc D with laser light having a spot diameter larger than the spot diameter when such elliptical shapes B and C are obtained as a light reception result, the four areas 56a, 56b, Instead of the focus control according to the amount of light received by each of 56c and 56d, focus control according to the total amount of light received in all areas of the light receiving element 56 may be performed. That is, when the spot diameter of the laser beam irradiated to the image recording layer of the optical disc D is increased, the entire return light cannot be received by the light receiving element 56, and the light receiving element 56 has a shape as indicated by a circle Z in FIG. Return light in an area larger than the light receiving area can be obtained. That is, the total amount of light received by the light receiving element 56 is reduced. Therefore, the servo circuit 13 drives the focus actuator 64 so that the total light reception amount of the light receiving element 56 is smaller than the total light reception amount when the light reception results such as the circles A, B, and C shown in FIG. By doing so, the image recording layer of the optical disc D can be irradiated with a laser beam having a larger spot diameter.

(Modification 8)
Further, when a highly transparent image recording layer of the optical disk D is used, even when the optical disk D is set so that the image recording layer and the optical pickup 10 face each other, the optical disk recording apparatus 100 returns from the optical disk D. The pregroove (guide groove) formed on the recording surface of the optical disc D can be detected from the light (reflected light). More specifically, contrary to the case where the recording surface is irradiated with laser light, the return light level is high when the pregroove is irradiated with laser light, and the land portion is irradiated. The return light is small. Therefore, the pregroove can be detected by detecting the level of the return light, and as a result, tracking control can be performed along the pregroove.

  When the optical disc D is set so that the image recording layer faces the optical pickup 10 as described above, tracking control along the pregroove formed on the opposite recording surface is possible. The laser light irradiation control for forming a visible image may be performed while moving the laser light irradiation position along the line. When the pregroove formed on the recording surface opposite to the image recording layer is detected and tracking control is performed so that the laser beam irradiation position moves along the pregroove, the rotation direction of the spindle motor 11 is determined. Is in the opposite direction to that for recording on the recording surface, and the optical disk D is rotated in the opposite direction. The reason for reverse rotation in this way will be described with reference to FIG. As shown in the upper part of FIG. 29, when a spiral pre-groove PB that is clockwise when viewed from the recording surface side is formed on the recording surface of the optical disc D, as shown in the lower part of FIG. From the image recording layer side, which is the opposite surface, it appears to be formed in a counterclockwise spiral shape. Therefore, when the optical disc D is rotated from the innermost circumferential position PBS along the pre-groove PB in the same rotation direction as during recording, the laser light irradiation position is moved along the pre-groove PB. I can't. Therefore, when forming a visible image by irradiating the image recording layer of the optical disk D with laser light, if the laser light irradiation position is moved along the pregroove PB, recording is performed on the recording surface. The optical disk D is rotated in the opposite direction to that when it is performed.

  Accordingly, in the case where the visible image formation similar to the above embodiment is performed by controlling the irradiation timing and power of the laser light according to the image data while moving the irradiation position of the laser light along the pregroove PB. The control unit 16 may instruct the servo circuit 13 to rotate the spindle motor 11 in the direction opposite to the time of recording on the recording surface.

  When a visible image is formed on the image recording layer while moving the laser light irradiation position along the pregroove PB formed on the recording surface as described above, the irradiation start position of the laser light is set on the pregroove PB. If the outermost position PBE is used, the laser light irradiation position can be moved along the pregroove PB even if the rotation direction of the optical disk D is the same as that during recording.

(Modification 9)
In the above-described embodiment, the control unit 16 irradiates a predetermined prohibited area KA in the image recording layer of the optical disc D shown in FIG. 30 with laser light (light level laser light) for image formation. You may make it control not to perform. As shown in the figure, when the laser beam irradiation position is moved clockwise from the above-described reference position (see FIG. 15), the prohibition area KA has a predetermined angle θ in the counterclockwise direction from the reference position. This is a fan-shaped area. That is, by rotating the optical disk D, when laser light irradiation for forming a visible image is performed while moving the laser light irradiation position from the reference position, the laser beam immediately before the laser light irradiation position returns to the reference position. A region through which the light irradiation position passes is a prohibited region KA.

  As control for prohibiting the formation of a visible image in such a prohibited area KA, the control unit 16 changes the gradation level of coordinates belonging to the prohibited area KA in the image data supplied from the host PC 110 to “0”. It is sufficient to perform data conversion such as. If such data conversion is performed, even if the drive pulse generation unit 35 faithfully generates a drive pulse according to the data, when the laser beam irradiation position passes through the prohibited area KA, the light level laser beam is not irradiated, As a result, no visible image is formed in the prohibited area KA.

  As described above, the following effects can be obtained by not irradiating the prohibited area KA with the laser beam for forming the visible image. That is, even when image formation is performed in synchronization with the clock signal supplied from the PLL circuit 33 as described above, the rotational speed during the rotation of the spindle motor 11 slightly fluctuates slightly. The period of the clock signal output from 33 may fluctuate. Due to the fluctuation of the clock signal which is a synchronizing signal for image formation in this way, as shown in FIG. 30, the laser beam irradiation is substantially performed after the laser beam for visible image formation is started from the reference position KK. The position trajectory (indicated by the alternate long and short dash line in the figure) rotates once, and the laser beam irradiated to express the image of the position KC immediately before the reference position is irradiated to the position KT that has passed the reference position. Can happen. That is, the laser beam that is originally irradiated to represent the image at the position KC immediately before the reference position is irradiated to the position KT in the region that has already been irradiated with the laser beam for forming a visible image. Laser light irradiation is performed, and as a result, a defect may occur in the formed visible image. Therefore, even when the clock signal generated by the PLL circuit 33 fluctuates, the image data is converted so that the forbidden area KA as described above is set, so that the visible image is formed twice at the same position. Therefore, it is possible to prevent a problem such as irradiation with a laser beam.

(Modification 10)
Further, instead of the optical disc recording apparatus 100 according to the above-described embodiment, an optical disc recording apparatus 100 ′ having a configuration as shown in FIG. 30 may be used. As shown in the figure, the difference between this optical disk recording apparatus 100 ′ and the optical disk recording apparatus 100 in the above embodiment is that it does not have the FIFO memory 34 and the drive pulse generation unit 35, and is replaced with an encoder 17. The encoder 320 is provided.

  The encoder 320 is a circuit that performs EFM modulation, CIRC (Cross Interleaved Reed-Solomon Code) conversion, and the like on the supplied data, like the encoder 17 shown in FIG. 2, and temporarily stores the supplied data in the memory. The accumulated data is subjected to the modulation processing as described above and output to the strategy circuit 18 ′. In addition, the encoder 320 performs processing such as EFM modulation on the data supplied from the buffer memory 36 based on the modulation on / off signal supplied from the control unit 16, or outputs the processed data or performs EFM modulation or the like. It is configured to be able to switch whether to output data without using it. When a signal indicating modulation on is supplied from the control unit 16, the encoder 320 performs EFM modulation or the like on the data supplied from the buffer memory 36 and outputs the data to the strategy circuit 18. On the other hand, when the modulation off signal is supplied from the control unit 16, the encoder 320 does not modulate the data supplied from the buffer memory 36, and the data is synchronized with the clock signal supplied from the PLL circuit 33. Output.

  The control unit 16 outputs a modulation on / off signal to the encoder 320 in accordance with an instruction from a user input via a user interface (not shown) or the like. More specifically, when receiving an instruction from the user to form a visible image on the image recording layer, an instruction to output information on the recording surface is output from the user by outputting a modulation off signal. When the signal is received, a modulation on signal is output. As described above, the control unit 16 may output the modulation on / off signal in accordance with an instruction from the user. However, depending on which surface of the optical disc D is set to face the optical pickup 10 Thus, a modulation on / off signal may be output. In this case, when the optical disc D is set so that the image recording layer faces the optical pickup 10, a modulation off signal is output, and when the recording surface is set on the optical disc D so that the recording surface faces the optical pickup 10, the modulation on signal is output. May be output.

  Under the above configuration, when the user instructs to record information on the recording surface, the control unit 16 outputs a modulation ON signal to the encoder 320. Then, recording data to be recorded on the recording surface of the optical disc D is supplied from the host PC 110 to the buffer memory 36 and transferred from the buffer memory 36 to the encoder 320. Upon receiving the modulation ON signal, the encoder 320 performs EFM modulation or the like on the recording data supplied from the buffer memory 36 and outputs it to the strategy circuit 18. The strategy circuit 18 ′ corrects the time axis of the EFM-modulated data, generates a drive pulse for driving the laser driver 19, and outputs it to the laser driver 19. In response to the drive pulse, the laser driver 19 supplies a drive current to the laser diode 53 (see FIG. 2) of the optical pickup 10 to irradiate the optical pickup 10 with laser light, and the recording surface of the optical disc D is subjected to the host. Recording of recording data supplied from the PC 110 is performed.

  On the other hand, when the user instructs the image recording layer to form a visible image, the control unit 16 outputs a modulation off signal to the encoder 320. Then, image data corresponding to a visible image to be formed on the image recording layer of the optical disc D is supplied from the host PC 110 to the buffer memory 36 and transferred from the buffer memory 36 to a memory built in the encoder 320. Receiving the modulation off signal, the encoder 320 does not perform processing such as modulation on the image data transferred from the buffer memory 36, and synchronizes with the clock signal supplied from the PLL circuit 33. Information indicating the degree of gradation) is sequentially output to the strategy circuit 18. The strategy circuit 18 ′ generates a drive pulse based on the data indicating the gradation for each coordinate that is sequentially supplied, like the drive pulse generator 35 in the above-described embodiment, and the generated drive pulse is transmitted to the laser driver 19. Output to. In response to this drive pulse, the laser driver 19 supplies a drive current to the laser diode 53 (see FIG. 2) of the optical pickup 10 to irradiate the optical pickup 10 with laser light, Visible image formation corresponding to the image data supplied from the host PC 110 is performed.

  As described above, by making it possible to switch whether or not the encoder 320 performs modulation between the case where a visible image is formed and the case where information is recorded, a FIFO memory used only for visible image formation. 34 and the drive pulse generator 35 can be omitted, and the optical disc recording apparatus 100 ′ can have a visible image forming function and an information recording function while having a simpler configuration.

(Modification 11)
Data (image data) to be recorded for forming a visible image may be stored in advance in a memory (not shown) of the optical disc recording apparatus 100. For example, data to be recorded in order to form numbers 0 to 9 as visible images on the optical disk D is prepared in a memory. Then, when the user designates a number to be formed on the optical disc D, recording data relating to the designated number may be read from the memory and recorded on the optical disc D to form a visible image. In addition, the original data is recorded from the inner periphery to the outer periphery of the disc, and after the data recording is completed, the time stamp information related to the date and time of recording is automatically formed as a visible image without the user's instruction. It may be. The time stamp information may be supplied from the external device (host PC 110) to the optical disc recording device 100. In addition, after the original data recording is finished, signature information indicating the user name and the content of the recorded data may be formed as a visible image. The signature information may be supplied to the optical disc recording apparatus 100 by the user operating the host PC 110. Alternatively, the user may directly input (register) signature information by operating the optical disc recording apparatus 100.

  Next, recording of information (digital information) on the information recording layer will be described. When the information recording layer is a dye type, first, laser light is irradiated from a laser pickup while rotating the above-mentioned unrecorded optical disk at a predetermined recording linear velocity. By this irradiation light, the dye of the information recording layer absorbs the light and the temperature rises locally, and a desired pit is generated and its optical characteristics are changed to record information.

  The recording waveform of the laser beam may be a pulse train or one pulse when one pit is formed. The ratio to the actual recording length (pit length) is important.

  The pulse width of the laser beam is preferably in the range of 20 to 95%, more preferably in the range of 30 to 90%, and still more preferably in the range of 35 to 85% with respect to the length to be actually recorded. Here, when the recording waveform is a pulse train, the sum is in the above range.

The power of the laser light varies depending on the recording linear velocity, but when the recording linear velocity is 3.5 m / s, the range of 1 to 100 mW is preferable, the range of 3 to 50 mW is more preferable, and the range of 5 to 45 mW is further increased. preferable. Further, when the recording linear velocity is doubled, the preferable range of the laser beam power is ^21/2 times or slightly larger than that, respectively.

  In order to increase the recording density, the NA of the objective lens used for the pickup is preferably 0.55 or more, and more preferably 0.60 or more.

  In the present embodiment, a semiconductor laser having an oscillation wavelength in the range of 350 to 850 nm can be used as the recording light.

  On the other hand, the case where the information recording layer is a phase change type will be described. In the case of the phase change type, it is made of the above-described material, and the phase change between the crystalline phase and the amorphous phase can be repeated by laser light irradiation.

  At the time of information recording, a concentrated laser light pulse is irradiated for a short time to partially melt the phase change recording layer. The melted portion is rapidly cooled by heat diffusion and solidified to form an amorphous recording mark. When erasing, the recording mark portion is irradiated with laser light, heated to a temperature below the melting point of the information recording layer and above the crystallization temperature, and cooled to crystallize the recording mark in an amorphous state. Return to the unrecorded state.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to a following example.

[Example 1]
The present embodiment is a DVD-R type optical disc formed by bonding two discs. A method for producing the optical disc will be described below.

  A substrate having a thickness of 0.6 mm and a diameter of 120 mm having spiral grooves (depth: 130 nm, width: 300 nm, track pitch: 0.74 μm) was molded from polycarbonate resin by injection molding. A coating solution (1) is prepared by dissolving 1.4 g of the following dye (1) in 100 ml of 2,2,3,3-tetrafluoro-1-propanol, and the coating solution (1) is prepared by spin coating. The information recording layer was formed by coating on the surface on which the groove was formed. Next, silver is sputtered on the information recording layer to form a reflective layer having a thickness of 120 nm, and then an ultraviolet curable resin (SD318 (manufactured by Dainippon Ink and Chemicals)) is applied by a spin coating method, and then ultraviolet rays are applied. Was applied to form a protective layer having a layer thickness of 10 μm, and the first disk was manufactured through the above steps.

  Next, in order to form an image recording layer, 0.9 g of the following dye A (cyanine dye) and 2.1 g of the following dye B (phthalocyanine dye) (mixing ratio (mass ratio) 30:70), 2, 2, A coating solution (2) dissolved in 100 ml of 3,3-tetrafluoro-1-propanol was prepared, and this coating solution (2) was formed on a substrate without grooves by spin coating. Next, silver is sputtered onto the image recording layer to form a reflective layer having a thickness of 120 nm, and then an ultraviolet curable resin (SD318 (manufactured by Dainippon Ink and Chemicals)) is applied by a spin coating method, and then ultraviolet rays are applied. The second disk was manufactured by the above process, and the optical density (OD: Optical Density) serving as an index of the thickness of the image recording layer was formed. Was 0.36.

  Next, the following steps were performed in order to bond the first disk and the second disk to complete one disk. First, a slow-acting cationic polymerization adhesive (Sony Chemical Co., Ltd., SDK7000) was printed on the protective layers of both disks by screen printing. At this time, the mesh size of the screen printing plate was 300 mesh. Next, immediately after irradiating with ultraviolet rays using a metal halide lamp, the first disk and the second disk were bonded from the respective protective layer sides, pressed from both sides, and allowed to stand for 5 minutes to produce the optical disk of Example 1. . The optical disk of Example 1 satisfied the above formula (M1). The reflectance spectrum before and after image recording in Example 1 is shown in FIG.

[Example 2]
The dye used for forming the image recording layer of Example 1 was changed to one obtained by mixing the dye A (cyanine dye) and the dye B (phthalocyanine dye) at a mixing ratio (mass ratio) of 30:70. The optical disc of Example 2 was produced in the same manner as in Example 1 except that the optical density (OD: Optical Density), which is an index of the thickness of the image recording layer, was 0.40. The optical disk of Example 2 satisfied the above formula (M1). The reflectance spectrum before and after image recording in Example 2 is shown in FIG.

[Example 3]
The dye used for forming the image recording layer of Example 1 was changed to a mixture of the following dye C (oxonol dye) and the following dye D (oxonol dye) at a mixing ratio (mass ratio) of 70:30. An optical disk was manufactured in the same manner as in Example 1 except for the above. The optical disk of Example 3 satisfied the formula (M1).

[Example 4]
The dye used for forming the image recording layer of Example 1 was changed to one in which the dye C (oxonol dye) and the dye D (oxonol dye) were mixed at a mixing ratio (mass ratio) of 30:70. An optical disk was manufactured in the same manner as in Example 1 except for the above. The optical disk of Example 4 satisfied the formula (M1).

[Example 5]
The dye used for forming the image recording layer of Example 1 was changed to one in which the dye C (oxonol dye) and the dye D (oxonol dye) were mixed at a mixing ratio (mass ratio) of 50:50. An optical disk was manufactured in the same manner as in Example 1 except for the above. The optical disk of Example 5 satisfied the formula (M1).

[Example 6]
The dye used for forming the image recording layer of Example 1 was changed to one obtained by mixing the following dye E (oxonol dye) and the dye D (oxonol dye) at a mixing ratio (mass ratio) of 50:50. An optical disk was manufactured in the same manner as in Example 1 except that. The optical disk of Example 6 satisfied the above formula (M1).

[Example 7]
The dye used for forming the image recording layer of Example 1 was changed to one obtained by mixing the following dye F (oxonol dye) and the dye D (oxonol dye) at a mixing ratio (mass ratio) of 50:50. An optical disk was manufactured in the same manner as in Example 1 except that. The optical disk of Example 7 satisfied the above formula (M1).

[Example 8]
The dye used for forming the image recording layer of Example 1 was changed to one obtained by mixing the following dye G (oxonol dye) and the dye D (oxonol dye) at a mixing ratio (mass ratio) of 50:50. An optical disk was manufactured in the same manner as in Example 1 except that. The optical disk of Example 8 satisfied the formula (M1).

[Comparative Example 1]
In the production of the second disk of Example 1, Comparative Example 1 was the same as Example 1 except that the dye A and the dye B in the coating liquid (2) were changed to 0.9 g of the dye (4) having the following structure. An optical disc was produced.

[Evaluation]
The absorbance of the manufactured optical disk of the example was measured. The measurement results are shown graphically in FIG. As shown in the graph, the optical disc of the example showed sufficient contrast and sufficient visibility.

  For contrast, Sv represented by the following formula (M2) was used as an evaluation index of contrast after drawing.

  Furthermore, five levels of evaluation criteria were provided based on the value of Sv determined by the formula (M2). The evaluation criteria are as shown in Table 5 below. In all of Examples 1 to 8, the evaluation was “3” or more.

  Note that the optical disc according to the present invention is not limited to the above-described embodiment, and various configurations can be adopted without departing from the gist of the present invention.

It is a block diagram which shows the structure of an example of the optical disk recording device which can handle the optical disk which concerns on this Embodiment. It is a figure which shows the structure of the optical pick-up which is a component of an optical disk recording device. It is a figure for demonstrating the content of the image data used in order to form a visible image with respect to the image recording layer of the optical disk by an optical disk recording device. It is a figure for demonstrating the irradiation control content of the laser beam for expressing the contrast of an image, when an optical disk recording device forms a visible image with respect to the image recording layer of the optical disk which concerns on this Embodiment. It is a figure for demonstrating the control method of the laser beam when an optical disk recording device forms a visible image with respect to the image recording layer of an optical disk. It is a figure for demonstrating the laser power control content by the laser power control circuit which is a component of an optical disk recording device. It is a figure which shows the return light of the laser beam irradiated to the image recording layer of the optical disk from the optical pick-up of an optical disk recording device. It is a figure which shows the FG pulse produced | generated according to the rotation amount of a spindle motor by the frequency generator 21 which is a component of an optical disk recording device, and the clock signal produced | generated based on the said FG pulse. 5 is a flowchart (part 1) for explaining the operation of the optical disc recording apparatus. 12 is a flowchart (part 2) for explaining the operation of the optical disc recording apparatus. It is a figure which shows disc ID recorded on the image recording layer of the optical disk. It is a figure which shows the shape of the return light of the laser beam received by the light receiving element of the optical pick-up of an optical disk recording device. It is a figure for demonstrating the size of the beam spot diameter of the laser beam which the optical pick-up of an optical disk recording device irradiates to the image recording layer of an optical disk. It is a figure for demonstrating the method to detect that the laser beam irradiation position of an optical disk recording device passed the reference | standard position of the optical disk. It is a figure for demonstrating the method to detect that the laser beam irradiation position of an optical disk recording device passed the reference | standard position of the optical disk. 6 is a timing chart for explaining the operation of the optical disk recording apparatus when a visible image is formed by irradiating an image recording layer of the optical disk with laser light. It is a figure which shows the image recording layer of the optical disk irradiated with the laser beam by the optical disk recording device. It is a figure for demonstrating the method of expressing the contrast of the visible image formed in the image recording layer of an optical disk with an optical disk recording device. It is a figure for demonstrating the method of expressing the contrast of the visible image formed in the image recording layer of an optical disk with an optical disk recording device. It is a figure for demonstrating the method of expressing the contrast of the visible image formed in the image recording layer of an optical disk with an optical disk recording device. It is a figure for demonstrating the method of expressing the contrast of the visible image formed in the image recording layer of an optical disk with an optical disk recording device. It is a figure for demonstrating the method of expressing the contrast of the visible image formed in the image recording layer of an optical disk with an optical disk recording device. It is a figure for demonstrating the method to move the irradiation position of a laser beam to the radial direction of an optical disk, when forming a visible image in the image recording layer of an optical disk with an optical disk recording device. It is a figure for demonstrating the laser power control content implemented by the optical disk recording device. The optical disc and optical pickup when the optical disc is set in the optical disc recording apparatus so that the image recording layer faces the optical pickup and when the optical disc is set so that the surface opposite to the image recording layer faces the optical pickup. It is a figure which shows these positional relationships. It is an external view which shows the adapter for adjusting the positional relationship of an optical disk and an optical pick-up. It is a figure which shows schematic structure of the optical disk recording device provided with the function to adjust the positional relationship of an optical disk and an optical pick-up. It is a figure for demonstrating the method for enlarging the beam spot diameter of the laser beam irradiated to the image recording layer of an optical disk. It is a figure for demonstrating the method to perform visible image formation by moving the irradiation position of a laser beam along the pregroove on the recording surface formed in the surface on the opposite side to the image recording layer of an optical disk. It is a figure for demonstrating the prohibition area | region of the optical disk for which the laser beam irradiation for visible image formation by an optical disk recording device is prohibited. It is a block diagram which shows the structure of the modification of an optical disk recording device. It is a figure which shows the reflectance spectrum in Example 1 before and behind image recording with a graph. It is a figure which shows the reflectance spectrum in Example 2 before and behind image recording with a graph. It is a figure which shows the light absorbency change with respect to the wavelength of the image recording layer of the optical disk of an Example by a graph.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Optical pick-up 11 ... Spindle motor (rotation drive means) 12 ... RF amplifier 13 ... Servo circuit 16 ... Control part 17 ... Encoder 18 ... Strategy circuit 19 ... Laser driver 20 ... Laser power control circuit 21 ... Frequency generator 30 ... Stepping Motor 31 ... Motor driver 32 ... Motor controller 33 ... PLL circuit 34 ... FIFO memory 35 ... Drive pulse generator 36 ... Buffer memory 53 ... Laser diode 53a ... Front monitor diode 56 ... Light receiving element 64 ... Focus actuator 65 ... Tracking actuator 100 ... Optical disk recording device 270 ... Chucking portion 271 ... Adapter 280 ... Drive mechanism 320 ... Encoder D ... Optical disk

Claims (5)

An optical disc comprising a laminate having, in this order, at least an image recording layer capable of recording a visible image by irradiation with laser light on a substrate,
When the reflectance is measured from the substrate side, the integrated value A of the reflectance in the region of the image recording layer having a wavelength of 500 to 600 nm before recording the visible image on the image recording layer, and the visible image are recorded. An optical disc in which the integrated value B of the reflectance in the region of the wavelength of 500 to 600 nm of the image recording layer after satisfying the relationship of the following formula (M1):
A <B Formula (M1) The optical disc according to claim 1,
An optical disc comprising the laminate and another laminate having at least an information recording layer and a reflective layer in this order on another substrate. The optical disk according to claim 1 or 2,
The optical disc, wherein the image recording layer contains a dye compound. The optical disk according to claim 3, wherein
An optical disc, wherein the image recording layer is formed using a coating liquid containing a dye compound. In the optical disc according to any one of claims 1 to 4,
An optical disc, wherein the substrate on which the image recording layer is formed is a substrate having no groove.

Images