JP2007176156A - Optical information recording medium, method for visible information recording, method for use of mixture and mixture - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical information recording medium capable of forming a label through the use of a laser beam and having a visible information recording layer superior in light fastness and heat fastness for visible information. <P>SOLUTION: The optical information recording medium 10 can record information by irradiation with laser beams 38 and is provided with the visible information recording layer 24 on which visible information is recorded. The visible information recording layer 24 contains a coloring matter and at least one metal atom selected from the group consisting of Na, Mg, K and Ca. The coloring matter is at least one material selected from the group consisting of oxonol coloring matter, cyanine coloring matter, azo coloring matter, phthalocyanine coloring matter and pyromethane coloring matter. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an optical information recording medium, and in particular, an optical information recording medium having a visible information recording layer capable of recording visible information, a visible information recording method for recording visible information on the optical information recording medium, and the visible information The present invention relates to a method of using a mixture in a recording layer and the mixture.

  Conventionally, an optical information recording medium (optical disc) capable of recording information only once by laser light is known. As this optical disc, there are a write-once type CD (so-called CD-R) and a write-once type digital vasatile disc (so-called DVD-R).

  By the way, on an optical disk, visible information (images) such as a title of music data recorded on the recording surface and a title for identifying the recorded data is provided on a surface opposite to the recording surface on which music data is recorded. ) 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.

  On the other hand, apart from the system for attaching the label sheet, a system for forming a label by irradiating an optical disk with laser light has been studied (see, for example, Patent Document 1).

  Further, it has been proposed to form a visible information recording layer on an optical disc and use a dye as a material for the visible information recording layer (see, for example, Patent Documents 2 to 4).

JP-A-11-66617 JP 2000-113516 A JP 2001-283464 A JP 2000-173096 A

  However, the above-mentioned optical disk on which a visible information recording layer using a dye has been conventionally used has a problem that light fastness or heat fastness after label formation is insufficient.

  The present invention has been made in view of the above-described conventional problems, and includes a visible information recording layer that can form a label using laser light and has excellent light fastness or heat fastness of visible information. It is an object of the present invention to provide an optical information recording medium, a method of using the mixture, and a mixture.

  Another object of the present invention is to provide a visible information recording method capable of minimizing the hardware resources of a recording device and allowing a general user to easily record visible information using these recording devices. Is to provide.

  An optical information recording medium according to a first aspect of the present invention is an optical information recording medium capable of recording information by irradiating a laser beam, and has a visible information recording layer on which visible information is recorded, and the visible information The recording layer contains a dye and at least one metal atom selected from the group consisting of Na, Mg, K and Ca.

  When the visible information recording layer contains at least one metal atom selected from the group consisting of Na, Mg, K and Ca, the light fastness or heat fastness of visible information is excellent. The reason why such an effect is obtained is not clear, but the present inventors speculate as follows.

  That is, in the visible information recording layer after recording, the dye density is different between the visible information recording area and the visible information non-recording area. In the visible information non-recorded area, the density of the dye is low, and when exposed to a long time exposure, deterioration easily occurs from the interface between the visible information recorded area and the visible information unrecorded area. Then, it is thought that the deterioration is suppressed and the light fastness or heat fastness is improved by containing the metal atom.

  Thus, in the first aspect of the present invention, there is provided an optical information recording medium comprising a visible information recording layer which can form a label using laser light and has excellent light fastness or heat fastness of visible information. Can be provided.

  In the first aspect of the present invention, the dye may be at least one selected from the group consisting of an oxonol dye, a cyanine dye, an azo dye, a phthalocyanine dye, and a pyromethene dye.

  In the first aspect of the present invention, the metal atom is preferably contained in a ratio of 0.1 to 100 g, more preferably 1 to 50 g, and more preferably 1 to 10 g with respect to 1 kg of the dye. If it exceeds the upper limit, it will crystallize in the visible information recording layer, making it difficult to record good visible information. If it is less than the lower limit, light fastness or heat fastness will be insufficient. The lower limit is more preferably 0.5 g, and the upper limit at this time is preferably 50 g, more preferably 10 g.

  Furthermore, from the viewpoint of the content of the metal atom, the visible information recording layer preferably contains the metal atom in a range of 0.001 to 1% by weight, and the lower limit is 0.001% by weight. More preferred.

  In the present specification, the upper limit value and the lower limit value are described in any of the above criteria, but the content of the metal atom is not particularly limited as long as the effect of the present invention is obtained. .

  In the first aspect of the present invention, a phthalocyanine dye whose central metal is Cu and a trimethine cyanine dye may be contained as the dye.

  In this case, it is preferable that the metal atoms are contained at a ratio of 0.1 to 10 g, preferably 1 to 5 g, with respect to 50 g of Cu as the central metal.

  In the first aspect of the present invention, the first substrate, the recording layer formed on the first substrate, the first reflective layer formed on the recording layer, and the first reflective layer are formed. An adhesive layer; a second reflective layer formed on the adhesive layer; the visible information recording layer formed on the second reflective layer; a second substrate formed on the visible information recording layer; You may make it have.

  In the first aspect of the present invention, the dye may be an oxonol dye having a structure represented by the following general formula (1-1).

Here, in the general formula (1-1), Za ²⁵ and Za ²⁶ are each independently an atomic group forming an acidic nucleus, and Ma ²⁷ , Ma ²⁸ and Ma ²⁹ are each independently substituted or non-substituted. Substituted 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 ^{23 s} , a plurality of Ma ²⁷ and Ma ²⁸ may be the same or different. A dye having a structure in which the dye represented by the general formula (1-1) is bonded with a linking group is also preferable.

  In the first aspect of the present invention, the dye may be an oxonol dye having a structure represented by the following general formula (1-2).

Here, in the general formula (1-2), Za ²¹ , Za ²² , Za ²³ , and Za ²⁴ each independently represent an atomic group that forms an acidic nucleus, and Ma ²¹ , Ma ²² , Ma ²³ , Ma ²⁴ , Ma ²⁵ and Ma ²⁶ each independently represents a substituted or unsubstituted methine group. L represents a divalent linking group that does not form a π-conjugated system with two bonds. Ka ²¹ and Ka ²² each independently represents an integer of 0 to 3. Q represents a monovalent cation that neutralizes the charge. Or 2Q represents a divalent cation. 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.

  In the first aspect of the present invention, the dye may be a cyanine dye represented by the general formula (2-1).

Here, in the general formula (2-1), 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 charge, and y2 represents a number necessary for neutralizing the charge.

  In the first aspect of the present invention, the dye may be a cyanine dye represented by the following general formula (2-2).

Here, in the general formula (2-2), 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 charge, and y3 represents a number necessary for neutralizing the charge.

  In the first aspect of the present invention, the dye may be an azo dye represented by the following general formula (3-1).

        A−N = N−B (3−1)

  Here, in the general formula (3-1), A represents a monovalent group derived from a coupler component, and B represents a monovalent group derived from a diazonium salt.

  In the first aspect of the present invention, the dye may be an azo dye represented by the following general formula (3-2).

Here, in general formula (3-2), A ¹ and B ² each independently represent an atomic group that forms a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aromatic heterocycle. . G represents a monovalent group having the ability to coordinate to a metal ion.

  In the first aspect of the present invention, the dye may be a phthalocyanine dye represented by the following general formula (4-1).

Here, in the general formula (4-1), Rα ^{1 to} Rα ⁸ and Rβ ^{1 to} Rβ ⁸ are each independently a hydrogen atom, halogen atom, cyano group, nitro group, formyl group, carboxyl group, sulfo group, carbon An alkyl group having 1 to 20 atoms, an aryl group having 6 to 14 carbon atoms, an aralkyl group having 7 to 15 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, an acyl group having 2 to 21 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, and a carbamoyl group having 1 to 25 carbon atoms Sulfamoyl group having 0 to 32 carbon atoms, alkoxycarbonyl group having 2 to 21 carbon atoms, aryloxycarbonyl group having 7 to 15 carbon atoms, acylamino having 2 to 21 carbon atoms , Sulfonylamino group having 1 to 20 carbon atoms, 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 first aspect of the present invention, the dye may be a pyromethene dye represented by the general formula (5-1).

  Here, in the general formula (5-1), A is a chelate ring formed of a pyromethene compound represented by the following general formula (5-2) and a metal M, and B is a nitrogen atom, an oxygen atom, and And / or a chelate ring formed with M having a sulfur atom. A and B may be the same or different.

  Here, in the general formula (5-2), Ya represents N or CRa3. Ra1, Ra2, Ra3, Ra4, Ra5, Ra6, Ra7 each represents a hydrogen atom or a substituent, and Ra1 and Ra2, Ra2 and Ra3, Ra5 and Ra6, and Ra6 and Ra7 form an aromatic ring or a heterocycle, respectively. The ring may have a substituent, and an aromatic ring or a hetero ring may be condensed to the ring.

  Next, a visible information recording method according to a second aspect of the present invention is a visible information recording method on the visible information recording layer of the above-described optical information recording medium according to the first aspect of the present invention. The same laser light as that used for recording on the recording layer is used for recording visible information.

  As a result, the hardware resources of the recording device can be minimized, and a general user can easily record visible information using these recording devices.

  Next, the third method of using the mixture according to the present invention is used for an optical information recording medium that can record information by irradiating laser light and has a visible information recording layer on which visible information is recorded. , A dye and a mixture of at least one metal atom selected from the group consisting of Na, Mg, K and Ca are used for the visible information recording layer of the optical information recording medium.

  Thereby, a label can be formed using a laser beam, and an optical information recording medium provided with a visible information recording layer excellent in light fastness or heat fastness of visible information can be provided.

  Next, the mixture according to the fourth aspect of the present invention is the visible information recording layer of the optical information recording medium which can record information by irradiating laser light and has a visible information recording layer on which visible information is recorded. And a mixture of at least one metal atom selected from the group consisting of a dye and Na, Mg, K and Ca.

  Thereby, a label can be formed using a laser beam, and an optical information recording medium provided with a visible information recording layer excellent in light fastness or heat fastness of visible information can be provided.

  As described above, according to the optical information recording medium, the method of using the mixture, and the mixture according to the present invention, the visible information recording layer provided separately from the recording layer uses laser light and is light and heat fast. Visible information with excellent properties can be recorded, and visible information with high contrast can be formed. That is, a label can be formed using a laser beam, and an optical information recording medium provided with a visible information recording layer excellent in light fastness or heat fastness of visible information can be provided.

  Further, according to the visible information recording method according to the present invention, the hardware resources of the recording device can be minimized, and the general user can easily record the visible information using these recording devices. .

  Embodiments of the optical information recording medium, visible information recording method, mixture utilization method, and mixture according to the present invention will be described below with reference to FIGS.

  The basic configuration of the optical information recording medium 10 according to the present embodiment includes a data recording medium unit 12 and a visible information recording medium unit 14 as shown in FIG. The data recording medium unit 12 includes a transparent first substrate 16, a data recording layer 18 formed on the first substrate 16, and a first reflective layer 20 formed on the data recording layer 18. . The visible information recording medium unit 14 includes a transparent second substrate 22, a visible information recording layer 24 formed on the second substrate 22, and a second reflective layer 26 formed on the visible information recording layer 24. And have. The data recording medium unit 12 and the visible information recording medium unit 14 are bonded via an adhesive layer 28 so that the first reflective layer 20 and the second reflective layer 26 face each other.

  The data recording layer 18 can record data (pit information) by, for example, laser light emitted from the first substrate 16 side.

  The visible information recording layer 24 can record visible information (images and characters) by laser light irradiated from the second substrate 22 side, for example.

  Further, in this optical information recording medium 10, a prepit area 30 is assigned to a part of the surface of the second substrate 22 (the surface on the side where the visible information recording layer 24 is formed), and one or more prepits are assigned to the prepit area 30. 32, preferably a plurality of prepits 32 are formed.

  As the information indicated by the combination of the prepits 32, various kinds of information regarding the optical information recording medium 10 can be considered. For example, whether the optical information recording medium 10 is the optical information recording medium 10 having the visible information recording layer 24 or not. This includes identification information, information relating to laser light output (for example, laser power) when drawing visible information on the visible information recording layer 24, information relating to the spot diameter, information relating to the gradation of visible information to be drawn, and the like. Therefore, by detecting the pre-pit 32, it is possible to easily detect whether the optical information recording medium 10 is the optical information recording medium 10 having the visible information recording layer 24, and the visible information recording layer 24 is visible. When drawing information, drawing can be performed with an optimum laser output (optimum laser power), and visible information can be recorded with high drawing characteristics. In addition, the information shown by the combination of the prepits 32 includes manufacturer information and the like.

  In the surface of the second substrate 22, the allocation position of the prepit area 30 is not particularly limited. For example, as shown in the optical information recording medium 10a according to the first modification of FIG. 2, the prepit area 30 may be located on the inner peripheral side of the drawing area 34 where the visible information recording layer 24 is formed. Since the pre-pit region 30 is on the inner peripheral side, the pre-pit 32 is not filled with the dye compound, so that there is an advantage that the return light from the pre-pit 32 can be easily detected. However, in order not to form the visible information recording layer 24 in the prepit area 30, a certain margin is required between the outermost periphery of the prepit area 30 and the innermost periphery of the drawing area 34.

  Of course, from the viewpoint of securing the drawing area 34 as wide as possible, the prepit area 30 and the drawing area 34 may partially overlap as shown in FIG. That is, at least a part of the visible information recording layer 24 may be formed on the prepit 32. In this case, since the formation position of the visible information recording layer 24 can be set relatively freely, the yield in the manufacturing process is improved.

  As shown in FIGS. 1 and 2, when the prepit region 30 is provided on the inner peripheral side of the second substrate 22, it is preferably provided within a radius of 21 to 24 mm from the center of the second substrate 22.

  The second substrate 22 having the pre-pits 32 as described above can be manufactured using a stamper described below. The stamper is provided with irregularities for forming the above-described pre-pit 32. It is preferable that the average height of the protrusions of the unevenness is 150 to 400 nm. By using the stamper, the above-described optical information recording medium 10 can be efficiently manufactured.

  As a process for manufacturing the stamper, a process substantially the same as that for manufacturing a stamper for manufacturing a normal CD-ROM can be employed. Specifically, a stamper can be manufactured by forming a photoresist film on a glass master, performing development, etc., sputtering a metal such as nickel, and performing electroforming.

  Note that a pregroove area in which a pregroove is formed instead of the prepit area 30 may be used. Alternatively, instead of the pre-pit area 30, a burst cutting area (BCA) in which a barcode pattern with unevenness is recorded may be used. In this case, identification information as to whether the optical information recording medium 10 is the optical information recording medium 10 having the visible information recording layer 24 or visible information is drawn on the visible information recording layer 24 by the pregroove or barcode pattern. It is possible to provide information on the output (for example, laser power) of the laser beam, information on the spot diameter, information on the gradation of visible information to be drawn, and the like.

  The configuration of the optical information recording medium 10 described above is not particularly limited as long as the configuration includes the visible information recording layer 24 capable of drawing visible information by laser light irradiation. That is, it can be any of a read-only type, a write-once type, a rewritable type, and the like. Of these, the write-once type is preferable. The recording format is not particularly limited, such as a phase change type, a magneto-optical type, and a dye type. Among these, a pigment type is preferable.

  In particular, the optical information recording medium 10 shown in FIG. 1 has a data recording layer 18 on a first substrate 16 and a visible information recording layer 24 on a second substrate 22, which are bonded together. Therefore, for example, it is preferable to apply to the configuration of DVD (including DVD-R, DVD-RW, HD DVD, etc. in addition to DVD).

  As the layer configuration of the optical information recording medium 10, in addition to the layer configuration shown in FIG.

  (1) As will be described later (see FIG. 5), the first layer structure is formed by sequentially forming the data recording layer 18, the first reflective layer 20, and the adhesive layer 28 on the first substrate 16. In addition, the second substrate 22 having the visible information recording layer 24 is bonded.

  (2) Although the second layer configuration is not shown, the data recording layer 18, the first reflective layer 20, the protective layer, and the adhesive layer 28 are sequentially formed on the first substrate 16, and the visible layer is visible on the adhesive layer 28. In this configuration, the second substrate 22 having the information recording layer 24 is bonded.

  (3) Although the third layer configuration is not shown, the data recording layer 18, the first reflective layer 20, the first protective layer, the adhesive layer 28, and the second protective layer are sequentially formed on the first substrate 16, The second substrate 22 having the visible information recording layer 24 is formed on the second protective layer.

  (4) Although the fourth layer configuration is not shown, the data recording layer 18, the first reflective layer 20, the first protective layer, the adhesive layer 28, the second protective layer, and the third protective layer are formed on the first substrate 16. Are sequentially formed, and the second substrate 22 having the visible information recording layer 24 is formed on the third protective layer.

  (5) In the fifth layer configuration, the data recording layer 18, the first reflective layer 20, the adhesive layer 28, and the second reflective layer 26 are sequentially formed on the first substrate 16, and on the second reflective layer 26. The second substrate 22 having the visible information recording layer 24 is formed. This layer structure is substantially the same as in FIG.

  (6) In the sixth layer configuration, the data recording layer 18, the first reflective layer 20, and the first protective layer are sequentially formed on the first substrate 16, while the visible information recording layer 24 is formed on the second substrate 22. The second reflective layer 26 and the second protective layer are sequentially formed, and the first protective layer and the second protective layer are bonded to each other with the adhesive layer 28 interposed therebetween.

  Note that the layer configuration shown in FIG. 1 and the layer configurations (1) to (6) described above are merely examples, and these layer configurations are not limited to the order described above, and may be partially replaced. A part (except the visible information recording layer 24) may be omitted. Furthermore, each layer may be composed of one layer or a plurality of layers.

  Further, as a modification of the optical information recording medium 10, the configurations of FIGS. 3 and 4 can be exemplified. In FIG. 4, the data recording layer 18 (see FIG. 1) is omitted.

  The optical information recording medium 10b according to the second modification shown in FIGS. 3 and 4 has substantially the same configuration as the optical information recording medium 10 described above, but is printed on the inner peripheral side of the main surface of the second substrate 22. The difference is that the region 36 is formed. Further, the prepit area 30 does not overlap the drawing area 34, and the drawing area 34, the prepit area 30, and the printing area 36 are arranged from the outer peripheral side to the inner peripheral side of the second substrate 22. Yes.

  For example, a cover sheet on which a barcode is printed or stamped is attached to the print region 36. The product name, manufacturer name, laser power, etc. can be recognized by the barcode printed or stamped on the cover sheet. By forming the printing area 36 on the innermost peripheral side of the second substrate 22, the innermost peripheral side of the optical information recording medium 10b is shielded, and the visual effect of the user can be enhanced.

  Next, a specific example having the basic configuration of the optical information recording medium 10 according to the present embodiment will be described with reference to FIGS. As shown in FIG. 5, the optical information recording medium 10 according to the present embodiment is an optical information recording medium 10 capable of recording information by irradiating a laser beam 12 and has visible information recorded thereon. A visible information recording layer 24 is provided. The visible information recording layer 24 contains a dye and at least one metal atom selected from the group consisting of Na, Mg, K and Ca.

  The dye may be at least one selected from the group consisting of an oxonol dye, a cyanine dye, an azo dye, a phthalocyanine dye, and a pyromethene dye. Moreover, it is preferable that a pigment | dye has a 0.05 or more light absorbency with respect to a laser beam. A pigment | dye may be used independently and may be used in combination of 2 or more type of pigment | dye.

  In the optical information recording medium 10 according to the present embodiment, the metal atoms are contained in a ratio of 0.1 to 100 g, more preferably 1 to 50 g, and more preferably 1 to 10 g with respect to 1 kg of the dye. preferable. If it exceeds the upper limit, it will crystallize in the visible information recording layer 24, making it difficult to record good visible information. If it is less than the lower limit, light fastness or heat fastness will be insufficient.

  Further, the optical information recording medium 10 according to the present embodiment may contain a phthalocyanine dye and a trimethine cyanine dye whose central metal is Cu as the dye. In this case, it is preferable that the metal atom is contained in a ratio of 0.1 to 10 g, preferably 1 to 5 g, with respect to 50 g of Cu as the central metal.

  Next, each layer, the first substrate 16 and the second substrate 22 will be described.

[Visible information recording layer 24]
As described above, the optical information recording medium 10 according to the present embodiment has the visible information recording layer 24 mainly composed of a dye, separately from the data recording layer 18 (preferably on the opposite side). Here, “having the dye as the main component” means that the dye content with respect to the total solid content in the visible information recording layer 24 is 50% or more (preferably 80% or more).

  The visible information recording layer 24 of the optical information recording medium 10 according to the present embodiment contains a dye and at least one metal atom selected from the group consisting of Na, Mg, K, and Ca.

  The metal atom is contained in a ratio of 0.1 to 100 g, preferably 1 to 50 g, more preferably 1 to 10 g with respect to 1 kg of the dye. If the upper limit is exceeded, it will crystallize in the visible information recording layer 24, making it difficult to record good visible information, and if it is less than the lower limit, light fastness or heat fastness will be insufficient.

  When a dye containing a phthalocyanine dye whose central metal is Cu and a trimethine cyanine dye is used as the dye, 0.1 to 10 g, preferably 50 g of Cu whose metal atom is the central metal, Is preferably contained in a ratio of 1 to 5 g.

  The visible information recording layer 24 records visible information (images and characters) desired by the user, such as characters, graphics, and patterns. Examples of visible information include a disc title, content information, content thumbnails, related patterns, design patterns, copyright information, recording date, recording method, recording format, and the like.

  The visible information recording layer 24 only needs to be able to record information such as characters, images, and patterns so as to be visible. In the present embodiment, the visible information recording layer 24 has a maximum absorption within a light wavelength range of 400 to 850 nm, and is used as a laser beam. It is preferable to use a dye having an absorbance of 0.05 or more (preferably 0.1 or more and 1.0 or less).

  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.

  A dye suitable for the wavelength of each recording laser beam 38 can be obtained, for example, by changing the length of the dye conjugated system. That is, when recording with a laser beam 38 of 750 to 850 nm, for example, a cyanine dye or a merocyanine dye preferably has a methine chain length of 5 to 7, and an oxonol dye has a methine chain length of 7 to 9 preferable.

  When recording with a laser beam 38 of 600 to 700 nm, for example, a cyanine dye or a merocyanine dye preferably has a methine chain length of 3 to 5, and an oxonol dye has a methine chain length of 5 to 7 preferable.

  Furthermore, in the case of recording with a laser beam 38 of 350 to 450 nm, an ultraviolet absorber or a near ultraviolet absorber can be used, but the above dye having a sub-absorption in the wavelength region of the laser beam 38 is preferably used. It is done. A cyanine dye having a methine chain length of 1 and an oxonol dye having a methine chain length of 1 are preferred.

  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 azo dyes; 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.

  In the case of a combination of pigments, the content ratio (mass ratio) between pigments is preferably 99: 1 to 1:99, more preferably 95: 5 to 30:70, and still more preferably 90:10 to 40:60.

  Here, the oxonol dye will be described. The oxonol dye is a compound represented by the following general formula (Formula-1), preferably a dye having a chain acidic nucleus or a cyclic acidic nucleus having a methine number of 5 to 7. In general formula (Formula-1), n is preferably an integer of 1 to 4. Rs can form a ring. More preferred is an oxonol dye represented by the general formula (1-1), more preferred is a dye represented by the general formula (1-2), and still more preferred is a general formula (formula-8) described later. It is a pigment | dye represented by these. In addition, dyes represented by the following general formulas (Chemical Formula-2), Chemical Formula-3, Chemical Formula-4, Chemical Formula-5, and Chemical Formula-6 are also used.

  The compound represented by the following general formula (Formula-2) includes examples of the compound represented by the general formula (Formula-8) described later.

In the general formula (Formula-2), 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 hetero group. R ²¹ , R ²² or R ³ represents any one of a cyclic group, 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 aryl Oxy 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 arylsulfonylamino group, substituted or unsubstituted carbamoyla It represents any of a mino group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, and a substituted or unsubstituted sulfamoyl group. . m represents an integer of 0 or more, and when m 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 (Formula-2) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocycle. Represents any of the groups. Examples of the substituted or unsubstituted alkyl group represented by R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ include alkyl groups having 1 to 20 carbon atoms. Further, when R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ each represent an alkyl group, they may be connected to each other to form a carbocyclic or heterocyclic ring. 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 an alkyl group having 1 to 5 carbon atoms. , R ¹¹ and R ^12, and R ¹³ and R ¹⁴ are bonded to each other to form a cyclic alkyl group having 1 to 8 carbon atoms and a substituted alkyl group having 1 to 20 carbon atoms.

Examples of the substituted or unsubstituted aryl group represented by R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ in the general formula (Formula-2) include aryl groups having 6 to 20 carbon atoms. 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 (Chemical Formula 2) is composed of a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom. It is a 6-membered saturated or unsaturated heterocyclic group. These may be benzo-fused. 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.

Substitution of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group represented by R ¹¹ , R ¹² , R ¹³ , R ¹⁴ in the general formula (Formula-2) Examples of the group include the substituent group S described later.

  Examples of the substituent represented by S include an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 20 carbon atoms. Aryloxy group, heterocyclic group, halogen atom, carboxyl group, alkoxycarbonyl group having 2 to 10 carbon atoms, cyano group, acyl group having 2 to 10 carbon atoms, carbamoyl having 1 to 10 carbon atoms, amino group, carbon number 1-20 substituted amino group, sulfo group, hydroxyl group, nitro group, alkylsulfonylamino group having 1 to 10 carbon atoms, carbamoylamino group having 1 to 10 carbon atoms, sulfonyl group having 1 to 10 carbon atoms, 1 carbon atom -10 sulfinyl groups and C 0-10 sulfamoyl groups are included. 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 (Formula-2) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, substituted or unsubstituted Substituted 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 Represents a group, 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 (Formula-2) 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 0 to 2. Is an integer.

In the general formula (Formula-2), 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 substituent.

In the general formula (Formula-2), 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, more preferably 4,4′-bipyridinium represented by the general formula (I-4) described in JP-A No. 2000-52658. Cation and 4,4′-bipyridinium cation disclosed in JP-A-2002-59652. In the general formula (Formula-2), x is preferably 1 or 2.

  In the case of an oxonol dye, the compound represented by the general formula (1-1) described above is preferable.

Next, the general formula (1-1) described above will be described in detail. In the general formula (1-1), 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 (1-2) described above, 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 each independently represent a substituted or unsubstituted methine group, and each of Ma ²¹ , Ma ²² , Ma ²³ , Ma ²⁴ , Ma ²⁵ , Ma ^{26 in} the general formula (1-2) It is synonymous, and a specific example and a preferable example 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 (1-2). 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 (1-1) described above is represented by the following general formulas (Chemical Formula-3), (Chemical Formula-4), (Chemical Formula-5), and (Chemical Formula-6). preferable.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ^{18 in the} general formulas (Chemical formula-3), (Chemical formula-4), (Chemical formula-5), (Chemical formula-6). , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ are each Independently, it is a hydrogen atom or a substituent. 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.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ^{18 in the} general formulas (Chemical formula-3), (Chemical formula-4), (Chemical formula-5), (Chemical formula-6). , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³² , R ³³ (the above may be indicated as “R”) are each independently a hydrogen atom Or, it represents a substituent. Substituents are halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heterocyclic groups, and cyano groups. , Hydroxyl group, nitro group, carboxyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted 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 aryloxycarbonyloxy, substituted or unsubstituted amino group, substituted or unsubstituted acylamino group, substituted or Unsubstituted aminocarboni Amino 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 Substituted 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 aryl A sulfinyl group, a substituted or unsubstituted alkyl and arylsulfonyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, Substituted or unsubstituted aryl and heterocyclic azo groups, substituted or unsubstituted imide groups, substituted or unsubstituted phosphino groups, substituted or unsubstituted phosphinyl groups, substituted or unsubstituted phosphinyloxy groups, substituted or unsubstituted Examples include a substituted phosphinylamino group or a substituted or unsubstituted silyl group.

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 the general formula (1-1) mentioned above, 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 (1-1) is preferably a dye having a structure represented by the following general formula (Formula-7).

  Here, the compound having a structure represented by the general formula (C-7) will be described in detail.

In the general formula (C-7), R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ are each independently a hydrogen atom or a substituent. Represents. 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 Is preferably a hydrogen atom. 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 An alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted acylamino group is represented. 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.

  Next, the dye having the structure represented by the general formula (1-2) will be described in detail.

In the general formula (1-2), Za ²¹ , Za ²² , Za ²³ , and Za ²⁴ are each independently an atomic group that forms an acidic nucleus, and examples thereof include the James edition, The Theory of the Photographic Process. , 4th edition, Macmillan, 1977, page 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 Nuclei such as carbocyclic rings (for example, hexane-1,3-dione, pentane-1,3-dione, indan-1,3-dione) and the like are preferable, and pyrazol-5-one, pyrazolidine-3,5 are preferable. -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 may each be substituted. In this case, 1,3-dioxane-4,6-dione is most preferred.

  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), acylamino groups having 1 to 20 carbon atoms (for example, acetylamino, benzoylamino), carbamoyl groups having 1 to 20 carbon atoms (for example, N, N- Dimethylcarbamoyl), sulfo group, hydroxy group, carboxy group, alkylthio group having 1 to 20 carbon atoms ( In example methylthio), cyano group, and the like. 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 (1-2) described above, Ka ²¹ and Ka ²² each independently represent an integer from 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. Among the quaternary ammonium ions, 4,4′- represented by the general formula (I-4) described in JP-A No. 2000-52658 is particularly preferable.
Bipyridinium cation and 4,4′-bipyridinium cation disclosed in JP-A No. 2002-59652. 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 (1-2) described above, the acidic nuclei formed by Za ²¹ , Za ²² , Za ²³ , Za ²⁴ are preferably each independently unsubstituted or substituted or unsubstituted having 1 to 20 carbon atoms. Pyrazol-5-one, pyrazolidine-3,5-dione, barbituric acid, 2-thiobarbituric acid substituted with an alkyl group or substituted or unsubstituted aryl group having 6 to 20 carbon atoms , 1,3-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 is either unsubstituted or a methine group substituted with an ethyl group, a methyl group, or a phenyl group, and L is 5 or 6 by combining two alkylene groups (preferably ethylene). Formed a member ring And a, Ka ^21, Ka ²² are both 2, and the cation is represented by 2Q, 4, 4 of the general formula described in JP 2000-52658 (I-4) ' This is the case of a bipyridinium cation and a 4,4′-bipyridinium cation disclosed in JP-A No. 2002-59652. Of the dyes represented by the general formula (1-2), dyes represented by the following general formula (Formula-8) are preferred.

In General Formula (Chemical Formula-8), R ¹ and R ² each independently represent 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.

The general formula (Formula-8) 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 each 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.

  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. 5,213,956 and 5,260,179 can be referred to. It is 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.

  Next, as a pigment | dye, the cyanine pigment | dye represented by the general formula (2-1) mentioned above may be sufficient.

Ma ²¹ , Ma ²² and Ma ^{23 in the} general formula (2-1) each independently represent a substituted or unsubstituted methine group. R ¹ and R ² each independently represent a substituent, but a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or A substituted or unsubstituted heterocyclic group is preferred. These groups may be further 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 from each other, but are preferably the same. 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.

  Q2 represents an ion for neutralizing the charge, and y2 represents a number necessary for neutralizing the 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.

  y2 represents a number necessary for charge neutralization. When Q2 is a divalent anion, if y2 is ½, the entire Q2y2 is considered as a monovalent anion.

  Next, as a pigment | dye, the pigment | dye represented by the general formula (2-2) mentioned above may be sufficient.

R ¹²¹ , R ¹²² and R ¹²³ in the general formula (2-2) are a hydrogen atom or a substituent. R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , and R ¹²⁷ are a hydrogen atom or a substituent, and the substituent is synonymous with the following R ^1a and R ^2a , and preferred examples are also the same. R ^1a and R ^2a have the same meanings as R ¹⁰¹ and R ¹⁰² in General Formula (2-1) described above, and preferred examples thereof are also the same. ka3 is synonymous with ka2 in the general formula (2-1), and preferred examples are also the same.

  Q3 represents an ion for neutralizing the charge, and y3 represents a number necessary for neutralizing the charge. 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. It is synonymous with y2 of general formula (2-1). 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 (2-1) or (2-2) used in the present embodiment, Ma ²¹ , Ma ²² , and Ma ²³ are preferably unsubstituted methine groups, and R ¹⁰¹ and R ¹⁰² are preferably each independently an unsubstituted alkyl group having 1 to 8 carbon atoms, and R ¹²⁴ , R ¹²⁵ , R ¹²⁶ and R ¹²⁷ are each independently a substituted or unsubstituted alkyl group. Preferably, Ka3 is preferably 1 or 2, Q3 is preferably an inorganic or organic anion, and y3 is preferably 1. Furthermore, what satisfies all the above preferred embodiments is most preferred.

  Specific examples of the cyanine compound having the structure represented by the general formula (2-1) used in this embodiment will be given. The present invention is not limited by this specific example.

  For general cyanine dyes, the cyanine dyes and related compounds (Cyanine Dyes and Related Compounds. John Wjley & Sons. It is described in.

  The cyanine dye according to the present embodiment (preferably the dye compound represented by the general formula (2-1)) has a complex refractive index coefficient n (real part: bendability) at the recording laser wavelength due to the optical characteristics of the amorphous film. Ratio) and 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.

  Next, an azo dye may be used as the dye. An azo dye is a dye synthesized by reacting an aryl or heteroaryl diazonium salt (diazo component) with a compound (coupler component) having an acidic hydrogen atom that forms an azo coupling reaction with the diazonium salt. It is. The azo dye used in the present embodiment is preferably a dye having a structure represented by the general formula (3-1) described above.

  Here, A is a residue of a compound (coupler component) having an acidic hydrogen atom that forms a dye by an azo coupling reaction with a diazonium salt, that is, a monovalent group derived from the coupler component. A is preferably a substituted or unsubstituted aryl group, a 5-membered carbon group having 1 to 20 carbon atoms containing a nitrogen atom, or a 6-membered heterocyclic group having 2 to 20 carbon atoms containing a nitrogen atom.

  The dye having the structure represented by the general formula (3-1) is preferably a dye represented by the general formula (3-2).

In the general formula of structure represented by (3-2) Dye, A ¹ together with the carbon atoms to which they are attached an aromatic hydrocarbon ring or represents an atomic group necessary for forming an aromatic hetero ring, formed by A ¹ Examples of the ring to be used include a substituted aromatic hydrocarbon ring (preferably a substituted benzene ring), a 5-membered carbon atom having 1 to 20 carbon atoms, or a 6-membered carbon atom having 2 to 20 carbon atoms. And an aromatic hydrocarbon ring having a substituent (preferably a substituted benzene ring) is more preferable.

Examples of structures formed by the substituent A or A ¹ are shown below.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² are each independently a hydrogen atom or a substituent.

  Among the above ring structures, preferred are the formulas (C-9), (C-10), and (C-11).

In the above general formula, R ¹¹ and R ¹³ are preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a cyano group, or a carbon number having 1 to 20 carbon atoms. A substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted aminocarbonyl group having 2 to 20 carbon atoms. R ¹⁴ is preferably a cyano group, a substituted or unsubstituted alkoxycarbonyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, or a substituted or unsubstituted group having 2 to 20 carbon atoms. Of the aminocarbonyl group. R ¹⁵ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aminocarbonylamino group having 1 to 20 carbon atoms.

Particularly preferably, R ¹³ is a cyano group, R ¹⁴ is an alkoxycarbonyl group having 1 to 20 carbon atoms, R ¹⁵ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. A substituted or unsubstituted aryl group.

B represents a monovalent group derived from a diazonium salt, preferably a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. That is, B is a diazo component. The diazo component is a partial structure that can be introduced by converting a heterocyclic compound having an amino group as a substituent or a benzene derivative into a diazo compound (diazonium salt) and diazo coupling reaction with a coupler. It is a frequently used concept in the field. In other words, it is an amino-substituted heterocyclic compound capable of diazotization reaction or a substituent that is a monovalent group by removing the amino group of the benzene derivative. B is preferably a ring formed by B ² . B ² represents an atomic group forming a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aromatic heterocycle. Examples of the ring formed by B ² include an aromatic hydrocarbon ring having a substituent (preferably a benzene ring having a substituent), a 5-membered member having 1 to 20 carbon atoms containing a nitrogen atom, or a 2-membered carbon atom containing a nitrogen atom. A 20-membered 6-membered heterocycle is preferable, a 5-membered carbon having 1 to 20 carbon atoms including a nitrogen atom or a 6-membered heterocycle having 2 to 20 carbon atoms including a nitrogen atom is more preferable. More preferred are 20 5-membered heterocycles.

  Examples of the monovalent heterocyclic group of A and B include the following (Chemical Formula-23) to (Chemical Formula-47).

In said general formula, R < ²¹ > -R < ⁵⁰ > is a hydrogen atom or a substituent each independently.

  b and c are integers from 0 to 6.

  a, p, q, r are integers from 0 to 4.

  d, e, f, g, t, and u are integers from 0 to 3.

  h, i, j, k, l, and o are integers from 0 to 2.

When a to u are 2 or more, two or more substituents represented by R ^{21 to} R ⁵⁰ may be the same or different.

  Among the structures of B, the following structures (Chemical-48) to (Chemical-60) are preferable.

In the above general formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ^{61 to} R ⁶⁶ , R ⁷¹ , R ⁷² are each independently a hydrogen atom or a substituent. Examples of the substituent are those described in the description of R ¹¹¹ .

  G in the general formula (3-2) represents a monovalent group having an ability to coordinate with a metal ion. Examples of G include hydroxyl group, carboxyl group, amino group (including alkylamino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or aryl Examples include sulfonylamino group, mercapto group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, carbamoyl group, aryl and heterocyclic azo group, phosphino group and phosphinyl group. G is preferably an alkylsulfonylamino group.

  The azo dye compound according to the present embodiment is also preferably an azo metal chelate dye coordinated with a metal ion. In particular, chelate dyes are superior in light resistance and are preferable. The metal ions used as the metal chelate dye are preferably Ni, Cu, Zn, Al, Ti, Fe, B, Cr, or Co. Among these, Ni, Co, and Al are more preferable.

  When taking a chelate structure, when a stable complex cannot be formed due to a shortage of ligands with respect to the central metal, a molecule other than the above-described dye of the general formula (3-1) is added as a ligand to stabilize the complex. It is also preferable to use a chelate dye. The ligand added separately is preferably a compound containing a nitrogen, oxygen, or sulfur atom. Among these, amine compounds (including aniline) and heterocyclic compounds containing at least one nitrogen atom are preferable. Most preferred are 5- or 6-membered amine compounds having 3 to 20 carbon atoms.

  As for the synthesis method of the azo dyes, JP-A-3-268994, JP-A-361088, JP-A-7-161069, JP-A-7-251567, JP-A-10-204070, JP-A-11-12483, JP-A-11-12483. 11-166125, JP-A-2001-199169, JP-A-2001-152040, and JP-A-2002-114922.

  The dye compound according to the present embodiment preferably has a complex refractive index coefficient n (real part: refractive index) and k (imaginary part: extinction coefficient) at the recording laser wavelength due to the optical characteristics of the amorphous film. 2.0 ≦ n ≦ 3.0 and 0.00 ≦ k ≦ 0.20. More preferably, 2.1 ≦ n ≦ 2.7 and 0.00 ≦ k ≦ 0.10. Most preferably, 2.15 ≦ n ≦ 2.50 and 0.00 ≦ k ≦ 0.05.

  The azo dye compound according to the present embodiment preferably has a thermal decomposition temperature in the range of 100 ° C to 350 ° C. 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.

  Next, a phthalocyanine dye may be used as the dye. The phthalocyanine dye is preferably represented by the general formula (4-1) described above.

In General Formula (4-1), 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 carbon atom. -20 alkyl group, aryl group having 6-14 carbon atoms, aralkyl group having 7-15 carbon atoms, heterocyclic group having 1-10 carbon atoms, alkoxy group having 1-20 carbon atoms, carbon atom number 6-14 aryloxy group, C2-C21 acyl group, C1-C20 alkylsulfonyl group, C6-C20 arylsulfonyl group, C1-C25 carbamoyl group, carbon atom A sulfamoyl group having 0 to 32 carbon atoms, an alkoxycarbonyl group having 2 to 21 carbon atoms, an aryloxycarbonyl group having 7 to 15 carbon atoms, an acylamino group having 2 to 21 carbon atoms, carbon Sulfonylamino group child 1-20, 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 (4-1), it is preferable that all of Rα ^{1 to} Rα ⁸ are not hydrogen atoms at the same time, and further ^one of Rα ¹ and Rα ² , one of Rα ³ and Rα ⁴ , Rα ⁵ And Rα ⁶ , Rα ⁷ and Rα ⁸ in total, it is preferable that the total four substituents are not hydrogen atoms at the same time. In particular, at this time, all of Rβ ^{1 to} Rβ ⁸ are simultaneously hydrogen atoms. Preferably there is.

In the general formula (4-1), 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 the number of carbon atoms. 6-10 aryl groups, alkoxy groups having 1 to 16 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, sulfonyl groups having 1 to 16 carbon atoms, sulfamoyl groups having 2 to 20 carbon atoms, carbon atoms Examples thereof include 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. As for things, a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a C1-C16 alkoxy group, a C6-C10 aryloxy group, carbon Alkylsulfonyl group having 1 to 14 children, arylsulfonyl group having 6 to 14 carbon atoms, sulfamoyl group having 2 to 16 carbon atoms, alkoxycarbonyl group having 2 to 13 carbon atoms, acylamino having 2 to 14 carbon atoms A sulfonylamino group having 1 to 14 carbon atoms, and more preferably, Rα ^{1 to} Rα ⁸ are a hydrogen atom, a halogen atom, a sulfo group, an alkoxy group having 8 to 16 carbon atoms, or a carbon atom having 1 to 12 carbon atoms. A sulfonyl group, a sulfamoyl group having 1 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a sulfonylamino group having 1 to 12 carbon atoms, and Rβ ^{1 to} Rβ ⁸ are a hydrogen atom or a halogen atom, preferably, at least one of Rα ¹ ~Rα ^8, a sulfo group, a sulfonyl group having 1 to 10 carbon atoms, a sulfamoyl group having 1 to 10 carbon atoms Rβ ¹ ~Rβ ⁸ is a hydrogen atom.

In the general formula (4-1), 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), aralkyl group having 7 to 18 carbon atoms (for example, benzyl group, anisyl group), alkenyl group having 2 to 20 carbon atoms (for example, vinyl group, 2-methylvinyl group), alkynyl groups having 2 to 20 carbon atoms (for example, ethynyl group, 2-methylethynyl group, 2-phenylethynyl group), halogen atoms (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), carbon atom 1 to 20 alkoxy groups (for example, methoxy group, butoxy group, cyclohexyloxy group), aryloxy groups having 6 to 20 carbon atoms (for example, phenoxy group, 1-naphthoxy group, toluoyl group), 1 to 20 alkylthio groups (for example, methylthio group, butylthio group, benzylthio group, 3-methoxypropylthio group), arylthio groups having 6 to 20 carbon atoms (for example, phenylthio group, 4-chlorophenylthio group), 1 carbon atom -20 alkylsulfonyl group (for example, methanesulfonyl group, butanesulfonyl group), arylsulfonyl group having 6 to 20 carbon atoms (for example, benzenesulfonyl group, paratoluenesulfonyl group), carbamoyl group having 1 to 17 carbon atoms (For example, unsubstituted carbamoyl group, methylcarbamoyl group, Tilcarbamoyl group, n-butylcarbamoyl group, dimethylcarbamoyl group), amide group having 1 to 16 carbon atoms (for example, acetamido group, benzamide group), acyloxy group having 2 to 10 carbon atoms (for example, acetoxy group, benzoyl) An oxy group), an alkoxycarbonyl group having 2 to 10 carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group), a 5- or 6-membered heterocyclic group (for example, pyridyl group, thienyl group, furyl group, thiazolyl group, imidazolyl). Group, an aromatic heterocyclic group such as pyrazolyl group; a heterocyclic group such as pyrrolidine ring group, piperidine ring group, morpholine ring group, pyran ring group, thiopyran ring group, dioxane ring group, dithiolane ring group).

In the general formula (4-1), 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 a group having 6 to 14 carbon atoms. Aryl group, aralkyl group having 7 to 15 carbon atoms, alkoxy group having 1 to 16 carbon atoms, aryloxy group having 6 to 14 carbon atoms, halogen atom, alkoxycarbonyl group having 2 to 17 carbon atoms, carbon atom A carbamoyl group having 1 to 10 carbon atoms, an amide group having 1 to 10 carbon atoms, among which a chain or cyclic alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, carbon Aryl group having 6 to 10 atoms, alkoxy group having 1 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, chlorine atom, alkoxycarbonyl group having 2 to 11 carbon atoms, 1 carbon atom A carbamoyl group having 7 carbon atoms, an amide group having 1 to 8 carbon atoms, particularly preferred are a branched or cyclic alkyl group having 1 to 8 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, and a carbon atom. These are an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 3 to 9 carbon atoms, a phenyl group, and a chlorine atom, and more preferably and preferably an alkoxy group having 1 to 6 carbon atoms.

  In the general formula (4-1), M is preferably a metal, and among them, zinc, magnesium, copper, nickel or palladium is preferable, copper or nickel is more preferable, and copper is particularly preferable.

  Examples of the phthalocyanine derivative used in the present embodiment include “Phthalocyanine—Chemistry and Function” (p. 1 to 62), published by Shirai-Kobayashi and published by IPC Co., Ltd. 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.

  Next, a pyromethene dye may be used as the dye. The pyromethene dye is preferably a pyromethene metal chelate compound represented by the following general formula (Formula-61).

  In general formula (Chemical Formula-61), A is a chelate ring formed of a pyromethene compound represented by the following general formula (Chemical Formula-62) and metal M, and B is a nitrogen atom, an oxygen atom and / or sulfur. It is a chelate ring formed with M having an atom. A and B may be the same or different.

  In the general formula (Chemical Formula-62), Ya represents N or CRa3. Ra1, Ra2, Ra3, Ra4, Ra5, Ra6, Ra7 each represents a hydrogen atom or a substituent, and Ra1 and Ra2, Ra2 and Ra3, Ra5 and Ra6, and Ra6 and Ra7 each combine to form an aromatic ring or a heterocycle. The ring may have a substituent, and an aromatic ring or a hetero ring may be condensed to the ring.

  In the general formula (Chemical Formula 62), Ra1, Ra2, Ra3, Ra4, Ra5, Ra6 and Ra7 are each independently a hydrogen atom or a substituent, preferably a halogen atom, nitro group, cyano group, hydroxy group, carboxyl group, sulfone. Acid group, alkyl group having 1 to 20 carbon atoms, aryl group, heteroaryl group, alkenyl group having 2 to 20 carbon atoms, aralkyl group, alkoxy group, hydroxyalkoxy group, alkoxyalkoxy group, alkylthioalkoxy group, aryloxy group, Heteroaryloxy group, alkylaminoalkoxy group, dialkylaminoalkoxy group, alkenyloxy group having 2 to 20 carbon atoms, alkylthio group, alkylthioalkyl group, arylthio group, heteroarylthio group, alkylsulfonyl group, arylsulfonyl group, heteroaryl Sulfo Group, alkylsulfonylalkyl group, amino group, alkylamino group, dialkylamino group, hydroxyalkylamino group, di (hydroxyalkyl) amino group, alkoxyalkylamino group, di (alkoxyalkyl) amino group, arylamino group, diaryl Amino group, heteroarylamino group, diheteroarylamino group, alkylcarbonylamino group, arylcarbonylamino group, halogenoalkyl group, aminoalkyl group, alkylaminoalkyl group, dialkylaminoalkyl group, hydroxyalkylaminoalkyl group, di ( Hydroxyalkyl) aminoalkyl group, alkoxyalkylaminoalkyl group, di (alkoxyalkyl) aminoalkyl group, hydroxyalkyl group, alkoxyalkyl group, alkylcarbonyl group Kill group, arylcarbonylalkyl group, aminocarbonyl group, alkylaminocarbonyl group, dialkylaminocarbonyl group, hydroxyalkylaminocarbonyl group, di (hydroxyalkyl) aminocarbonyl group, alkoxyalkylaminocarbonyl group, di (alkoxyalkyl) aminocarbonyl A group, an arylaminocarbonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkenyloxycarbonyl group having 2 to 20 carbon atoms, an alkoxycarbonylalkoxycarbonyl group, an alkylcarbonylalkoxycarbonyl group, or an aralkyloxycarbonyl group. Ra1 and Ra2, Ra2 and Ra3, Ra5 and Ra6, Ra6 and Ra7 may combine to form an aromatic ring or a heterocyclic ring, or may have a substituent.

  Pyrromethene dyes are disclosed in JP-A Nos. 10-226172, 10-162430, 10-287819, 11-43491, 11-92479, 11-92682, 11-165465, 11- No. 227332, No. 11-227333, No. 11-255774, No. 11-256056, No. 11-256057, No. 11-302551, No. 302253, JP-A No. 2000-48406, No. 2000-260064, 2002-212456, 2002-154271, 2002-155076, 2002-2111136, 2002-363437, 2003-64274, 2003-73574, 2003-140300, 2003 -182219, 2003-28 No. 415, No. 2003-266947, No. 2004-66459, No. 2004-114394, No. 2004-122585, or International Publication (WO) 03 / 082593A1, and the like. Specific examples and synthesis methods described in the above-mentioned patent documents can be applied.

  The optical information recording medium 10 according to the present embodiment is not particularly limited as long as it has the dye as the visible information recording layer 24 (preferably the data recording layer 18), but the optical information according to the present embodiment. When the recording medium 10 is applied to a CD-R, a transparent disk having a thickness of 1.2 ± 0.2 mm on which a pregroove 40 (see FIG. 1) having a track pitch of 1.4 to 1.8 μm is formed. On the first substrate 16, the data recording layer 18 containing the dye, the first reflective layer 20, the adhesive layer 28, the second reflective layer 26, the visible information recording layer 24 containing the dye, and the second substrate 22 are arranged in this order. It is preferable that it is the structure which has. Moreover, when applying to DVD-R, it is preferable that it is the following two aspects.

  (1) A data recording layer 18 containing the dye on a transparent disk-shaped first substrate 16 having a thickness of 0.6 ± 0.1 mm on which a pregroove 40 having a track pitch of 0.6 to 0.9 μm is formed. And the two laminated bodies provided with the light reflecting layer are joined so that the data recording layer 18 is inside, and has a thickness of 1.2 ± 0.2 mm, and at least one of the first substrates 16. An optical information recording medium having a visible information recording layer 24 provided thereon.

  (2) The data recording layer 18 containing the dye on the transparent disk-shaped first substrate 16 having a thickness of 0.6 ± 0.1 mm on which the pregroove 40 having a track pitch of 0.6 to 0.9 μm is formed. And a laminated body provided with a light reflecting layer and a transparent disk-shaped protective substrate having the same shape as the disk-shaped first substrate 16 of the laminated body are bonded so that the data recording layer 18 is inside, An optical information recording medium having a thickness of 1.2 ± 0.2 mm and having a visible information recording layer 24 provided on at least one of the substrates. Note that the DVD-R type optical information recording medium may have a configuration in which a protective layer is further provided on the light reflecting layer.

  The visible information recorded in the visible information recording layer 24 means a visually recognizable image, and includes all visually recognizable information such as characters (columns), designs, figures, and the like. 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 visible information recording layer 24 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 data recording layer 18 described later can be used. Other additives, coating methods, and the like can be performed in the same manner as the recording layer described later.

  The layer thickness of the visible information recording layer 24 is preferably 0.01 to 200 μm, more preferably 0.05 to 100 μm, and further preferably 0.1 to 50 μm.

  The thickness ratio of the visible information recording layer 24 / data recording layer 18 is preferably 1/100 to 100/1, more preferably 1/10 to 10/1.

[Data recording layer 18]
The data recording layer 18 is a layer in which code information (encoded information) such as digital information is recorded, and includes a write-once type (preferably a dye write-once type), a phase change type, a magneto-optical type, and the like. Although not preferred, it is preferably a pigment type.

  Specific examples of the dye contained in the dye-type data recording layer 18 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, JP-A-11-53758, JP-A-11-334204, JP-A-11-334205, JP-A-11-334206, JP-A-11-334207, JP-A-2000- The dyes described in each publication such as 43423, 2000-108513 and 2000-158818 are preferably used.

  The data recording layer 18 is prepared by dissolving a recording material such as a dye in a suitable solvent together with a binder or the like to prepare a coating solution, and then coating the coating solution on a substrate to form a coating film, followed by drying. 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%.

  The data recording layer 18 can be formed by a method such as vapor deposition, sputtering, CVD, or solvent coating, but solvent coating is preferred. In this case, after preparing a coating solution by dissolving a quencher, a binder and the like in a solvent in addition to the above-described pigment, and then coating the coating solution on the surface of the first substrate 16 to form a coating film. It can be performed by drying.

  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 data recording layer 18 may be a single layer or a multilayer. The thickness of the data recording layer 18 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 data recording layer 18 can contain various anti-fading agents in order to improve the light resistance of the data recording layer 18. As the antifading 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 of the material constituting the phase change type data recording layer 18 include Sb—Te alloy, Ge—Sb—Te alloy, Pd—Ge—Sb—Te alloy, Nb—Ge—Sb—Te alloy, 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.

  The layer thickness of the phase change type data recording layer 18 is preferably 10 to 50 nm, more preferably 15 to 30 nm.

  The above phase change type data recording layer 18 can be formed by a vapor phase thin film deposition method such as a sputtering method or a vacuum deposition method.

  The content of the metal atoms in the materials constituting the visible information recording layer 24 and the data recording layer 18 described above can be measured by a normal quantitative method.

  For example, using an atomic absorption device (AA240FS manufactured by Varian), the contents of metal atoms Na and K can be quantified by a flame method or an absolute calibration curve method. It can be quantified by the method and absolute calibration curve method. Moreover, as pre-processing, 2g sample powder is extract | collected from a sample, HNo3 is added to this sample powder, multiwave ashing is carried out, Then, a sample is eluted in water and 50 ml sample liquid is prepared. And the content of a metal atom is measured with the quantitative method mentioned above with respect to the obtained sample liquid.

  Further, even after the optical information recording medium 10 is manufactured, the material can be collected from the visible information recording layer 24 and the content of metal atoms can be measured by the same method as described above.

[First substrate 16]
The first substrate 16 of the optical information recording medium 10 according to the present embodiment can be arbitrarily selected from various materials used as a substrate of a conventional optical information recording medium.

  Examples of the material of the first substrate 16 include acrylic resins such as glass, polycarbonate and polymethyl methacrylate, vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers, epoxy resins, amorphous polyolefins and polyesters. These may be used together if desired.

  Note that these materials can be used as a film or as the rigid first substrate 16. Among the above materials, polycarbonate is preferable from the viewpoints of moisture resistance, dimensional stability, price, and the like.

  The thickness of the first substrate 16 is preferably 0.1 to 1.2 mm, and more preferably 0.2 to 1.1 mm.

  On the surface side (the surface side on which the pregroove 40 is formed) of the first substrate 16 on the side where the data recording layer 18 is provided, for the purpose of improving the flatness, improving the adhesive force, and preventing the data recording layer 18 from being altered. An undercoat layer may be provided.

[First Reflective Layer 20 and Second Reflective Layer 26]
The first reflective layer 20 may be provided adjacent to the data recording layer 18 for the purpose of improving the reflectance during information reproduction. Further, the second reflective layer 26 may be provided adjacent to the visible information recording layer 24 for the purpose of improving the focusing of the laser beam 38 when writing the visible information to the visible information recording layer 24.

  The light-reflective substance that is the material of the first reflective layer 20 and the second reflective layer 26 is a substance having a high reflectivity with respect to the laser light 38. Examples thereof include Mg, Se, Y, Ti, Zr, Hf, and V. Nb, Ta, Cr, Mo, 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 other metals and metalloids, and stainless steel. These substances may be used alone or in combination of two or more or as an alloy. The first reflective layer 20 and the second reflective layer 26 can be formed on the data recording layer 18 and the visible information recording layer 24, for example, by vapor deposition, sputtering, or ion plating of the light reflective material. . The thicknesses of the first reflective layer 20 and the second reflective layer 26 are generally in the range of 10 to 300 nm, and preferably in the range of 50 to 200 nm.

[Adhesive layer 28]
The adhesive layer 28 is a layer formed in order to improve the adhesion between the data recording medium unit 12 and the visible information recording medium unit 14.

  As a material constituting the adhesive layer 28, 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. . The thickness of the adhesive layer 28 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 provide elasticity.

[Second substrate 22]
The second substrate 22 (protective substrate) can be made of the same material as the first substrate 16 described above.

  Below, the protective layer employ | adopted by another structure is demonstrated.

[Protective layer]
Protective layers are provided for the purpose of physically and chemically protecting the first reflective layer 20 and the data recording layer 18 and for the purpose of physically and chemically protecting the second reflective layer 26 and the visible information recording layer 24, respectively. Sometimes.

  It is to be noted that the same form as in the production of the DVD-R type optical information recording medium, that is, two substrates (including the case where one is the first substrate 16) are bonded together with the two data recording layers 18 inside. In the case of adopting a configuration, it is not always necessary to form a protective layer.

  The optical information recording medium 10 according to the present embodiment can be applied to a so-called read-only optical information recording medium having a recording part (pit) in which information reproducible by laser light is recorded. As described above.

[Visible information recording method]
The visible information recording method according to the present embodiment is a visible information recording method onto the visible information recording layer 24 of the optical information recording medium 10 according to the present embodiment described above. In the recording, the same laser beam 38 (see FIG. 5) as the laser beam 38 used for recording on the data recording layer 18 is used.

  The visible information recording method of this embodiment is performed using a recording apparatus capable of recording visible information on the visible information recording layer 24 of the optical information recording medium 10 according to this embodiment.

  Here, two recording methods (first recording method and second recording method) of the visible information recording method according to the present embodiment will be specifically described.

  First, the first recording method is a method for recording visible information on the visible information recording layer 24 of the optical information recording medium 10 according to the present embodiment, and the visible information is recorded on the visible information recording layer 24. Recording is performed using the same laser beam 38 as the laser beam 38 used for recording.

  In the second recording method, visible information is recorded on the visible information recording layer 24 using a laser beam 38 that swings in the radial direction of the optical information recording medium 10 and is irradiated a plurality of times on substantially the same locus. In the first recording method, it is preferable to record the visible information using the same laser beam 38 as the laser beam 38 used for data recording on the data recording layer 18 as in the first recording method.

  According to the first recording method, visible information can be recorded by using the same laser beam 38 as the laser beam 38 used for data recording on the data recording layer 18, so that one recording device shares the laser light source. In addition, the hardware resources of the recording device can be minimized, and a general user can easily record visible information using these devices. Furthermore, since the optical information recording medium 10 according to the present embodiment includes a dye in the visible information recording layer 24, there is an advantage that visible information (image or the like) having high contrast and excellent visibility can be formed. Recording of visible information such as an image on the optical information recording medium 10 to the visible information recording layer 24 is most preferably performed by the first recording method and the second recording method, but is not limited thereto.

  In the first recording method and the second recording method, recording of visible information such as an image on the visible information recording layer 24 and data recording on the data recording layer 18 are performed by one optical disc drive having a recording function on both layers ( Recording apparatus). Thus, when one optical disk drive is used, after recording on one of the visible information recording layer 24 and the data recording layer 18, it can be reversed and recording can be performed on the other layer. As an optical disk drive having a function of recording visible information on the visible information recording layer 24, for example, an optical disk drive described in JP-A-2003-203348, JP-A-2003-242750, or the like is used. it can.

  Further, when recording visible information on the visible information recording layer 24, the recording apparatus relatively moves the optical information recording medium 10 and the laser pickup along the surface of the optical information recording medium 10, and synchronizes with the relative movement. The visible light can be recorded by modulating the laser beam 38 according to image data such as characters and pictures to be imaged and irradiating the laser light 38 toward the visible information recording layer 24. Such a configuration is described in, for example, Japanese Patent Application Laid-Open No. 2002-203321.

  In normal digital data recording, it is normal to irradiate the laser beam 38 once with a substantially elliptical locus. In general, when forming pits in a dye recording layer, it is important to form pits with sufficient reflectivity and degree of modulation to be recognized by an optical disk drive (recording apparatus). As the dye, a dye that can obtain a sufficient reflectance and degree of modulation by one-time irradiation of the laser beam is selected.

  On the other hand, in recent years, a system described in JP-A-2002-203321 has been proposed as a new image forming method. In this system, visible information such as an image is recorded on the visible information recording layer 24 containing a dye by irradiating a laser beam 38 on a substantially identical locus a plurality of times. In addition, since the position where pits are formed in the radial direction is specified in a normal optical disc, the laser beam 38 cannot swing in the radial direction of the optical information recording medium 10, whereas in the above system, Visible information is formed by the laser beam 38 oscillating in the radial direction of the optical information recording medium 10 and being irradiated a plurality of times on substantially the same locus. Any of the dyes used in the present embodiment is suitable for the above-described system, and can form visible information with high contrast and clearness and excellent light resistance by the recording method described above.

  Details of the above-described visible information recording method will be described with reference to FIGS.

  FIG. 6 shows the locus of the laser light 38 irradiated for image formation.

  First, as shown in FIG. 6, the laser light source is positioned on the inner circumference side of the optical information recording medium 10 and at a radial position where the first image forming portion exists, and then the circumferential position θ is detected. The laser power is switched to a predetermined high output (a value at which the visible light characteristic of the visible information recording layer 24 changes, for example, a value of 1 mW or more) at each image forming position in the circumferential direction indicated by the image data for the radial position. As a result, the visible light characteristic of the visible information recording layer 24 changes (discoloration, etc.) at the location irradiated with the high-power laser beam 38, and image formation is performed. The laser power of the laser light 38 is controlled based on laser power control information corresponding to the color information of the colored substrate 22a. The laser power control information is acquired by detecting information recorded in the prepits 32 and BCA formed in the prepit area 30 of the optical information recording medium 10.

  Thereafter, when the optical information recording medium 10 is rotated once and returned to the reference position in the circumferential direction, the laser light source is transferred by a predetermined pitch Δr by a feed motor or the like, and the radial position is designated by the image data. Image formation is performed by switching the laser power to a predetermined high output at each image forming position in the direction. Thereafter, this operation is repeated, and image formation is performed by sequentially moving in the outer circumferential direction at a predetermined pitch Δr every round.

  FIG. 6 shows the locus of the laser beam 38 on the surface of the optical information recording medium 10 (surface on the visible information recording layer 24 side, hereinafter also referred to as “label surface”) by this image forming operation. The laser power is switched to a high output at a portion 46 drawn with a thick line, and image formation is performed. FIG. 7 is an enlarged view of the locus of the laser beam 38 at the portion 46 drawn by the bold line. As shown in FIG. 7, an image is formed by oscillating the laser beam 38 in the radial direction of the optical information recording medium 10 and irradiating a substantially identical locus a plurality of times. Here, the swinging width of the laser beam 38 and the number of times of irradiation of the laser beam 38 in substantially the same locus are set for each recording apparatus.

  In the image forming method described above, the image forming is performed by moving to the radius position where the next image forming portion is located at a time without scanning the radius position where there is no image forming portion. When the pitch Δr is large, even if the image should originally be formed in the radial direction, a gap occurs and an image is formed. If the pitch Δr is reduced, the gap can be made inconspicuous, but the number of turns required to form an image on the entire label surface increases, and the image formation takes time.

  If the apparatus described in Japanese Patent Laid-Open No. 2002-203321 is used, the tracking actuator is driven by a vibration signal (sine wave, triangular wave, etc.) generated from a vibration signal generation circuit during image formation, and the objective lens is moved in the disk radial direction. I try to vibrate. Therefore, even if the laser beam 38 vibrates in the disk radial direction and the pitch Δr is relatively large, an image can be formed without a gap (or with a small gap). The frequency of the vibration signal can be set to about several kHz, for example. The pitch Δr can be set to about 50 to 100 μm, for example.

  JP-A-2002-203321 can be referred to for details of the above image forming method.

  The recording apparatus that records data on the data recording layer 18 has at least a laser pickup that emits laser light 38 and a rotation mechanism that rotates the optical information recording medium 10, and rotates recording and reproduction on the data recording layer 18. This can be performed by irradiating a laser beam 38 from a laser pickup toward the data recording layer 18 of the optical information recording medium 10 in such a state. The configuration of such a recording apparatus itself is well known.

  Next, recording of data (pit information) on the data recording layer 18 will be described. When the data recording layer 18 is of the dye type, first, the laser light 38 is irradiated from the laser pickup while rotating the above-mentioned optical information recording medium 10 which has not been recorded at a predetermined recording linear velocity. By this irradiation light, the dye of the data recording layer 18 absorbs the light and the temperature rises locally, and a desired void (pit) is generated and its optical characteristics are changed to record information.

  The recording waveform of the laser beam 38 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 38 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 beam 38 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 20 mW is preferable. Further preferred. When the recording linear velocity is doubled, the preferable range of the power of the laser beam 38 is ^21/2 times, respectively. In order to increase the recording density, the NA (numerical aperture) 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 laser light 38.

  Next, the case where the data recording layer 18 is a phase change type will be described. In the case of the phase change type, the phase change type is composed of the above-described material, and the phase change between the crystalline phase and the amorphous phase can be repeated by irradiation with the laser beam 38. At the time of information recording, the pulse of the concentrated laser beam 38 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. At the time of erasing, the recording mark portion is irradiated with laser light 38, heated to a temperature not higher than the melting point of the data recording layer 18 and not lower than the crystallization temperature, and then cooled, whereby the amorphous recording mark is crystallized. To the original 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 optical information recording medium according to Example 1 is a DVD-R type optical information recording medium in which two discs are bonded together. A method for manufacturing the optical information recording medium according to Example 1 will be described below.

  A first substrate 16 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) is formed from polycarbonate resin by injection molding. did.

  Thereafter, 1.5 g of each oxonol dye represented by the following general formulas (Chemical Formula 63) and Chemical Formula 64 is dissolved in 100 ml of 2,2,3,3-tetrafluoro-1-propanol to prepare a coating solution. Then, this coating solution was applied on the surface of the first substrate 16 on which the pregroove 40 was formed by spin coating to form the data recording layer 18.

  Next, after the silver was sputtered on the data recording layer 18 to form the first reflective layer 20 having a film thickness of 120 nm, an ultraviolet curable resin (SD318 (manufactured by Dainippon Ink & Chemicals, Inc.)) was applied by a spin coating method. Thereafter, the first protective layer having a thickness of 10 μm was formed by irradiating with ultraviolet rays, and the data recording medium portion 12 was produced through the above-described steps.

  Next, in order to form the visible information recording layer 24, a total of 1.50 g of a phthalocyanine dye of the following general formula (Chemical Formula 65) and a trimethine cyanine dye of the following general formula (Chemical Formula 66), and the metal shown in FIG. A coating solution for a visible information recording layer was prepared by dissolving atoms in 100 ml of 2,2,3,3-tetrafluoro-1-propanol. The visible information recording layer coating solution was formed on a second substrate 22 having a thickness of 0.6 mm and a diameter of 120 mm by spin coating.

  Next, silver is sputtered on the visible information recording layer 24 to form a second reflective layer 26 having a film thickness of 120 nm, and then an ultraviolet curable resin (SD318 (manufactured by Dainippon Ink & Chemicals, Inc.) is applied by spin coating. After that, the film was cured by irradiation with ultraviolet rays to form a second protective layer having a layer thickness of 10 μm.

  Next, the data recording medium unit 12 and the visible information recording medium unit 14 were bonded together to complete the optical information recording medium 10 as one sheet. First, a slow-acting cationic polymerization type adhesive (SDK 7000, manufactured by Sony Chemical Corporation) is printed on the first protective layer of the data recording medium unit 12 and the second protective layer of the visible information recording medium unit 14 by screen printing. did. At this time, the mesh size of the screen printing plate was 300 mesh. Next, immediately after irradiation with ultraviolet rays using a metal halide lamp, the data recording medium section 12 and the visible information recording medium section 14 are bonded together from the respective protective layer sides, pressed from both sides, and left for 5 minutes. Such an optical information recording medium was produced.

(Examples 2 to 4)
In the optical information recording media according to Examples 2 to 4, when forming the visible information recording layer 24 of the visible information recording medium unit 14 in Example 1, the content of metal atoms in the visible information recording layer coating liquid is set. An optical information recording medium 10 was manufactured in the same manner as in Example 1 except that the changes were made as shown in FIG.

(Contrast evaluation)
About the produced optical information recording medium which concerns on Examples 1-4, it recorded as follows.

  Drawing of the image for evaluation on the visible information recording layer 24 has a recording apparatus described in Japanese Patent Application Laid-Open No. 2002-203321, that is, a laser pickup that emits laser light 38 and a rotation mechanism that rotates an optical information recording medium. A recording apparatus (laser light source was a semiconductor laser having a wavelength of 660 nm) was used under the drive drawing conditions shown in FIG. 9A. In this case, while the optical information recording medium and the laser pickup are relatively moved along the surface of the optical information recording medium, the laser light 38 is modulated according to desired image data in synchronization with the relative movement, and the linear velocity 3. Visible information was recorded by irradiating the visible information recording layer 24 in a focused state under conditions of 5 m / sec and recording power of 8 mW. At this time, the laser light 38 swayed in the radial direction of the optical information recording medium, and the visible information was recorded by irradiating the substantially same locus a plurality of times. Further, the pit information can be recorded by irradiating the data recording layer 18 with the laser beam 38 from the laser pickup while the optical information recording medium is rotated by the rotating mechanism.

  For Examples 1 to 4 in which visible information was recorded as described above, the absolute reflectances of the laser irradiation portion and the laser non-irradiation portion of the visible information recording layer 24 were measured under the measurement conditions by the spectrophotometer shown in FIG. 9B. Then, Sv represented by the following equation was obtained, and this Sv was used as an evaluation index for contrast. The CIE standard spectral luminous efficiency is shown in FIG.

  Furthermore, five levels of evaluation criteria were provided from the value of Sv obtained by the above formula. The evaluation criteria are as shown in FIG. And contrast was evaluated according to the evaluation criteria of FIG. The evaluation results are shown in FIG.

  In each of Examples 1 to 4, the obtained images were excellent in light fastness and heat fastness. Further, as can be seen from the contrast evaluation results in FIG. 8, all of Examples 1 to 4 have good contrast and clear image recording.

  The optical information recording medium, the visible information recording method, the method of using the mixture, and the mixture according to the present invention are not limited to the above-described embodiments, and can take various configurations without departing from the gist of the present invention. Of course.

It is sectional drawing which abbreviate | omits and shows the structure of the optical information recording medium concerning this Embodiment. It is a top view which shows the optical information recording medium which concerns on a 1st modification. It is a top view which shows the optical information recording medium which concerns on a 2nd modification. It is sectional drawing which abbreviate | omits and shows the optical recording medium which concerns on a 2nd modification. It is sectional drawing which abbreviate | omits and shows a specific structural example of the optical information recording medium based on this Embodiment. It is explanatory drawing which shows the locus | trajectory of the laser beam irradiated for image formation. It is an enlarged view which shows the locus | trajectory of the laser beam in the part drawn with the thick line in FIG. It is a table | surface figure which shows contrast evaluation of the optical information recording medium which concerns on Examples 1-4. FIG. 9A is a table showing drive drawing conditions when an evaluation image is recorded, and FIG. 9B is a table showing measurement conditions by a spectrophotometer. It is a table | surface figure which shows CIE standard spectral luminous efficiency. It is a table | surface which shows the evaluation criteria of contrast based on the formula which shows the evaluation index of contrast.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10, 10a, 10b ... Optical information recording medium 12 ... Data recording medium part 14 ... Visible information recording medium part 16 ... 1st board | substrate 18 ... Data recording layer 20 ... 1st reflection layer 22 ... 2nd board | substrate 24 ... Visible information recording layer 26 ... Second reflective layer 28 ... Adhesive layer 38 ... Laser light 40 ... Pre-groove

Claims (9)

An optical information recording medium capable of recording information by irradiating a laser beam,
It has a visible information recording layer in which visible information is recorded,
The optical information recording medium, wherein the visible information recording layer contains a dye and at least one metal atom selected from the group consisting of Na, Mg, K and Ca. The optical information recording medium according to claim 1,
An optical information recording medium, wherein the dye is at least one selected from the group consisting of an oxonol dye, a cyanine dye, an azo dye, a phthalocyanine dye, and a pyromethene dye. The optical information recording medium according to claim 1 or 2,
An optical information recording medium characterized in that the metal atom is contained at a ratio of 0.1 to 100 g with respect to 1 kg of the dye. The optical information recording medium according to any one of claims 1 to 3,
An optical information recording medium comprising a phthalocyanine dye having a central metal of Cu and a trimethine cyanine dye as the dye. The optical information recording medium according to claim 4,
The optical information recording medium, wherein the metal atom is contained at a ratio of 0.1 to 10 g with respect to 50 g of Cu as the central metal. In the optical information recording medium according to any one of claims 1 to 5,
A first substrate;
A recording layer formed on the first substrate;
A first reflective layer formed on the recording layer;
An adhesive layer formed on the first reflective layer;
A second reflective layer formed on the adhesive layer;
The visible information recording layer formed on the second reflective layer;
An optical information recording medium comprising: a second substrate formed on the visible information recording layer. It is the visible information recording method to the said visible information recording layer of the optical information recording medium of any one of Claims 1-6,
A visible information recording method, wherein the same laser light as that used for recording on the recording layer is used for recording visible information on the visible information recording layer. Information can be recorded by irradiating laser light, and used for an optical information recording medium having a visible information recording layer on which visible information is recorded,
A method of using a mixture, wherein a mixture of a dye and at least one metal atom selected from the group consisting of Na, Mg, K and Ca is used for the visible information recording layer of the optical information recording medium. It is a material used for the visible information recording layer of an optical information recording medium capable of recording information by irradiating laser light and having a visible information recording layer on which visible information is recorded,
A mixture of a dye and at least one metal atom selected from the group consisting of Na, Mg, K and Ca.

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