WO2006082802A1 - Optical information recording medium and production method thereof - Google Patents
Optical information recording medium and production method thereof Download PDFInfo
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- WO2006082802A1 WO2006082802A1 PCT/JP2006/301518 JP2006301518W WO2006082802A1 WO 2006082802 A1 WO2006082802 A1 WO 2006082802A1 JP 2006301518 W JP2006301518 W JP 2006301518W WO 2006082802 A1 WO2006082802 A1 WO 2006082802A1
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/2403—Layers; Shape, structure or physical properties thereof
- G11B7/24035—Recording layers
- G11B7/24038—Multiple laminated recording layers
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/2403—Layers; Shape, structure or physical properties thereof
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
- G11B7/247—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes methine or polymethine dyes
- G11B7/2478—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes methine or polymethine dyes oxonol
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
Definitions
- the present invention relates to an optical information recording medium, and more particularly to a write-once digital 'versatile' disc.
- the present invention relates to a heat mode type optical information recording medium such as (DVD-R) and a method for manufacturing the same.
- optical information recording medium capable of recording information only once with a laser beam.
- One such optical information recording medium is a write-once CD (so-called CD-R).
- This CD-R has the advantage of being able to provide a small amount of CD at a reasonable price and quickly compared to conventional CD production. For this reason, the demand for personal computers has increased with the recent spread of personal computers.
- the typical structure of a CD-R type optical information recording medium consists of a transparent disk-shaped substrate, a recording layer made of organic dye, a reflective layer made of metal such as gold, and a protective layer made of resin in this order. Laminated.
- optical information recording medium having a higher recording density
- it is effective to reduce the light diameter of the laser to be irradiated, and it is theoretically advantageous to increase the density because one laser beam with a shorter wavelength can be reduced.
- optical discs for recording / reproduction using laser light having a wavelength shorter than 780 nm which has been used in the past, has been developed.
- DVD-R write-once digital versatile discs
- the optical disc called is called up.
- This optical disc has a recording layer made of dye on a transparent disk-shaped substrate with a diameter of 120 mm or 80 mm with a pre-groove with a track pitch of less than 1.6 m of CD-R of 0.8 m, Usually, a reflective layer and a protective layer are not provided on the recording layer. It is manufactured to have a structure in which two discs or a disc-like protective substrate having substantially the same dimensions as the disc are bonded with an adhesive with the recording layer as an inner layer. DVD-R records and plays back by irradiating visible laser light (usually laser light with a wavelength in the range of 600 nm to 700 nm), enabling higher density recording than CD-R type optical discs. It is said that
- the DVD-R type optical information recording medium can record information several times as much as the conventional CD-R type, and thus has high recording sensitivity. In particular, it is necessary to quickly process a large amount of information. It is desirable that the error rate be low even for high-speed recording.
- a recording layer made of a dye generally has low stability over time with respect to heat or light, the development of a recording layer that can maintain stable performance against heat or light over a long period of time is an issue. .
- a CD-R type information recording medium in which a recording layer having an oxonol coloring power is provided on a substrate has been proposed (see, for example, Patent Document 1).
- An oxonol dye compound has also been proposed for providing an optical information recording medium that exhibits high light resistance and durability and exhibits good recording characteristics (see, for example, Patent Documents 2 and 3).
- the optical information recording medium containing the dye in the recording layer when a recording layer is a single layer and a so-called multi-layer write-once optical disc composed of two or more recording layers is manufactured,
- a pressure-sensitive adhesive or an adhesive that forms the intermediate layer may cause contact with the dye constituting the recording layer, which may adversely affect the storage stability of the recorded information.
- an optical information recording medium having a buffer layer provided between the recording layer and the adhesive layer and having two recording layers has been proposed! Speak (see, for example, Patent Document 4).
- the buffer layer may not be able to prevent the mixing of the dye with the adhesive or the adhesive, but the buffer layer is used for the signal of information recording. There is a risk of deteriorating properties.
- Patent Document 1 Japanese Patent Application Laid-Open No. 63-209995
- Patent Document 2 Japanese Patent Laid-Open No. 2000-52658
- Patent Document 3 Japanese Patent Laid-Open No. 2002-249674
- Patent Document 4 Japanese Patent Laid-Open No. 2003-331473
- the present invention has been made to solve the above-described conventional problems.
- a plurality of recording layers containing a dye are provided, and protection is provided adjacent to the plurality of recording layers.
- a layer and Z or an intermediate layer it is possible to prevent interference between information signals recorded on each recording layer, and to provide an optical information recording medium exhibiting good recording characteristics and a method for manufacturing the same.
- At least two recording layers containing a dye are formed on a substrate, and the first recording layer and the second recording layer out of the recording layers having at least two layers.
- An optical information recording characterized in that at least one of the dyes contained in the layer is an oxonol dye, and an intermediate layer is formed between the first recording layer and the second recording layer. It is a medium.
- a second aspect of the present invention is the optical information recording medium according to the first aspect, wherein the oxonol dye has a structure represented by the following general formula (1).
- a third aspect of the present invention is the optical information according to the first or second aspect, wherein the first recording layer, the reflective layer, and the second recording layer are formed in this order on the substrate. It is a recording medium.
- a fourth aspect of the present invention is the method according to the second or third aspect, wherein the ion represented by Q in the general formula (1) has a structure represented by the following general formula (2).
- An optical information recording medium is the ion represented by Q in the general formula (1).
- the oxonol dye has a structure represented by the following general formula (3): The optical information recording medium according to the second aspect.
- R 4 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, or R 1 and R 2 , or R 3 and R 4 may be bonded to each other to form a ring structure
- R 3 ° each independently represents a hydrogen atom or a force representing a substituent or R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , and R 3 ° next to Two adjacent substituents may be bonded to each other to form a ring structure.
- a sixth aspect of the present invention is the optical information recording medium according to any one of the first to fifth aspects, wherein the thermal decomposition temperature of the oxonol dye is in the range of 100 ° C to 350 ° C. is there.
- a protective layer is provided adjacent to the at least one recording layer. It is a recording medium.
- the material of the protective layer is SiO, SiO, MgF, SnO, Si N
- optical information recording medium wherein the optical information recording medium is at least one selected from the group consisting of organic substance powers of curable resin.
- the intermediate layer comprises a thermoplastic resin, a thermosetting resin, an electron beam curable resin, an ultraviolet curable resin, a pressure-sensitive double-sided tape, and Si02.
- a tenth aspect of the present invention includes a pair of opposing substrates, two or more recording layers containing a dye between the opposing pair of substrates, and the two or more recording layers.
- a dye protective layer formed adjacent to the laser light incident side of at least one recording layer, and the refractive index (n) of the at least one recording layer and the dye adjacent to the recording layer
- An eleventh aspect of the present invention is the optical information recording medium according to the tenth aspect, wherein the material forming the dye protective layer is an inorganic material.
- a twelfth aspect of the present invention is the optical information recording medium according to the tenth aspect, wherein the inorganic material is a metal oxide.
- the metal oxide is at least one selected from the group oxide consisting of a composite oxide of zinc oxide and gallium oxide, acid-tantalum, and acid-niobium force. so
- the optical information recording medium according to the twelfth aspect characterized in that there is provided.
- a fourteenth aspect of the present invention is the optical information recording medium according to the twelfth aspect, wherein the metal oxide is gallium oxide.
- a fifteenth aspect of the present invention is a dual-layer write-once digital versatile tile, wherein the disc has a first recording layer, a dye protective layer, and a second recording layer from the side on which laser light is incident.
- the dye protective layer and the second recording layer are adjacent to each other, and the refractive index (n) of the second recording layer and the refractive index of the dye protective layer adjacent to the recording layer ( n)
- optical information recording medium according to any one of the tenth to fourteenth aspects, wherein the condition of formula (1) is satisfied.
- a sixteenth aspect of the present invention is the optical information recording medium according to the tenth aspect, wherein the dye is oxonol represented by the following general formula (1).
- Za 1 and Za 2 each independently represent an atomic group that forms an acidic nucleus
- Ma 1 , and Ma 3 each independently represent a substituted or unsubstituted methine group
- ka Represents an integer from 0 to 3
- multiple Ma 1 and Ma 2 may be the same or different Q represents an ion that neutralizes charge, and y is necessary for charge neutralization
- the ion represented by Q in the general formula (1) is oxonol represented by the following general formula (2): An optical information recording medium according to the sixteenth aspect.
- R U , R 12 , R ′′, R 15 , R 16 , R ′′, R 19 , and R 2 ° each independently represents a hydrogen atom or a monovalent substituent
- R 13 and R 18 each independently represent a monovalent substituent.
- a nineteenth aspect of the present invention is the eighteenth aspect, comprising a step of providing a protective layer on at least one of the first laminate and the second laminate. This is a method for manufacturing an optical information recording medium.
- a twentieth aspect of the present invention includes a step of providing an intermediate layer and a Z or reflective layer between at least two recording layers in the first laminated body and the second laminated body. 20. The method for producing an optical information recording medium according to the eighteenth or nineteenth aspect.
- a twenty-first aspect of the present invention is an optical information recording medium manufactured by the manufacturing method according to any one of the eighteenth to twentieth aspects.
- a twenty-second aspect of the present invention is a method for producing an optical information recording medium, wherein at least two recording layers containing at least one oxonol dye are provided on a substrate,
- At least two recording layers are laminated in the order of a first recording layer, a reflective layer, an intermediate layer, and a second recording layer.
- a twenty-third aspect of the present invention is produced by the manufacturing method according to the twenty-second aspect.
- An optical information recording medium characterized by the above.
- a plurality of recording layers containing an oxonol dye are provided, and information recorded on each recording layer is provided by providing an intermediate layer and a Z or protective layer between the plurality of recording layers. It is possible to provide an optical information recording medium that can prevent interference between signals and exhibit good recording characteristics.
- FIG. 1 is a schematic cross-sectional view showing an example of a layer structure of an optical information recording medium of the present invention.
- FIG. 2 is a schematic sectional view showing an example of another layer structure of the optical information recording medium of the present invention.
- At least two recording layers containing a dye are formed on a substrate.
- at least an oxonol dye is used as the dye contained in the first recording layer and the second recording layer.
- At least an intermediate layer and a Z or protective layer are formed between the first recording layer and the second recording layer.
- the intermediate layer and the Z or protective layer By forming the intermediate layer and the Z or protective layer, interference between the information signal recorded on the first recording layer and the information signal recorded on the second recording layer can be prevented, and good recording and reproduction can be performed on both layers. A signal can be obtained.
- the details of the intermediate layer and Z or the protective layer will be described later.
- the intermediate layer and the Z or protective layer are preferably formed between the respective layers.
- the optical information recording medium of the present invention comprises a pair of opposing substrates and at least two recording layers formed between the pair of opposing substrates.
- a configuration in which the first recording layer, the dye protective layer, and the second recording layer are provided from the laser beam incident side, and the dye protective layer and the second recording layer are adjacent to each other is exemplified. it can.
- the dye protective layer By forming the dye protective layer, mixing of the dye in the recording layer with the pressure-sensitive adhesive or adhesive can be prevented.
- the recording layer adjacent to the dye protective layer is referred to as a second recording layer.
- the “laser beam incident side” is the information on the optical information recording medium (optical disc). It means the side irradiated with laser light during recording / reproduction.
- the material used for the dye protective layer is preferably an inorganic material, more preferably a metal oxide.
- metal oxides there are few “complex oxides of zinc oxide and gallium oxide (ZnO—Ga 2 O 3)”, “tantalum oxide” and “niobium oxide”.
- the above-mentioned metal oxides can more reliably prevent the mixture of a dye, a pressure-sensitive adhesive, and an adhesive, and the mixture of a dye with a low diffusion, and a pressure-sensitive adhesive or an adhesive, over a long period of time. Also, by using these metal oxides, the balance between the reflectivity of L1 and the recording laser power (recording power) is improved. Furthermore, in order to allow a wide margin for the same viewpoint and reflectivity standard (two-layer type standard defined by the DVD + RW Alliance), the metal oxide must be acid gallium. Is preferred.
- the optical information recording medium of the present invention has a refractive index (n
- the condition is met.
- N is preferably “n ⁇ 0. 6 ⁇ n ⁇ n +0.1”.
- the dye protective layer may be formed by a method such as sputtering using the above-described metal oxide material as the dye protective layer.
- the dye protective layer may be formed using a compound such as a metal nitride or a metal fluoride.
- the extinction coefficient of the dye protective layer is preferably 0.5 or less, more preferably 0 to 0.2. When it is 0.5 or less, absorption by light in the dye protective layer can be suppressed, and laser light used for recording and reproduction can be effectively utilized.
- the refractive index and extinction coefficient can be easily measured by the rotating photon method (ellipsometer). JAWOOLLAM model V- VASE- S is an example of a measuring device.
- the recording layer is a layer on which information is recorded and reproduced by a laser beam used for recording and reproduction.
- code information such as digital information is recorded.
- the recording layer may be a dye recording layer or a phase change recording layer, but a dye recording layer is preferred.
- the dye contained in the recording layer include cyanine dyes, oxonol dyes, azo dyes, phthalocyanine dyes, triazole compounds (including benzotriazole compounds), triazine compounds, merocyanine compounds.
- examples thereof include compounds, aminobutadiene compounds, cinnamic acid compounds, benzoxazole compounds, pyromethene compounds, squarylium compounds, and the like. In addition, these may have a metal atom in the coordination center.
- cyanine dyes oxonol dyes, azo dyes (including Ni and Co complexes), and pyromethene compounds are preferable.
- an oxonol dye as a dye contained in at least the first recording layer.
- an oxonol dye By using an oxonol dye, high light resistance and durability can be exhibited, and better recording characteristics can be exhibited.
- oxonol dye examples include those described in F. M. Harmer, Heterocyclic Compounds-Cyanme Dyes and Related Compounds, John & Wiley & Sons New York, London, 1964.
- oxonol dyes those having a structure represented by the following general formula (1) are preferred in the present invention.
- Za 1 and Za 2 each independently represent an atomic group that forms an acidic nucleus
- Ma 1 , Ma 2 , and Ma 3 each independently represent a substituted or unsubstituted methine group
- ka represents an integer from 0 to 3
- Q represents an ion that neutralizes the charge
- y represents the number of Q necessary for neutralizing the charge.
- Za 2 A specific example of Za 2 is defined by “James, The Theory of the Photographic Procedure, 4th edition, Macmillan, 1977, p. 198”. More specifically, pyrazole-1-5-one, virazolidine-1,3,5-dione, imidazoline-5-one, hydantoin, 2 or 4 thiohydantoin, 2-iminooxazolidine 4one, 2 oxazoline 5 on, 2 thoxazoline 2, 4 dione, isorhodanine, rhodanine, 5, 6 membered carbocycle (eg indan 1, 3 dione), thiophen 3 on, thiophen 3 on 1, 1 dioxide, indoline 2 on, indoline 3 on, 2-oxosoindazolium, 5,7 dioxo6,7 dihydrothiazolo [3,2-a] pyrimidine, 3,4-dihydroisoquinolinone-4-one, 1,3 dioxane-1,4,
- Ma 2 and Ma 3 each independently represents a substituted or unsubstituted methine group.
- Substituents in Ma 1 , Ma 2 and Ma 3 are substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, substituted or unsubstituted aryloxy groups, substituted or Unsubstituted heterocyclic group, halogen atom, carboxyl group, substituted or unsubstituted alkoxycarbo group, cyano group, substituted or unsubstituted acyl Group, substituted or unsubstituted force rubamoyl group, amino group, substituted amino group, sulfo group, hydroxyl group, nitro group, substituted or unsubstituted sulfonylamino group, substituted or unsubstituted aminocarbo-lamino group, substituted Or an unsubstituted alky
- the substituent is 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 group having 1 to 2 carbon atoms.
- alkoxy groups, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, and halogen atoms more preferably substituted or unsubstituted carbon atoms 1 to: LO alkyl group, substituted or unsubstituted carbon numbers
- An alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon ring group having 2 to 10 carbon atoms, a halogen atom is most preferred, and an unsubstituted alkyl group having 1 to 5 carbon atoms and an unsubstituted carbon number
- Ma 3 is more preferably an unsubstituted methine group, an unsubstituted alkyl group having 1 to 5 carbon atoms, an unsubstituted alkoxy group having 1 to 5 carbon atoms, or a substituted or unsubstituted carbon number 2 to 6 And a methine group substituted with a halogen atom.
- Ka represents an integer of 0 to 3, more preferably an integer of 1 or 2.
- ka is 2 or more, multiple Ma 1 Ma 2 may be the same or different.
- a compound is a cation, an anion, or has a net ionic charge depends on the substituent of the compound.
- the ion represented by Q in the general formula (1) may represent a cation or an anion, and the dye molecule may be uncharged. There is no Q.
- the ion represented by Q is not particularly limited and may be an ion composed of an inorganic compound or an ion composed of an organic compound.
- the charge of the ion represented as Q may be monovalent or polyvalent.
- Examples of the cation represented by Q include metal ions such as sodium ion and potassium ion, quaternary ammonium ion, oxo-um ion, sulfo-mu ion, phospho-mu ion, seleno-mu ion, and cation.
- metal ions such as sodium ion and potassium ion, quaternary ammonium ion, oxo-um ion, sulfo-mu ion, phospho-mu ion, seleno-mu ion, and cation.
- ion ions such as dawn ion.
- examples of the anion represented by Q include halogen anions such as salt chloride ions, bromide ions, and fluoride ions, sulfate ions, phosphate ions, hydrogen phosphate ions, and the like.
- Examples thereof include organic polyvalent anions such as telopolyacid ion, oxalate ion, maleate ion, fumarate ion and aromatic disulfonate ion, tetrafluoroborate ion and hexafluorophosphate ion.
- the cation represented by Q is preferably an ion, and more preferably a quaternary ammonium ion.
- the 4, 4′-bibilidium cation represented by the general formula (1-4) of JP 2000-52658 A and JP 2002-59652 A are particularly preferable.
- the ion represented by Q preferably has a structure represented by the following general formula (2).
- R U , R 12 , R W , R 15 , R 16 , R 17 , R 19 , and R 2 ° each independently represent a hydrogen atom or a monovalent substituent
- R 13 and R 18 each independently represents a monovalent substituent.
- Examples of the monovalent substituent include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), a alkenyl group (including a cycloalkyl group and a bicycloalkenyl group), an alkyl group.
- R u , R 12 , R 14 , R 15 , R 16 , R 17 , R 19 , and R 2 ° are each independently a halogen atom (for example, chlorine atom, bromine atom, iodine atom)
- an alkyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkyl group.
- alkyl groups preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2 —Cyanoethyl, 2 —ethylhexyl
- a cycloalkyl group preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl
- Bicycloalkyl group preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a bicycloalkane force having 5 to 30 carbon atoms is a monovalent group in which one hydrogen atom is removed.
- An alkyl group for example, an alkyl group of an alkylthio group
- substituents described below also represents such an alkyl group.
- Alkenyl group [Represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. These include an alkyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as bur, aryl, prenyl, galle, oleyl), a cycloalkenyl group (preferably a carbon A substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms has been removed, such as 2 -cyclopentene 1-yl, 2 —Cyclohexene 1-yl), bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms
- alkyl group preferably a substituted or unsubstituted alkyl group having 2 to 30 carbon atoms, such as ethul, propargyl, trimethylsilyl ether
- aryl group preferably a substituted or unsubstituted group having 6 to 30 carbon atoms.
- Substituted aryl groups such as phenyl, p-tolyl, naphthyl, m-chloroform, o-hexadecanolaminophenol, heterocyclic groups (preferably 5- or 6-membered substitution) Or a monovalent group obtained by removing one hydrogen atom from an unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic having 3 to 30 carbon atoms.
- Rubamoyloxy group (preferably a substituted or unsubstituted rubamoyloxy group having 1 to 30 carbon atoms, for example, N, N dimethylcarbamoyloxy, N, N jetylcarbamoyloxy, morpholinocarbonyloxy, N, N di n— Octylaminocarbonyloxy, N—n-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms such as methoxycarbonyloxy, ethoxy Carbonyloxy, t-butoxycarbonyl Roxy, n-octylcarbo-loxy), aryloxy-carboxoxy group (preferably substituted or unsubstituted aryloxycarbo-loxy group having 7 to 30 carbon atoms, such as phenoxycarbo-loxy, p —Methoxyphenoxycarbox
- amino group preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, such as amino-containing methylamino, dimethylamino-anilino, N —Methylaniline-containing diphenylamino), an acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbolumino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcoyl group having 6 to 30 carbon atoms) Amino group such as formylamino, acetylamino-containing bivaloylamino-containing lauroylamino, benzoylami-containing 3, 4, 5-tree n-octyloxyphenylcarbonylamino, aminocarbo-lamino group (preferably having 1
- Alkoxycarbolamino group (preferably a substituted or unsubstituted alkoxycarbolamino group having 2 to 30 carbon atoms, for example, methoxycarbolami-containing ethoxycarbolami-in t-butoxycarbonylamino, n-octadecyloxycarbonyl Amino-containing N-methylmethoxycarbolamino), aryloxycarbolamino group (preferably a substituted or unsubstituted aryloxycarbolamino group having 7 to 30 carbon atoms, for example, phenylcarbonyl Amino, p-cyclophenoxycarbonylamino, m-n-octyloxyphenoxycarbolamino), sulfamoylamino group (preferably substituted or unsubstituted sulfamoyl having 0 to 30 carbon atoms) Amino groups such as N, N-dimethylaminosulfonylamino,
- Aryl and heterocyclic azo groups preferably substituted or unsubstituted aryl azo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo , ⁇ -black mouth phenylazo, 5-ethylthio-1,3,4-thiadiazole-2-ylazo), imide group (preferably N-succinimide, N-phthalimide), phosphino group (preferably 2 to 30 carbon atoms)
- Substituted or unsubstituted phosphino groups such as dimethyl phosphite-containing diphenylphosphite-containing methylphenoxyphosphino, phosphier groups (preferably 2 to 30 carbon atoms substituted or unsubstituted phosphier groups such as Phosphinyl, dioctyloxyphosphier, diethoxyphosphier), phosphieroxy group (
- those having a hydrogen atom may be further substituted with the above groups.
- a functional group include an alkyl carbo- aminosulfol group, an aryl carbo-amino amino group, an alkyl sulfonylamino group, and an aryl sulfonylamino group.
- examples thereof include methylsulfoaminocarbonyl, p-methylphenylsulfoluminocarbon, acetylaminosulfol, and benzoylaminosulfol groups.
- R U , R 12 , R ", R 15 , R 16 , R", R 19 , and R 2 ° are preferably all hydrogen atoms.
- R 13 and R 18 are each independently preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Of these, a substituted or unsubstituted aryl group is more preferable. Furthermore, a substituted aryl group is preferable.
- R 13 and R 18 are a substituted aryl group
- the substituent is a hydroxyl group, a substituted or unsubstituted aryl And a substituted or unsubstituted alkyl group and a halogen atom are preferred.
- the most preferred structure of the oxonol dye is
- R 4 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or R 1 and R 2 , and R 3 And R 4 may be bonded to each other to form a ring structure
- R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 29 and R 3 ° each independently represents a hydrogen atom or a substituent, or R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , And R 3 °, two adjacent substituents may be bonded to each other to form a ring structure.
- R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , And R 3 ° each independently represents a hydrogen atom, a hydroxyl group, a cyano group, a halogen atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group.
- R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , And R 3 ° is preferable, for example, R 23 and R 28 are hydroxy groups, and R 22 and R 27 are substituted or unsubstituted phenol groups, and more preferable examples are further Others are hydrogen atoms.
- Preferred specific examples (pigments 1 to 34) of the compound represented by the above general formula (1) are shown below. Is limited to There is no.
- Dye 1-6 is a specific example of the following general formula (4)
- Dye 7-12 is a specific example of the following general formula (5)
- Dye 13-16 is a specific example of the following general formula (6)
- dyes 17 to 21 are specific examples of the following general formula (7).
- oxonol dyes A and B described below may be used in addition to the oxonol dye.
- oxonol dye A a compound represented by the following general formula (8) is preferred U.
- R U , R 12 , R 13 , and R each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted helic group.
- R 21 , R 22 , and R 3 are hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, substituted or unsubstituted Is an unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a halogen atom, a force carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a cyano group, a substituted or unsubstituted acyl group, a substituted or unsubstituted Rubbamoyl group, amino group, substituted amino group, sulfo group, hydroxyl group, nitro group, substituted or unsubstituted alkylsulfo-lumino group, substituted or unsubstituted arylosulfo-lumino group, substituted Or unsubstituted rubam
- R U , R 12 , R 13 , and R 14 in the general formula (8) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heter Represents any of the ring ring groups.
- Examples of the substituted or unsubstituted alkyl group represented by R u , R 12 , R 13 , and R 14 include an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl, butyl, i-butyl, t-butyl, i-amyl, cyclopropyl, cyclohexyl, benzyl, phenethyl).
- R u , R 12 , R 13 , and R ′′ each represents an alkyl group, they are connected to each other to form a carbocyclic ring (for example, cyclopropyl, cyclobutyl, cyclopentinole, cyclohexenole, 2-methinorecycloto
- it is a chain alkyl group or cyclic alkyl group having 1 to 8 carbon atoms, and most preferably a chain (linear or branched) alkyl group having 1 to 5 carbon atoms, R 11 and R 12 And R 13 and R "each bonded to form a cyclic alkyl group having 1
- the substituted or unsubstituted aryl group represented by R u , R 12 , R 13 , and R "in the general formula (8) is an aryl group having 6 to 20 carbon atoms (for example, a phenyl group).
- the aryl group represented by R u , R 12 , R 13 , and R 14 is preferably an aryl group having 6 to 10 carbon atoms.
- R u of the general formula (8), R 12, heterocyclic group R 13, and substituted or unsubstituted to the represented by R 14 is composed of carbon atoms, nitrogen atom, oxygen atom or sulfur atom, 5- or 6-membered saturated or unsaturated heterocyclic group such as pyridyl group, pyrimidyl group, pyridazyl group, piperidyl group, triazyl group, pyrrolyl group, imidazolyl group, triazolyl group, fulleryl group, Nyl group, thiazolyl group, oxazolyl group, isothiazolyl group, isoxazolyl group and the like.
- the substituted or unsubstituted heterocyclic group represented by R u , R 12 , R 13 , and R 14 is preferably a substituted or unsubstituted heterocyclic group having 6 to carbon atoms: LO.
- substituent 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 (for example, methyl, ethyl, propyl, carboxymethyl, ethoxycarboromethyl), and an aralkyl group having 7 to 20 carbon atoms (for example, Benzyl, phenethyl), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy), an aryl group having 6 to 20 carbons (for example, phenyl, naphthyl), an aryl group having 6 to 20 carbon atoms (for example, Phenoxy, naphthoxy), heterocyclic groups (eg, pyridyl, pyrimidyl, pyridazyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, 2 pyrrolidinone 1-yl, 2 piperidone 1-yl, 2, 4 Dioxyimidazolidine 3 yl, 2,4-
- R 21 , R 22 , and R 3 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 aryloxy group, substituted or unsubstituted heterocyclic group, halogen atom, carboxyl group, substituted or unsubstituted alkoxycarbo yl group, cyano group, substituted or unsubstituted acyl group, substituted or unsubstituted Substitutive force Rubamoyl group, amino group, substituted amino group, sulfo group, hydroxyl group, nitro group, substituted or unsubstituted alkyl sulfol amino group, substituted or unsubstituted force ruberamoylamino group, substituted or unsubstituted alkyl Any
- R 3 is 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 number 1 to 20
- An alkoxy group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a halogen atom more preferably a hydrogen atom, a substituted or unsubstituted carbon atom having 1 to: an L0 alkyl group, a substituted or unsubstituted carbon atom, An alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 10 carbon atoms, and most preferably a halogen atom, a hydrogen atom, an unsubstituted alkyl group having 1 to 5 carbon atoms, an unsubstituted group It is any one of
- m is 0, and R 21 and R 22 are both hydrogen atoms.
- M is 1 R 21 , R 22 , and R 3 are preferably all hydrogen atoms.
- m in the general formula (8) 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. It is an integer of ⁇ 2.
- the plurality of R 3 may be the same or different and each independently represents a hydrogen atom or the above substituent.
- Z x + represents a cation
- X represents an integer of 1 or more.
- the cation represented by Z x + is preferably a quaternary ammonium ion, and more preferably 4, 4 represented by the general formula (1-4) of JP-A-2000-52658. 4'-bibilidium cations and 4,4'-bilibium cations disclosed in JP 2002-59652.
- X is preferably 1 or 2.
- the oxonol dye B is preferably a compound represented by the following general formula (9).
- Za 25 and Za 26 are each independently an atomic group that forms an acidic nucleus
- Ma 27 , Ma 28 , and Ma 29 are each independently a substituted or unsubstituted methine group.
- Ka 23 represents an integer from 0 to 3
- Q represents a cation that neutralizes the charge.
- Za 25 and Za 26 are described in James, The Theory of the Photographic Process, 4th edition, Macmillan, 1977, page 198. Specifically, pyrazol 5-one, azolidinone 3,5-dione, imidazoline-5-one, hydantoin, 2 or 4 thiohydantoin, 2-iminooxazolidin 4-one, 2— Oxazoline 5 ON, 2 Thioxazoline 2, 4 Dione, Isorhodanine, Rhodanine, Thiophene 3 ON, Thiophene 3 ON 1, 1 Oxide, Indoline-2one, Indoline-3on, 2oxoindazolium, 5,7-dioxo6,7 Dihydrothiazolo [3,2-a] pyrimidine, 3,4-dihydroisoquinoline 4on, 1,3 dioxane 4, 6 diones (eg Meldrum's acid), barbituric acid, 2 thiobarbituric acid, coumarin 1, 2, 4 dione, indazoline
- Za 25 and Za 26 are each most preferably an optionally substituted 1,3 dioxane-1,4,6 dione.
- Substituents for substituting acidic nuclei include halogen atoms, alkyl groups (including cycloalkyl groups and bicyclic alkyl groups), alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkyls.
- aryl group aryl group, heterocyclic group, cyan group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic group, acyloxy group, rubermoyloxy group, alkoxycarbo-loxy group, Aryloxycarboxy, amino (including amino), acylamino, aminocarboamino, alkoxycarbolumino, aryloxycarboamino, sulfamoylamino, alkyl and arylsulfo -Luamino group, mercapto group, alkylthio group, arylthio group, heterocycle Thio group, sulfamoyl group, sulfo group, alkyl and aryl sulfier group, alkyl group and aryl sulfonyl group, acyl group, allyloxy carboxylic group, alkoxy carbo yl group
- the acidic nucleus is 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 Is preferred.
- the acidic nucleus formed by Za 25 and Za 26 is preferably indandione, pyrazolone, pyrazoline dione, or benzothiophenone dioxide. Of these, pyrazolone is most preferred.
- Ma 27 , Ma 28 , and Ma 29 are each independently a substituted or unsubstituted methine group, preferably an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, isopropyl).
- halogen atoms eg, chlorine, bromine, iodine, fluorine
- alkoxy groups having 1 to 20 carbon atoms eg, methoxy, ethoxy, isopropyl
- aryl groups having 6 to 26 carbon atoms eg, phenyl, 2 —Naphthyl
- a heterocyclic group having 0 to 20 carbon atoms eg, 2-pyridyl, 3-pyridyl
- an aryloxy group having 6 to 20 carbon atoms eg, phenoxy, 1-naphthoxy, 2-naphthoxy
- C 1-20 acylamine groups eg acetylamino-containing benzoylamino
- C 1-20 strong rubamoyl groups eg N, N-dimethylcarbamoyl
- sulfo groups hydroxy groups, carboxyl groups Examples thereof include a ruboxy group, an alkylthio group having 1 to 20
- Ma 27 , Ma 28 , and Ma 29 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.
- Ka 23 represents an integer from 0 to 3. When Ka 23 is 2 or 3, a plurality of Ma 27 , Ma 28 and Ma 29 may be the same or different. Ka 23 is preferably both 2. Q represents a cation that neutralizes the charge.
- dyes having the structure represented by the general formula (9) those represented by the following general formulas (10), (11), (12), and (13) are particularly preferable.
- Substituents are halogen atoms, substituted or unsubstituted alkyl groups (including cycloalkyl groups and bicycloalkyl groups), substituted or unsubstituted alkyl groups (including cycloalkenyl groups and bicycloalkenyl groups), Substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, substituted or unsubstituted alkoxy group, substituted or Unsubstituted aryloxy group, substituted or unsubstituted silyloxy group, substituted or unsubstituted heterocyclicoxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted force ruberamoyloxy group, substituted or unsubstituted alkoxy Carboxyoxy group
- R represents a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group.
- a halogen atom for example, a chlorine atom, a bromine atom, an iodine atom
- an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group.
- alkyl groups preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanethyl, 2- Ethylhexyl
- a cycloalkyl group preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl
- a bicycloalkyl group preferably Is a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group in which a bicycloalkane force having 5 to 30 carbon atoms is also removed from one hydrogen atom, for example, bicyclo [1, 2, 2 ] Heptan
- Alkenyl group [Represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms). For example, bur, aryl, prenyl, galle, oleyl), cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a cycloalkene having 3 to 30 carbon atoms).
- Monovalent groups from which one hydrogen atom is removed for example, 2-cyclopentene-1-yl, 2-cyclohexene-1-yl, bicycloalkenyl groups (substituted or unsubstituted bicycloalkenes).
- a cycloalkyl group preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed.
- alkyl group preferably a substituted or unsubstituted alkyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, or trimethylsilylethyl group
- aryl group preferably a substituted or substituted group having 6 to 30 carbon atoms
- Unsubstituted aryl groups such as phenyl, p-tolyl, naphthyl, m-chlorophenol, o-hexadecanolaminophenol, heterocyclic groups (preferably 5- or 6-membered substitutions) Or a monovalent group obtained by removing one hydrogen atom from an unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic having 3 to 30 carbon atoms.
- a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted hexoxy group having 2 to 30 carbon atoms).
- Terocyclicoxy group 1-phenyltetrazole-5-oxy, 2-tetrahydroviraroxy, acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, carbon number 6 To 30 substituted or unsubstituted arylocarboxyl groups such as formyloxy Ci, acetyloxy, bivaluloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarboxoxy, rubamoyloxy group (preferably a substituted or unsubstituted C 1-30 rubamoyloxy group such as N, N dimethyl Carbamoyloxy, N, N Jetylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, N-n-octylcarbamoyloxy), alkoxycarbonyloxy group (
- amino group preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, such as amino-containing methylamino, dimethylamino-anilino, N —Methylaniline-containing diphenylamino), an acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbolumino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcoyl group having 6 to 30 carbon atoms) Amino group such as formylamino, acetylamino-containing bivaloylamino-containing lauroylamino, benzoylami-containing 3, 4, 5-tree n-octyloxyphenylcarbonylamino, aminocarbo-lamino group (preferably having 1
- an unsubstituted sulfamoyl group such as N-ethyl sulfamoyl, N— (3-dodecyloxypropyl) sulfamoyl, N, N dimethyl sulfamoyl, N-acetyl sulfamoyl, N-benzoylsulfamoyl, N— (sulfo group, Alkyl and arylsulfier groups (preferably substituted or unsubstituted alkyl Alkyl groups, 6 to 30 substituted or unsubstituted arylsulfyl groups such as methylsulfuryl, ethylsulfuryl, phenolsulfuryl, ⁇ -methylphenylsulfuryl), alkyl and arylsulfol groups ( Preferably, it is a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms,
- Aryl and heterocyclic azo groups preferably substituted or unsubstituted aryl azo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo , ⁇ -black mouth phenylazo, 5-ethylthio-1,3,4-thiadiazole-2-ylazo), imide group (preferably N-succinimide, N phthalimide), phosphino group (preferably substituted with 2 to 30 carbon atoms) Or an unsubstituted phosphino group such as dimethyl phosphide-containing diphenylphosphite-containing methylphenoxyphosphino, a phosphier group (preferably a substituted or unsubstituted phosphier group having 2 to 30 carbon atoms such as phosphinyl, Dioctyloxyphosphier, diethoxyphosphier), phosphiroxy
- R U , 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 28 is most preferably a hydrogen atom.
- R 31 , R M , R ", R 42 , R 43 , R” may be the same as the above R as a substituent, A primary atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group is preferred. Of 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.
- K a 23 each independently represents an integer of 0 to 3.
- Q represents a monovalent cation that neutralizes the charge.
- Ka 23 is 2 or 3
- a plurality of Ma 27 and Ma 28 may be the same or different.
- Oxonol dyes can be synthesized by a condensation reaction between the corresponding active methylene compound and a methine source (a compound used to introduce a methine group into a methine dye).
- a methine source a compound used to introduce a methine group into a methine dye.
- the oxonol dyes represented by the above general formulas (1) and (3) may be used alone or in combination of two or more. Further, the aforementioned oxonol dye and other dye compounds may be used in combination. Examples of the dye used in combination include azo dyes (including those complexed with metal ions), pyromethene dyes, cyanine dyes, squarylium dyes, and the like.
- dyes for use in the present invention further preferably those thermal decomposition temperature is in the range of 100 ° C ⁇ 350 ° C ⁇
- Chino force S preferably is in the range of 150 o C ⁇ 300 o C ⁇ . Further, it is preferable that the temperature is within a range of 300 ° C, such as 200 ° C force.
- the complex refractive index coefficient n (real part: bending) due to the optical properties of the amorphous film of the dye used in the recording layer ("Oxonol dye described above” or “Oxonol dye described above and dye used together with it") (Incidence factor) and k (imaginary part: extinction coefficient) are preferably 2.0 ⁇ n ⁇ 3.0 and 0.005 ⁇ k ⁇ 0.30. More preferably, 2. 1 ⁇ 2.7, 0.01.ltoreq.k ⁇ 0.15. Most preferably, 2.15 ⁇ n ⁇ 2.50, 0.03 ⁇ k ⁇ 0.10.
- the optical information recording medium of the present invention has at least two recording layers, each recording layer contains the same or different oxonol dye, and an intermediate layer is formed between the recording layers. If it is a structure, it will not specifically limit.
- the recording layer may contain a dye other than the oxonol dye.
- the layer structure is a structure in which a first recording layer, a reflective layer, and a second recording layer are formed in this order on a substrate.
- the optical information recording medium shown in FIG. 1 is a so-called bonded optical information recording medium. That is, the first laminate in which the first recording layer L0 and the reflective layer 3 are formed on the substrate 1, and the reflective layer 7, the second recording layer L1, and the protective layer or the dye protective layer 5 on the substrate 8.
- a second laminate formed with Body and force The structure is such that each recording layer is bonded to the inner layer 4 via the intermediate layer 4.
- the reflective layer 3 is translucent.
- the optical information recording medium shown in FIG. 2 is a so-called laminated optical information recording medium.
- the first recording layer L0, the reflective layer 3, the intermediate layer 4, the second recording layer Ll, the reflective layer 7, and the substrate 8 are laminated on the substrate 1 in this order.
- the reflective layer 3 is translucent.
- the substrate can be arbitrarily selected from various materials used as a substrate of a conventional information recording medium.
- the substrate material include glass; polycarbonate; acrylic resin such as polymethyl methacrylate; vinyl chloride resin such as poly salt resin and chlorinated copolymer; epoxy resin; amorphous polyolefin and polyester And may be used in combination as desired.
- These materials can be used as a film or as a rigid substrate.
- polycarbonate is preferable from the viewpoints of moisture resistance, dimensional stability and price.
- the substrate is provided with irregularities (pregroups) representing information such as tracking guide grooves or address signals.
- the track pitch of the pregroup is preferably in the range of 300 to 900 nm, more preferably 400 to 800 nm.
- the range of the depth (groove depth) of the pregroup differs between the stacked type and the bonded type. In the laminated type, the range of 100 to 200 nm is preferable, and the range of 110 to 150 nm is more preferable.
- the depth of the pre-group of the substrate close to the light incident surface is preferably in the range of 100 to 200 nm, more preferably in the range of 110 to 150 nm.
- the depth of the pre-group of the substrate far from the light incident surface is preferably lOOnm or less, more preferably 60 nm or less, and even more preferably 15 to 40 nm.
- the preferable range of the half width of the pre-group differs between the stacked type and the bonded type.
- the range is 200 to 400 nm. It is preferable.
- the half width of the pre-group of the substrate close to the light incident surface is preferably in the range of 200 to 400 nm, more preferably in the range of 230 to 380 nm. Further, the half width at the convex portion of the pre-group of the substrate far from the light incident surface is preferably in the range of 300 to 550 nm, more preferably 400 to 520 nm.
- An undercoat layer may be provided on the surface of the substrate on which the recording layer is provided for the purpose of improving flatness, improving adhesive force, and preventing alteration of the recording layer.
- the material for the undercoat layer include polymethylmethacrylate, acrylic acid 'methacrylic acid copolymer, styrene' hydrous maleic acid copolymer, polybulal alcohol, N-methylolacrylamide, and styrene 'bulutoluene.
- Polymers chlorosulfonated polyethylene, nitrocellulose, polychlorinated butyl, chlorinated polyolefin, polyester, polyimide, butyl acetate salt butyl copolymer, ethylene, butyl acetate copolymer, polyethylene, polypropylene, polycarbonate, etc.
- surface modifiers such as polymeric substances; and silane coupling agents.
- the undercoat layer is prepared by dissolving or dispersing the above substances in an appropriate solvent to prepare a coating solution, and then applying the coating solution to the substrate surface by a coating method such as spin coating, dip coating, or etching coating. It can form by apply
- a coating method such as spin coating, dip coating, or etching coating. It can form by apply
- the substrate (or the subbing layer if a subbing layer is provided) is formed with irregularities (predura loops) representing information such as tracking grooves or address signals! .
- This pre-loop is preferably formed directly on the substrate at the track pitch when a resin material such as polycarbonate is injection-molded or extruded.
- the pre-group may be formed by providing a pre-groove layer.
- a material of the pre-dalup layer a mixture of at least one monomer (or oligomer) of monoester, diester, triester and tetraester of acrylic acid and a photopolymerization initiator can be used.
- the pre-dloop layer is formed by first applying a liquid mixture comprising the above-described acrylic ester and polymerization initiator on a precisely manufactured master (stamper), and further placing a substrate on this coating liquid layer. Then, the coating layer is cured by irradiating ultraviolet rays through the substrate or the matrix, and the substrate and the coating layer are fixed. Then the substrate It can be obtained from cocoon peeling off from the mother mold.
- the oxonol dye is as described above.
- the recording layer may further contain various anti-fading agents for improving light resistance.
- anti-fading agent include metal complexes represented by the general formula (111), (IV) or (V) described in JP-A-3-224793, diimum salts, and amylum salts.
- metal complexes represented by the general formula (111), (IV) or (V) described in JP-A-3-224793 diimum salts, and amylum salts.
- diimum salts diimum salts
- amylum salts As disclosed in JP-A-2-300287, JP-A-2-300288, nitroso compounds, and TCNQ derivatives as disclosed in JP-A-10-151861 can be mentioned.
- the recording layer is formed by preparing a coating solution by dissolving the oxonol dye described above, and further, if necessary, a quencher, a binder, etc. in a solvent, and then applying the coating solution on the substrate surface in the following manner. It can be performed by forming a film and then drying it.
- Solvents in the coating solution for forming the dye recording layer include esters such as butyl acetate, ethyl lactate, and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone; dichloromethane, 1,2-dichloroethane, and black mouth Chlorinated hydrocarbons such as form; Amides such as dimethylformamide; Hydrocarbons such as cyclohexane; Ethers such as tetrahydrofuran, ethyl ether, dioxane; Ethanol, n-propanol, isopropanol, n-butanol, diacetone alcohol, etc.
- esters such as butyl acetate, ethyl lactate, and cellosolve acetate
- ketones such as methyl ethyl ketone, cyclohexanone, and methyl isobuty
- Fluorine solvents such as 2, 2, 3, 3-tetrafluoropropanol; ethylene glycol monomethyl ether, ethylene glycol monoremonoechinoleatenore, propyleneglycolinoremonomethinoreatenore, etc. No And the like can be mentioned co-ethers.
- the above solvents may be used alone or in combination of two or more in consideration of the solubility of the compound used.
- Various additives such as anti-oxidation agents, UV absorbers, plasticizers and lubricants may be added to the coating solution depending on the purpose.
- binder examples include, for example, gelatin, cellulose derivatives, dextran, rosin, and gossip.
- Natural organic polymer materials such as polyethylene; and hydrocarbon resins such as polyethylene, polypropylene, polystyrene, polyisobutylene; polysalt-bulls, polysalt-vinylidenes, polysalt-vinyls, polyacetate butls Bull resin such as copolymer; Acrylic resin such as poly (methyl acrylate) and poly (methyl methacrylate); Poly (bulb alcohol, chlorinated polyethylene, epoxy resin, petital resin, rubber derivatives, phenol formaldehyde resin And synthetic organic polymers such as an initial condensate of thermosetting rosin.
- the amount of binder used is generally 0.01 to 50 times the mass of the dye, including the oxonol dye described above (mass ratio). ), Preferably in the range of 0.1 to 5 times the mass (mass ratio).
- the pigment concentration of the coating solution thus prepared is generally in the range of 0.01 to 10% by mass, preferably in the range of 0.1 to 5% by mass.
- Examples of the coating 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 recording layer may be a single layer or a multilayer.
- the thickness of the recording layer is generally in the range of 20 to 500 nm, preferably in the range of 50 to 300 nm.
- a reflective layer is preferably provided on the recording layer for the purpose of improving the reflectance during information reproduction.
- the light-reflective material that is the material of the reflective layer is a material that has a high reflectivity for laser light. Examples include Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W. , Mn, Re, Fe, Co, Ni ⁇ Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi And metals such as metal and semi-metal or stainless steel. Of these, Cr, Ni, Pt, Cu, Ag, Au, Al, and stainless steel are preferable, and Ag is particularly preferable. These substances may be used alone or in combination of two or more or as an alloy.
- the reflective layer can be formed on the recording layer, for example, by vapor deposition, sputtering or ion plating of the reflective material.
- the thickness of the reflective layer is generally in the range of 10 to 300 nm, preferably in the range of 50 to 200 nm. It should be noted that the reflective layer is a semi-transparent reflective layer (reflective layer 3 in FIGS. 1 and 2). In this case, the layer thickness is preferably in the range of 2 to 150 nm.
- the material for the dye protective layer is as described above.
- the dye protective layer can be provided by a method such as vacuum evaporation, sputtering, or coating.
- the thickness of the dye protective layer is generally in the range of lnm to: LO ⁇ m.
- a protective layer (also referred to as a barrier layer) may be provided on the recording layer for the purpose of physically and chemically protecting the recording layer and the like.
- This protective layer may be provided on the side of the substrate where the recording layer is not provided for the purpose of enhancing scratch resistance and moisture resistance.
- Examples of materials used for the protective layer include SiO, SiO, MgF, SnO, Si N, and Zn.
- Inorganic substances such as O-GaO; such as thermoplastic resin, thermosetting resin, UV curable resin
- the protective layer can be provided by a method such as vacuum deposition, sputtering, or coating.
- a thermoplastic resin or a thermosetting resin prepare a coating solution in which these are dissolved in an appropriate solvent, then apply this coating solution and dry it. can do.
- UV curable resin it can also be formed by preparing the coating solution as it is or by dissolving it in a suitable solvent, and then applying this coating solution and curing it by irradiation with UV light. Can do.
- various additives such as an antistatic agent, an antioxidant and a UV absorber may be added according to the purpose.
- the thickness of the protective layer is generally in the range of In m to 10 ⁇ m.
- the intermediate layer is provided at least between the first recording layer and the second recording layer. Further, in the case where the optical information recording medium of the present invention is a bonded type, it also has a function of adhering two laminated bodies.
- the material for the intermediate layer examples include thermoplastic resins, thermosetting resins, electron beam curable resins, ultraviolet ray curable resins, pressure-sensitive double-sided tapes, and inorganic materials such as Si02. These materials may be used alone or in combination, and may be used as a multilayer film as well as a single layer. Such an intermediate layer is formed by spin coating, casting, or sputtering. be able to.
- the thickness of the intermediate layer is 5 to: 10 to 70 m, more preferably LOO m. All of the disclosures of Japanese applications 2005-24961, 2005-24962 and 2006-3775 are incorporated by reference into this book.
- the information recording method of the optical information recording medium of the present invention is performed, for example, as follows.
- a recording laser beam such as a semiconductor laser beam is irradiated from the substrate side while rotating the information recording medium at a constant linear velocity or a constant angular velocity.
- This light irradiation forms a cavity at the interface between the recording layer and the reflective layer (the formation of the cavity is accompanied by deformation of the recording layer or the reflective layer, or deformation of both layers), substrate
- the information is recorded when the thickness of the material changes, or the refractive index changes due to discoloration, change in association state, etc. in the recording layer.
- a semiconductor laser beam having an oscillation wavelength in the range of 600 nm to 700 nm (preferably 620 to 680 nm, more preferably 630 to 660 nm) is used.
- the information recorded as described above is reproduced by irradiating a semiconductor laser beam having the same wavelength as that during recording while rotating the information recording medium at the same constant linear velocity as described above, and then reflecting the reflected light. This can be done by detecting light.
- polycarbonate resin is formed into a substrate with a thickness of 0.570 mm and a diameter of 120 mm with a spiral group (depth 120 nm, groove width 365 nm, track pitch 0.74 m).
- a substrate for forming a recording layer was obtained.
- “Oxonol dye A” l.OOg represented by the following chemical formula was dissolved in 100 ml of 2,2,3,3-tetrafluoropropanol to prepare a coating solution. This coating solution was applied to the surface on which the group of substrates was formed by spin coating to form the first recording layer (L0).
- polycarbonate resin is made into a spiral group (depth 25nm).
- An Omm substrate was formed and used as a substrate for forming the second recording layer.
- UV curable resin (Dicure Clear SD640 manufactured by Dainippon Ink & Chemicals, Inc.) as an adhesive, the first and second laminates were bonded together so that the recording layer was the inner layer. An optical information recording medium was prepared. The intermediate layer had a thickness of 55 m.
- Spiral group of polycarbonate resin by injection molding depth 120nm, groove A substrate having a width of 365 nm, a track pitch of 0.74 m) and a thickness of 0.570 mm and a diameter of 120 mm was formed, and this was used as a substrate for forming the first recording layer.
- “Oxonol dye A” l.OOg represented by the following chemical formula was dissolved in 100 ml of 2,2,3,3-tetrafluoropropanol to prepare a coating solution. This coating solution was applied to the surface on which the group of substrates was formed by spin coating to form the first recording layer (L0).
- the polycarbonate resin is formed into a snoral group (depth 25nm by injection molding).
- a 0 mm substrate was molded and used as a substrate for forming the second recording layer.
- an AgNdCu alloy (target composition) is formed on the surface on which the group of substrates is formed.
- Oxonol dye A 2.OOg was dissolved in 100 ml of 2,2,3,3-tetrafluoropropanol to prepare a coating solution. This coating solution was applied to the surface of the substrate on which the group was formed by spin coating to form a second recording layer (L1).
- the refractive index of the second recording layer measured at 632 nm was 2.2, and the refractive index of the dye protective layer was 1 It was eight. Further, the extinction coefficient of the dye protective layer measured by an ellipsometer (model ESM-1 manufactured by ULVAC) under the condition of a wavelength of 632 ⁇ m was 0.1 or less.
- An optical information recording medium was produced in the same manner as in Example 1 except that the following comparative compound (1) was used instead of Dye A.
- An optical information recording medium was produced in the same manner as in Example 1 A except that a dye protective layer (layer thickness: 48 nm) having a SiN force was used.
- the dye protective layer had a refractive index of 1.6 and an extinction coefficient of 0.1 or less.
- Ta O target is used instead of ZnO-Ga O target.
- An optical information recording medium was produced in the same manner as in Example 1 except that 2 3 2 5 was used and a dye protective layer (layer thickness: 2.5 nm) having an acid-tantalum power was formed.
- the refractive index of the dye protective layer was 2.0, and the extinction coefficient was 0.1 or less.
- An optical information recording medium was produced in the same manner as in Example 1 except that a dye protective layer (layer thickness: 5 nm) made of niobium oxide was formed using 2 3 2 4.83.
- the dye protective layer had a refractive index of 2.3 and an extinction coefficient of 0.1 or less.
- An optical information recording medium was produced in the same manner as in Example 1-A, except that a dye protective layer was not formed.
- Example 1 A (Target composition Ag: 98.4 at%, Nd: 0.7 at%, Cu: 0.9 at%) was used to form a dye protective layer (layer thickness: 5 nm) made of Ag—Nd —Cu alloy.
- An optical information recording medium was produced in the same manner as Example 1 A except for the above.
- the refractive index of the dye protective layer is 0.2 and the extinction coefficient is 4. Met.
- An optical information recording medium was produced in the same manner as in Example 1A except that the dye protective layer was used.
- the refractive index of the dye protective layer was 1.4.
- An optical information recording medium was produced in the same manner as in Example 1-A, except that a dye protective layer was formed using a target.
- the refractive index of the dye protective layer was 2.7.
- Example 1 Examples and comparative examples using a DDU-1000 and a multi-signal generator (both manufactured by Pulstec Industrial Co., Ltd., laser wavelength: 660 nm, objective lens numerical aperture: 0.65) with a linear velocity of 9.2 m / s 8-16 modulation signals were recorded on the optical information recording medium.
- a DDU-1000 and a multi-signal generator both manufactured by Pulstec Industrial Co., Ltd., laser wavelength: 660 nm, objective lens numerical aperture: 0.65
- D Recorded signals are played back and played back using DDU-1000 (Pulstec Industries, laser wavelength: 660 nm, objective lens numerical aperture: 0.60) at a linear velocity of 3.8 mZs.
- the signal was evaluated for the optical information recording media of Example 1 and Comparative Example 1 above.
- Table 2 below shows the results of measuring the optimum recording power, reflectivity, modulation factor, jitter, and PI error for the optical information recording media of Example 1 and Comparative Example 1.
- the first recording layer (L0) and the second recording layer (L1) had good and low optimum recording power in Example 1 compared to Comparative Example 1. Further, both the first recording layer (L0) and the second recording layer (L1) were good in terms of the reflectivity and the degree of modulation in Example 1 as compared with Comparative Example 1. Further, both the first recording layer (L0) and the second recording layer (L1) had good jitter and PI error in Example 1 as compared with Comparative Example 1.
- the recorded signals of the optical information recording media obtained from Examples 1—A, 2, 3, and 4 and Comparative Example 1—A and 2 were DDU-1000 (Pulstec Industrial Co., Ltd.). Reproduction was performed at a linear velocity of 3.8 mZs using a laser wavelength of 660 nm and an objective lens numerical aperture of 0.60), and jitter was evaluated. The results are shown in Table 1-A below.
- the recording laser emission pattern (recording strategy) used was optimized for each disc.
- the laser was irradiated from the first recording layer side.
- the optical information recording media of Examples 1A, 2 to 4 and Comparative Example 1 A and 2 all have the same low jitter.
- the optical information recording media of Examples 1A and 2 to 4 had lower jitter. That is, it was proved that the optical information recording media of Examples 1-A and 2 to 4 have good signal characteristics. Further, from Table 2-A above, it was confirmed that Examples 1-A and 2-4 showed good recording characteristics.
- Example 1 and Comparative Example 1 Using the disk of Example 1 and Comparative Example 1 with DDU-1000 and a multi-signal generator (both manufactured by Pulstec Industrial Co., Ltd., laser wavelength: 660 nm, objective lens numerical aperture: 0.65), the linear velocity was 9. An 8-16 modulated signal was recorded on the optical information recording medium of Example 1 and Comparative Example 1 at 2 mZs, and the PI error at that time was measured.
- the strategies shown in Table 1 above were used for the optical information recording medium of Example 1 and Comparative Example 1.
- optical information recording media obtained from Examples 1-A and 2 to 4 and Comparative Examples 1-A and 2 were also evaluated for wet heat storage in the same manner, after signal recording.
- the optical information recording medium was kept in an environment of 80 ° C8 5% RH for 50 hours, and then PI error was measured again. Results for the optical information recording media of Examples 1-A, 2 to 4 and Comparative Example 1 A and 2 are shown in Table 3-A below.
- Example 1 and Comparative Example 1 Using the disk of Example 1 and Comparative Example 1 with a DDU-1000 and a multi-signal generator (La, pulse is manufactured by Pulstec Industrial Co., Ltd., laser wavelength: 660 nm, objective lens numerical aperture: 0.65) 8-16 modulation signals were recorded at a velocity of 9.2 mZs, and the PI error at that time was measured.
- the strategy shown in Table 1 above was used.
- polycarbonate resin is formed into a substrate with a thickness of 0.575 mm and a diameter of 120 mm with a spiral group (depth 120 nm, groove width 365 nm, track pitch 0.74 m).
- a substrate for forming a recording layer was obtained.
- a first recording layer (L0 layer) was formed by coating on the formed surface.
- an AgNdCu alloy (target composition Ag 98.4 at%: NdO. 7 at%: CuO. 9 at%) was sputtered on the first recording layer to form a transflective layer having a thickness of 13 nm.
- a laminated body having the first recording layer was obtained.
- polycarbonate resin is molded into a substrate with a thickness of 0.600mm and a diameter of 120mm having a snorted group (depth 33nm, substrate land width 450nm, track pitch 0.74m) by injection molding. This was used as a substrate for forming the second recording layer.
- an AgNdCu alloy target composition Ag98.4 at%: Nd0.7 at%: CuO. 9 at%) was sputtered onto the surface on which the substrate group was formed to form a reflective layer having a thickness of 120 nm.
- “Oxonol Dye A as described above” A coating solution in which OOg was dissolved in 100 ml of 2, 2, 3, 3-tetrafluoropropanol was prepared, and this coating solution was prepared by spin coating.
- the second recording layer (L1 layer) was formed by coating on the surface on which the group of substrates was formed.
- Ga O is deposited by RF sputtering to a thickness of 3.4 nm.
- a thin film was formed. As a result, a laminate having a second recording layer was obtained.
- the refractive index of the second recording layer (L1 layer) was 2.2.
- the refractive index of the dye protective layer was 1.8, and the extinction coefficient was 0.1 or less.
- Dye B UV curable resin (Dicure Clear SD640, manufactured by Dainippon Ink and Chemicals) is used as an adhesive, and the recording layer is composed of a laminate having the first recording layer and a laminate having the second recording layer.
- the optical information recording medium was produced by bonding so as to be an inner layer.
- the thickness of the adhesive layer (intermediate layer) was 50 / zm.
- An optical information recording medium was produced in the same manner as in Example 5 except that the thickness of the dye protective layer was changed to 6.7 nm.
- the dye protective layer had a refractive index of 1.8 and an extinction coefficient of 0.1 or less.
- An optical information recording medium was produced in the same manner as in Example 5 except that the thickness of the dye protective layer was 10. lnm.
- the refractive index of the dye protective layer is 1.8, and the extinction coefficient is 0.1 or less.
- An optical information recording medium was produced in the same manner as in Example 5 except that the thickness of the dye protective layer was 16.8 nm.
- the refractive index of the dye protective layer is 1.8, and the extinction coefficient is 0.1 or less.
- An optical information recording medium was produced in the same manner as in Example 5 except that a dye protective layer (thickness 5 nm) composed of 0 wt% was formed.
- the refractive index of the dye protective layer was and the extinction coefficient was as follows. [Evaluation of optical information recording media]
- linear velocity is 30.72 mZs
- 8-16 modulation signal was recorded only in L1.
- the recording laser emission pattern (recording strategy) used was optimized for each disc.
- the recorded signal was reproduced using the DDU-1000 (manufactured by Pulstec Inc., laser wavelength 651. On m, objective lens numerical aperture 0.60) at a linear velocity of 3.84 mZs. The signal characteristics of the L1 layer were evaluated.
- Table 5 below shows the signal characteristic evaluation results of the L1 layer in Examples 5 to 8 and the reference example.
- the reflectivity of the L1 layer almost reached the target value of 16%
- the reflectivity of the L1 layer in Examples 5 to 8 shows a good value of the target value of 16% or more. Yes.
- the other signal characteristics of the L1 layer in Examples 5 to 8 were found to be at a level that cleared the target value.
- Example 5 Example 6 Example 7 Example 8 Reference Example Dye Protective Layer
- the optical information recording medium of the present invention achieved sufficiently low jitter and PI error, and showed high reflectivity and high modulation degree in each recording layer. That is, it was confirmed that the optical information recording medium exhibited good recording characteristics. It was also confirmed that it has good fastness to light and heat.
- the optical information recording medium of the present invention can achieve stable recording / reproduction characteristics over a long period of time by containing an oxonol dye, and at least the first recording layer and the second recording layer.
- an oxonol dye By forming an intermediate layer and a Z or protective layer between them, the information signal recorded on the first recording layer and the information signal recorded on the second recording layer can be prevented from interfering with each other. Recording / reproducing signals can be obtained.
- It can be used as a heat mode type optical information recording medium such as write-once digital 'versatile' disk (DVD-R).
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Abstract
An optical information recording medium comprising a substrate and at least two layers of recording layers containing dye and formed on the substrate, characterized in that at least one kind of dye contained in a first recording layer and a second recording layer out of the at least two layers of recording layers is oxonol dye, and an intermediate layer is formed between the first recording layer and the second recording layer. An optical information recording medium comprising a pair of facing substrates, and at least two layers of recording layers formed between the pair of facing substrates, characterized in that a dye protection layer is formed adjacent to the laser-beam-incident side of at least one recording layer out of the at least two layers of recording layers, and the refractive index (n1)of the at least one recording layer and the refractive index (n2) of the dye protection layer adjacent to that recording layer satisfy the following expression (1). Expression (1): n1-0.8 < n2 < n1+0.5
Description
明 細 書 Specification
光情報記録媒体及びその製造方法 Optical information recording medium and manufacturing method thereof
技術分野 Technical field
[0001] 本発明は光情報記録媒体に関し、特に、追記型のデジタル 'バーサタイル'ディスク [0001] The present invention relates to an optical information recording medium, and more particularly to a write-once digital 'versatile' disc.
(DVD— R)のようなヒートモード型の光情報記録媒体及びその製造方法に関する。 背景技術 The present invention relates to a heat mode type optical information recording medium such as (DVD-R) and a method for manufacturing the same. Background art
[0002] 従来から、レーザー光により一回限りの情報の記録が可能な光情報記録媒体 (光 ディスク)が知られている。このような光情報記録媒体の一つとして、追記型 CD (所謂 CD-R)が挙げられる。この CD— Rは、従来の CDの作製に比べて少量の CDを手 頃な価格でしかも迅速に提供できる利点を有している。そのため、最近のパーソナル コンピュータの普及に伴ってその需要も増大している。 CD— R型の光情報記録媒体 の代表的な構造は、透明な円盤状基板上に有機色素からなる記録層、金などの金 属からなる反射層、更に榭脂製の保護層をこの順に積層したものである。 Conventionally, an optical information recording medium (optical disc) capable of recording information only once with a laser beam is known. One such optical information recording medium is a write-once CD (so-called CD-R). This CD-R has the advantage of being able to provide a small amount of CD at a reasonable price and quickly compared to conventional CD production. For this reason, the demand for personal computers has increased with the recent spread of personal computers. The typical structure of a CD-R type optical information recording medium consists of a transparent disk-shaped substrate, a recording layer made of organic dye, a reflective layer made of metal such as gold, and a protective layer made of resin in this order. Laminated.
[0003] そして、光ディスクへの情報の記録は、近赤外域のレーザー光(通常 780nm付近 の波長のレーザー光)を照射して記録層を局所的に発熱変形させることにより行われ る。一方、情報の読み取り(再生)は、通常、記録用のレーザー光と同じ波長のレー ザ一光を照射して、記録層が発熱変形された部位 (記録部分)と変形されない部位( 未記録部分)との反射率の違!ヽを検出することにより行われて!/ヽる。 [0003] Recording of information on an optical disk is performed by irradiating a near-infrared laser beam (usually a laser beam having a wavelength of approximately 780 nm) to locally generate heat and deform the recording layer. On the other hand, reading (reproducing) information is usually performed by irradiating a laser beam having the same wavelength as the recording laser beam, and the recording layer is heated and deformed (recorded part) and not deformed (unrecorded part). ) Difference in reflectance! Done by detecting spears! / Speak.
[0004] 近年、記録密度のより高い光情報記録媒体が求められている。記録密度を高める には、照射されるレーザーの光径を小さく絞ることが有効であり、また波長が短いレー ザ一光ほど小さく絞ることができるため、高密度化に有利であることが理論的に知ら れている。従って、従来力も用いられている 780nmより短波長のレーザー光を用い て記録再生を行うための光ディスクの開発が進められており、例えば、追記型デジタ ル ·バーサタイル ·ディスク(所謂 DVD— R)と称される光ディスクが上巿されて ヽる。 この光ディスクは、トラックピッチが CD— Rの 1. 6 mより狭い 0. 8 mのプレグルー ブが形成された直径 120mmあるいは直径が 80mmの透明な円盤状基板上に、色 素からなる記録層、そして通常は記録層の上に更に反射層および保護層を設けてな
るディスクを二枚、あるいはディスクと略同一寸法の円盤状保護基板とを記録層を内 層にして接着剤で貼り合わせた構造となるように製造されている。そして、 DVD-R は、可視レーザー光(通常 600nm〜700nmの範囲の波長のレーザー光)を照射す ることにより、記録及び再生が行われ、 CD— R型の光ディスクより高密度の記録が可 能であるとされる。 In recent years, an optical information recording medium having a higher recording density has been demanded. In order to increase the recording density, it is effective to reduce the light diameter of the laser to be irradiated, and it is theoretically advantageous to increase the density because one laser beam with a shorter wavelength can be reduced. Known to. Therefore, the development of optical discs for recording / reproduction using laser light having a wavelength shorter than 780 nm, which has been used in the past, has been developed. For example, write-once digital versatile discs (so-called DVD-R) The optical disc called is called up. This optical disc has a recording layer made of dye on a transparent disk-shaped substrate with a diameter of 120 mm or 80 mm with a pre-groove with a track pitch of less than 1.6 m of CD-R of 0.8 m, Usually, a reflective layer and a protective layer are not provided on the recording layer. It is manufactured to have a structure in which two discs or a disc-like protective substrate having substantially the same dimensions as the disc are bonded with an adhesive with the recording layer as an inner layer. DVD-R records and plays back by irradiating visible laser light (usually laser light with a wavelength in the range of 600 nm to 700 nm), enabling higher density recording than CD-R type optical discs. It is said that
[0005] DVD— R型の光情報記録媒体は、従来の CD— R型に比べて数倍の情報量を記 録することができるため、高い記録感度を有していることは勿論のこと、特に大量の情 報を速やかに処理する必要力 高速記録に対してもエラーの発生率が少ないことが 望まれる。また色素からなる記録層は、一般に熱、または光に対する経時的な安定 性が低いため、長期間にわたって熱、または光に対しても安定した性能を維持できる 記録層の開発が課題となっている。 [0005] The DVD-R type optical information recording medium can record information several times as much as the conventional CD-R type, and thus has high recording sensitivity. In particular, it is necessary to quickly process a large amount of information. It is desirable that the error rate be low even for high-speed recording. In addition, since a recording layer made of a dye generally has low stability over time with respect to heat or light, the development of a recording layer that can maintain stable performance against heat or light over a long period of time is an issue. .
[0006] そこで、このような課題を解消するため、ォキソノール色素力もなる記録層が基板上 に設けられた CD— R型の情報記録媒体が提案されている(例えば、特許文献 1参照 )。また、高い耐光性と耐久性を示し、良好な記録特性を発揮する光情報記録媒体を 提供するためのォキソノール色素化合物も提案されている(例えば、特許文献 2およ び 3参照)。 [0006] In order to solve such problems, a CD-R type information recording medium in which a recording layer having an oxonol coloring power is provided on a substrate has been proposed (see, for example, Patent Document 1). An oxonol dye compound has also been proposed for providing an optical information recording medium that exhibits high light resistance and durability and exhibits good recording characteristics (see, for example, Patent Documents 2 and 3).
[0007] 上記の記録層に色素を含有する光情報記録媒体は、記録層が単層であり、また、 2 層以上の記録層からなる、所謂、多層方式の追記型光ディスクを製作する場合、中 間層を形成する粘着剤や接着剤の使用により、記録層を構成する色素との接触が発 生し、記録情報の保存性に悪影響を及ぼす可能性があった。このような可能性を防 ぐために、記録層と接着層との間にバッファ層を設け、 2つの記録層を有する光情報 記録媒体が提案されて!ヽる (例えば、特許文献 4参照)。 [0007] In the optical information recording medium containing the dye in the recording layer, when a recording layer is a single layer and a so-called multi-layer write-once optical disc composed of two or more recording layers is manufactured, The use of a pressure-sensitive adhesive or an adhesive that forms the intermediate layer may cause contact with the dye constituting the recording layer, which may adversely affect the storage stability of the recorded information. In order to prevent such a possibility, an optical information recording medium having a buffer layer provided between the recording layer and the adhesive layer and having two recording layers has been proposed! Speak (see, for example, Patent Document 4).
[0008] しかし、記録層を複数有する光情報記録媒体の場合、当該バッファ層は、色素と粘 着剤や接着剤との混和を防止できる力もしれないものの、そのノ ッファ層が情報記録 の信号特性を低下する恐れがある。また、情報記録の際にジッタを適正値にするた めには、このバッファ層の光学定数を厳密に制御する必要もある。 [0008] However, in the case of an optical information recording medium having a plurality of recording layers, the buffer layer may not be able to prevent the mixing of the dye with the adhesive or the adhesive, but the buffer layer is used for the signal of information recording. There is a risk of deteriorating properties. In addition, it is necessary to strictly control the optical constant of the buffer layer in order to set the jitter to an appropriate value during information recording.
特許文献 1:特開昭 63 - 209995号公報 Patent Document 1: Japanese Patent Application Laid-Open No. 63-209995
特許文献 2:特開 2000— 52658号公報
特許文献 3:特開 2002— 249674号公報 Patent Document 2: Japanese Patent Laid-Open No. 2000-52658 Patent Document 3: Japanese Patent Laid-Open No. 2002-249674
特許文献 4:特開 2003 - 331473号公報 Patent Document 4: Japanese Patent Laid-Open No. 2003-331473
発明の開示 Disclosure of the invention
発明が解決しょうとする課題 Problems to be solved by the invention
[0009] 以上から、本発明は上記従来の課題を解決するためになされたものであり、本発明 は、色素を含有する記録層が複数層設けられ、また複数の記録層に隣接して保護層 及び Z又は中間層を設けることにより、各記録層に記録された情報信号の間の干渉 を防ぐことができ、良好な記録特性を発揮する光情報記録媒体及びその製造方法を 提供する。 [0009] As described above, the present invention has been made to solve the above-described conventional problems. In the present invention, a plurality of recording layers containing a dye are provided, and protection is provided adjacent to the plurality of recording layers. By providing a layer and Z or an intermediate layer, it is possible to prevent interference between information signals recorded on each recording layer, and to provide an optical information recording medium exhibiting good recording characteristics and a method for manufacturing the same.
課題を解決するための手段 Means for solving the problem
[0010] 上記目的は本発明の下記態様により達成される。 [0010] The above object is achieved by the following aspects of the present invention.
[0011] 本発明の第 1の態様は、基板上に、色素を含有する記録層が少なくとも 2層形成さ れ、少なくとも 2層ある前記記録層のうち、第 1の記録層および第 2の記録層に含有さ れる前記色素の少なくとも 1種がォキソノール色素であり、前記第 1の記録層と第 2の 記録層との間に中間層が形成されて!ヽることを特徴とする光情報記録媒体である。 [0011] In the first aspect of the present invention, at least two recording layers containing a dye are formed on a substrate, and the first recording layer and the second recording layer out of the recording layers having at least two layers. An optical information recording characterized in that at least one of the dyes contained in the layer is an oxonol dye, and an intermediate layer is formed between the first recording layer and the second recording layer. It is a medium.
[0012] 本発明の第 2の態様は、前記ォキソノール色素が、下記一般式(1)で表される構造 を有する第 1の態様に記載の光情報記録媒体である。 [0012] A second aspect of the present invention is the optical information recording medium according to the first aspect, wherein the oxonol dye has a structure represented by the following general formula (1).
[0013] [化 1] [0013] [Chemical 1]
上記一般式(1)中、 Za1及び Za2は各々独立に酸性核を形成する原子群を表わし、
及び Ma3は各々独立に、置換または無置換のメチン基を表わし、 kaは 0 から 3までの整数を表わし、 kaが 2以上のとき、複数存在する Ma1と Ma2は同じでも異 なってもよぐ Qは電荷を中和するイオンを表わし、 yは電荷の中和に必要な数を表わ す。
[0014] 本発明の第 3の態様は、前記基板上に、前記第 1の記録層、反射層、第 2の記録層 がこの順に形成されてなる第 1又は 2の態様に記載の光情報記録媒体である。 In the general formula (1), Za 1 and Za 2 each independently represent an atomic group that forms an acidic nucleus, And Ma 3 each independently represents a substituted or unsubstituted methine group, ka represents an integer from 0 to 3, and when ka is 2 or more, multiple Ma 1 and Ma 2 are the same or different. Mogu Q represents the ion that neutralizes the charge, and y represents the number necessary for neutralizing the charge. [0014] A third aspect of the present invention is the optical information according to the first or second aspect, wherein the first recording layer, the reflective layer, and the second recording layer are formed in this order on the substrate. It is a recording medium.
[0015] 本発明の第 4の態様は、前記一般式(1)中の Qで表されるイオンが、下記一般式 (2 )で表される構造を有する第 2又は 3の態様に記載の光情報記録媒体である。 [0015] A fourth aspect of the present invention is the method according to the second or third aspect, wherein the ion represented by Q in the general formula (1) has a structure represented by the following general formula (2). An optical information recording medium.
[0016] [化 2] [0016] [Chemical 2]
(一般式(2)中、 RU、 R12、 R14、 R15、 R16、 R"、 R19、及び R2°は、各々独立に水素原子 または、 1価の置換基を表し、 R13及び R18は、各々独立に、 1価の置換基を表す。 ) 本発明の第 5の態様は、ォキソノール色素が、下記一般式 (3)で表される構造を有 することを特徴とする前記第 2の態様に記載の光情報記録媒体である。 (In the general formula (2), R U , R 12 , R 14 , R 15 , R 16 , R ", R 19 , and R 2 ° each independently represents a hydrogen atom or a monovalent substituent, R 13 and R 18 each independently represents a monovalent substituent.) According to a fifth aspect of the present invention, the oxonol dye has a structure represented by the following general formula (3): The optical information recording medium according to the second aspect.
[0017] [化 3] [0017] [Chemical 3]
…一般式 (31 ... General formula (31
(一般式(3)中、
及び R4は、各々独立に、置換または無置換のアルキ ル基、置換または無置換のァリール基、又は置換または無置換のへテロ環基を表す カゝ、または R1と R2、又は R3と R4が、互いに結合して、環構造を形成してもよぐ R21、 R2 、 R23、 R24、 R25、 R26、
及び R3°は、各々独立に、水素原子または、置換 基をあらわす力 又は R21、 R22、 R23、 R24、 R25、 R26、 R27、 R28、 R29、及び R3°のうち、隣
接する 2つの置換基が、互いに結合し、環構造を形成してもよい。 ) (In general formula (3), And R 4 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, or R 1 and R 2 , or R 3 and R 4 may be bonded to each other to form a ring structure R 21 , R 2 , R 23 , R 24 , R 25 , R 26 , And R 3 ° each independently represents a hydrogen atom or a force representing a substituent or R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , and R 3 ° next to Two adjacent substituents may be bonded to each other to form a ring structure. )
本発明の第 6の態様は、ォキソノール色素の熱分解温度が 100°C〜350°Cの範囲 にあることを特徴とする前記第 1〜5のいずれかの態様に記載の光情報記録媒体で ある。 A sixth aspect of the present invention is the optical information recording medium according to any one of the first to fifth aspects, wherein the thermal decomposition temperature of the oxonol dye is in the range of 100 ° C to 350 ° C. is there.
[0018] 本発明の第 7の態様は、前記少なくとも一つの記録層に隣接して保護層が設けら れていることを特徴とする前記第 1〜6のいずれかの態様に記載の光情報記録媒体 である。 [0018] In a seventh aspect of the present invention, the optical information according to any one of the first to sixth aspects, wherein a protective layer is provided adjacent to the at least one recording layer. It is a recording medium.
[0019] 本発明の第 8の態様は、前記保護層の材料が、 SiO、 SiO、 MgF、 SnO、 Si N [0019] In an eighth aspect of the present invention, the material of the protective layer is SiO, SiO, MgF, SnO, Si N
2 2 2 3 4 2 2 2 3 4
、及び ZnO— Ga Oの無機物質並びに、熱可塑性榭脂、熱硬化性榭脂、及び UV , And ZnO-GaO inorganic materials, thermoplastic resins, thermosetting resins, and UV
2 3 twenty three
硬化性榭脂の有機物質力 なる群より選ばれる少なくとも 1種であることを特徴とする 前記第 7の態様に記載の光情報記録媒体である。 The optical information recording medium according to the seventh aspect, wherein the optical information recording medium is at least one selected from the group consisting of organic substance powers of curable resin.
[0020] 本発明の第 9の態様は、前記中間層が熱可塑性榭脂、熱硬化性榭脂、電子線硬 化性榭脂、紫外線硬化性榭脂、感圧式両面テープ及び Si02からなる群より選ばれ る少なくとも 1種であることを特徴とする前記第 1の態様に記載の光情報記録媒体で ある。 [0020] In a ninth aspect of the present invention, the intermediate layer comprises a thermoplastic resin, a thermosetting resin, an electron beam curable resin, an ultraviolet curable resin, a pressure-sensitive double-sided tape, and Si02. The optical information recording medium according to the first aspect, wherein the optical information recording medium is at least one selected from the above.
[0021] 本発明の第 10の態様は、 対向する一対の基板と、前記対向する一対の基板の間 に、色素を含有する 2層以上の記録層と、前記 2層以上の記録層のうち少なくとも 1つ の記録層のレーザー光が入射する側に隣接して形成された色素保護層とを含んで おり、前記少なくとも 1つの記録層の屈折率 (n )と当該記録層に隣接する前記色素 [0021] A tenth aspect of the present invention includes a pair of opposing substrates, two or more recording layers containing a dye between the opposing pair of substrates, and the two or more recording layers. A dye protective layer formed adjacent to the laser light incident side of at least one recording layer, and the refractive index (n) of the at least one recording layer and the dye adjacent to the recording layer
1 1
保護層の屈折率 (n )とが、下記式 (1)の条件を満たすことを特徴とする光情報記録 An optical information recording characterized in that the refractive index (n) of the protective layer satisfies the condition of the following formula (1):
2 2
媒体である。 It is a medium.
式(1): n -0. 8<n <n +0. 5 Formula (1): n -0. 8 <n <n +0.5
1 2 1 1 2 1
本発明の第 11の態様は、前記色素保護層を形成する材料が、無機材料であること を特徴とする前記第 10の態様に記載の光情報記録媒体である。 An eleventh aspect of the present invention is the optical information recording medium according to the tenth aspect, wherein the material forming the dye protective layer is an inorganic material.
[0022] 本発明の第 12の態様は、前記無機材料が、金属酸化物であることを特徴とする前 記第 10の態様に記載の光情報記録媒体である。 [0022] A twelfth aspect of the present invention is the optical information recording medium according to the tenth aspect, wherein the inorganic material is a metal oxide.
[0023] 本発明の第 13の態様は、前記金属酸化物が、酸化亜鉛と酸化ガリウムとの複合酸 化物、酸ィ匕タンタル、および、酸ィ匕ニオブ力 なる群力 選択される少なくとも 1種で
あることを特徴とする前記第 12の態様に記載の光情報記録媒体である。 [0023] In a thirteenth aspect of the present invention, the metal oxide is at least one selected from the group oxide consisting of a composite oxide of zinc oxide and gallium oxide, acid-tantalum, and acid-niobium force. so The optical information recording medium according to the twelfth aspect, characterized in that there is provided.
[0024] 本発明の第 14の態様は、前記金属酸化物が、酸ィ匕ガリウムであることを特徴とする 前記第 12の態様に記載の光情報記録媒体である。 [0024] A fourteenth aspect of the present invention is the optical information recording medium according to the twelfth aspect, wherein the metal oxide is gallium oxide.
[0025] 本発明の第 15の態様は、 2層方式の追記型デジタルヴアーサタイルディスクであり 当該ディスクが、レーザー光が入射する側から第 1の記録層、色素保護層および第 2の記録層を有し、前記色素保護層と第 2の記録層とが隣接しており、前記第 2の記 録層の屈折率 (n )と当該記録層に隣接する前記色素保護層の屈折率 (n )とが、前 [0025] A fifteenth aspect of the present invention is a dual-layer write-once digital versatile tile, wherein the disc has a first recording layer, a dye protective layer, and a second recording layer from the side on which laser light is incident. The dye protective layer and the second recording layer are adjacent to each other, and the refractive index (n) of the second recording layer and the refractive index of the dye protective layer adjacent to the recording layer ( n)
1 2 記式(1)の条件を満たすことを特徴とする前記第 10〜14の態様のいずれかに記載 の光情報記録媒体である。 12. The optical information recording medium according to any one of the tenth to fourteenth aspects, wherein the condition of formula (1) is satisfied.
[0026] 本発明の第 16の態様は、 前記色素が、下記一般式(1)で表されるォキソノール であることを特徴とする前記第 10の態様に記載の光情報記録媒体である。 [0026] A sixteenth aspect of the present invention is the optical information recording medium according to the tenth aspect, wherein the dye is oxonol represented by the following general formula (1).
[0027] [化 4] [0027] [Chemical 4]
(一般式(1)中、 Za1及び Za2は各々独立に酸性核を形成する原子群を表わし、 Ma1 、 及び Ma3は各々独立に、置換または無置換のメチン基を表わし、 kaは 0から 3の整数を表わし、 kaが 2以上のとき、複数存在する Ma1と Ma2は同じでも異なっても よぐ Qは電荷を中和するイオンを表わし、 yは電荷の中和に必要な数を表わす。 ) 本発明の第 17の態様は、前記一般式(1)中の Qで表されるイオンが、下記一般式 (2)で表されるォキソノールであることを特徴とする前記第 16の態様に記載の光情報 記録媒体である。 (In the general formula (1), Za 1 and Za 2 each independently represent an atomic group that forms an acidic nucleus, Ma 1 , and Ma 3 each independently represent a substituted or unsubstituted methine group, and ka is Represents an integer from 0 to 3, and when ka is 2 or more, multiple Ma 1 and Ma 2 may be the same or different Q represents an ion that neutralizes charge, and y is necessary for charge neutralization ) According to a seventeenth aspect of the present invention, the ion represented by Q in the general formula (1) is oxonol represented by the following general formula (2): An optical information recording medium according to the sixteenth aspect.
(一般式(2)中、 RU、 R12、 R"、 R15、 R16、 R"、 R19、及び R2°は、各々独立に水素原子 または、 1価の置換基を表し、 R13、 R18は、各々独立に、 1価の置換基を表す。 ) 本発明の第 18の態様は、基板上に、少なくとも 1種のォキソノールの色素を含有す る記録層を少なくとも 2層設けた光情報記録媒体の製造方法であって、 (In the general formula (2), R U , R 12 , R ″, R 15 , R 16 , R ″, R 19 , and R 2 ° each independently represents a hydrogen atom or a monovalent substituent, R 13 and R 18 each independently represent a monovalent substituent.) In an eighteenth aspect of the present invention, at least two recording layers containing at least one oxonol dye are formed on a substrate. A method of manufacturing an optical information recording medium provided,
第 1の基板上に、少なくとも 1種のォキソノールの色素を含有する記録層を少なくとも 1層設けた第 1積層体を作製する工程、 Producing a first laminate in which at least one recording layer containing at least one oxonol dye is provided on a first substrate;
第 2の基板上に、少なくとも 1種のォキソノールの色素を含有する記録層を少なくと も 1層設けた第 2積層体を作製する工程、及び Producing a second laminate in which at least one recording layer containing at least one oxonol dye is provided on the second substrate; and
前記第 1積層体と第 2積層体とを中間層を介して貼り合わせる工程 The step of bonding the first laminate and the second laminate via an intermediate layer
を含んでなる、光情報記録媒体の製造方法である。 Is a method for manufacturing an optical information recording medium.
[0029] 本発明の第 19の態様は、前記第 1積層体及び第 2積層体の少なくとも一つの積層 体の上に保護層を設ける工程を含むことを特徴とする前記第 18の態様に記載の光 情報記録媒体の製造方法である。 [0029] A nineteenth aspect of the present invention is the eighteenth aspect, comprising a step of providing a protective layer on at least one of the first laminate and the second laminate. This is a method for manufacturing an optical information recording medium.
[0030] 本発明の第 20の態様は、前記第 1積層体と第 2積層体において、少なくとも 2層の 記録層の間に中間層及び Zまたは反射層を設ける工程を含むことを特徴とする前記 第 18又は 19の態様に記載の光情報記録媒体の製造方法である。 [0030] A twentieth aspect of the present invention includes a step of providing an intermediate layer and a Z or reflective layer between at least two recording layers in the first laminated body and the second laminated body. 20. The method for producing an optical information recording medium according to the eighteenth or nineteenth aspect.
[0031] 本発明の第 21の態様は、前記第 18から 20のいずれかの態様に記載の製造方法 により作製されることを特徴とする光情報記録媒体である。 [0031] A twenty-first aspect of the present invention is an optical information recording medium manufactured by the manufacturing method according to any one of the eighteenth to twentieth aspects.
[0032] 本発明の第 22の態様は、基板上に、少なくとも 1種のォキソノールの色素を含有す る記録層を少なくとも 2層設けた光情報記録媒体の製造方法であって、 [0032] A twenty-second aspect of the present invention is a method for producing an optical information recording medium, wherein at least two recording layers containing at least one oxonol dye are provided on a substrate,
前記基板上に、すくなくとも 2層の記録層を、第 1の記録層、反射層、中間層、第 2 の記録層の順に積層することを特徴とする光情報記録媒体の製造方法である。 On the substrate, at least two recording layers are laminated in the order of a first recording layer, a reflective layer, an intermediate layer, and a second recording layer.
[0033] 本発明の第 23の態様は、前記第 22の態様に記載の製造方法により作製されること
を特徴とする光情報記録媒体である。 [0033] A twenty-third aspect of the present invention is produced by the manufacturing method according to the twenty-second aspect. An optical information recording medium characterized by the above.
発明の効果 The invention's effect
[0034] 本発明によれば、ォキソノール色素を含有する記録層が複数層設けられ、また複数 の記録層の間に中間層及び Z又は保護層を設けることにより、各記録層に記録され た情報信号の間の干渉を防ぐことができ、良好な記録特性を発揮する光情報記録媒 体を提供することができる。 According to the present invention, a plurality of recording layers containing an oxonol dye are provided, and information recorded on each recording layer is provided by providing an intermediate layer and a Z or protective layer between the plurality of recording layers. It is possible to provide an optical information recording medium that can prevent interference between signals and exhibit good recording characteristics.
図面の簡単な説明 Brief Description of Drawings
[0035] [図 1]本発明の光情報記録媒体の層構成の一例を示す概略断面図である。 FIG. 1 is a schematic cross-sectional view showing an example of a layer structure of an optical information recording medium of the present invention.
[図 2]本発明の光情報記録媒体の他の層構成の一例を示す概略断面図である。 発明を実施するための最良の形態 FIG. 2 is a schematic sectional view showing an example of another layer structure of the optical information recording medium of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION
[0036] 本発明の光情報記録媒体は、基板上に、色素を含有する記録層が少なくとも 2層 形成されている。そして、少なくとも 2層ある記録層のうち、第 1の記録層および第 2の 記録層に含有される色素として、少なくともォキソノール色素が使用されている。ォキ ソノール色素を含有させることで長期間に渡り安定した記録再生特性の維持を実現 することができる。 [0036] In the optical information recording medium of the present invention, at least two recording layers containing a dye are formed on a substrate. Of the at least two recording layers, at least an oxonol dye is used as the dye contained in the first recording layer and the second recording layer. By containing an oxonol dye, it is possible to maintain stable recording / reproduction characteristics over a long period of time.
[0037] また、少なくとも、第 1の記録層と第 2の記録層との間には中間層及び Z又は保護 層が形成されている。当該中間層及び Z又は保護層を形成することで、第 1の記録 層に記録された情報信号と第 2の記録層に記録された情報信号の干渉を防ぎ、両方 の層で良好な記録再生信号を得ることができる。なお、中間層及び Z又は保護層の 詳細については後述する。また、当該中間層及び Z又は保護層は、記録層が 3層以 上ある場合は、それぞれの層の間に形成されて ヽることが好ま 、。 [0037] Further, at least an intermediate layer and a Z or protective layer are formed between the first recording layer and the second recording layer. By forming the intermediate layer and the Z or protective layer, interference between the information signal recorded on the first recording layer and the information signal recorded on the second recording layer can be prevented, and good recording and reproduction can be performed on both layers. A signal can be obtained. The details of the intermediate layer and Z or the protective layer will be described later. In addition, when there are three or more recording layers, the intermediate layer and the Z or protective layer are preferably formed between the respective layers.
[0038] また、本発明の第 10の態様において、本発明の光情報記録媒体は、対向する一 対の基板と、対向する一対の基板の間に形成された少なくとも 2層の記録層とを有す る。具体的には、レーザー光が入射する側から第 1の記録層、色素保護層および第 2 の記録層を有し、前記色素保護層と第 2の記録層とが隣接した構成を挙げることがで きる。色素保護層が形成されていることで、記録層中の色素と粘着剤や接着剤との混 和を防ぐことができる。以下、色素保護層と隣接する記録層を第 2の記録層という。ま た、「レーザー光が入射する側」とは、光情報記録媒体 (光ディスク)における情報の
記録再生の際にレーザー光が照射される側を意味する。 [0038] In the tenth aspect of the present invention, the optical information recording medium of the present invention comprises a pair of opposing substrates and at least two recording layers formed between the pair of opposing substrates. Yes. Specifically, a configuration in which the first recording layer, the dye protective layer, and the second recording layer are provided from the laser beam incident side, and the dye protective layer and the second recording layer are adjacent to each other is exemplified. it can. By forming the dye protective layer, mixing of the dye in the recording layer with the pressure-sensitive adhesive or adhesive can be prevented. Hereinafter, the recording layer adjacent to the dye protective layer is referred to as a second recording layer. The “laser beam incident side” is the information on the optical information recording medium (optical disc). It means the side irradiated with laser light during recording / reproduction.
[0039] 色素保護層に用いられる材料としては、無機材料であることであることが好ましぐ 金属酸ィ匕物であることがより好ましい。金属酸ィ匕物としては、「酸化亜鉛と酸化ガリゥ ムとの複合酸化物(ZnO— Ga O )」、「酸化タンタル」、および「酸化ニオブ」の少なく [0039] The material used for the dye protective layer is preferably an inorganic material, more preferably a metal oxide. As metal oxides, there are few “complex oxides of zinc oxide and gallium oxide (ZnO—Ga 2 O 3)”, “tantalum oxide” and “niobium oxide”.
2 3 twenty three
ともいずれかであることが好ましい。上記列挙した金属酸ィ匕物は、色素や粘着剤、接 着剤との混和、拡散が少なぐ色素と粘着剤や接着剤との混和をより確実に、かつ、 長期にわたって防ぐことができる。また、これらの金属酸ィ匕物を用いることで、 L1の反 射率と記録レーザーパワー(記録パワー)のバランスが良くなる。さらに、上記と同様 の観点および反射率規格 (DVD+RWアライアンスが定める 2層タイプの規格)に対 し、広くマージンをかせぐためには、金属酸ィ匕物としては、酸ィ匕ガリウムであることが 好ましい。 It is preferable that either of them. The above-mentioned metal oxides can more reliably prevent the mixture of a dye, a pressure-sensitive adhesive, and an adhesive, and the mixture of a dye with a low diffusion, and a pressure-sensitive adhesive or an adhesive, over a long period of time. Also, by using these metal oxides, the balance between the reflectivity of L1 and the recording laser power (recording power) is improved. Furthermore, in order to allow a wide margin for the same viewpoint and reflectivity standard (two-layer type standard defined by the DVD + RW Alliance), the metal oxide must be acid gallium. Is preferred.
[0040] また、本発明の光情報記録媒体は、上記構成例の場合、第 2の記録層の屈折率 (n [0040] Further, in the case of the above configuration example, the optical information recording medium of the present invention has a refractive index (n
)とこの第 2の記録層と隣接する既述の色素保護層の屈折率 (n )とが、下記式(1)の ) And the refractive index (n) of the above-described dye protective layer adjacent to the second recording layer are expressed by the following formula (1):
1 2 1 2
条件を満たしている。 The condition is met.
式(1): n -0. 8<n <n +0. 5 Formula (1): n -0. 8 <n <n +0.5
1 2 1 1 2 1
「n -0. 8≥n」の場合、もしくは、 「n≥n +0. 5」の場合、ディスクからの反射率 If "n -0. 8≥n" or "n≥n +0.5", reflectivity from disc
1 2 2 1 1 2 2 1
は高くなる力 記録を行うために高パワーのレーザー光が必要となってしまう。すなわ ち、上記記録層の屈折率と色素保護層の屈折率との差が大きい場合には、記録層 In order to perform recording, a high power laser beam is required. In other words, when the difference between the refractive index of the recording layer and the refractive index of the dye protective layer is large, the recording layer
—色素保護層界面での反射が大きくなるために、反射率としては大きくなるが、逆に-Reflectivity at the dye protective layer interface increases, so the reflectivity increases.
、記録層で吸収される光が少なくなる。その結果、記録に必要なレーザーパワーが必 要となる。「n」は、「n -0. 6≤n≤n +0. 1」であることが好ましい。 , Less light is absorbed by the recording layer. As a result, the laser power necessary for recording is required. “N” is preferably “n −0. 6 ≦ n ≦ n +0.1”.
2 1 2 1 2 1 2 1
[0041] 上記式(1)を満たすには、色素保護層として既述の金属酸ィ匕物材料を用いて、ス ノ ッタリングなどの方法により、色素保護層を形成するとよいが、金属酸化物以外の 場合でも、金属窒化物、金属フッ化物などの化合物を使用して色素保護層を形成す ればよい。 In order to satisfy the above formula (1), the dye protective layer may be formed by a method such as sputtering using the above-described metal oxide material as the dye protective layer. In other cases, the dye protective layer may be formed using a compound such as a metal nitride or a metal fluoride.
[0042] また、色素保護層の消衰係数は、 0. 5以下であることが好ましぐ 0〜0. 2であるこ とがより好ましい。 0. 5以下であることで、色素保護層での光に吸収を抑制することが でき、記録再生に用いるレーザー光を有効に活用することができる。
[0043] なお、屈折率および消衰係数は、回転光子法 (エリプソメーター)で容易に計測で きる。測定装置としては、 J.A.WOOLLAM社のモデル V— VASE— Sが挙げられる [0042] Further, the extinction coefficient of the dye protective layer is preferably 0.5 or less, more preferably 0 to 0.2. When it is 0.5 or less, absorption by light in the dye protective layer can be suppressed, and laser light used for recording and reproduction can be effectively utilized. [0043] The refractive index and extinction coefficient can be easily measured by the rotating photon method (ellipsometer). JAWOOLLAM model V- VASE- S is an example of a measuring device.
[0044] 記録層は、記録及び再生に使用されるレーザー光により情報の記録及び再生が行 われる層である。特に、デジタル情報などの符号情報 (コードィ匕情報)が記録される。 記録層としては、色素記録層でも相変化型記録層でもよいが、色素記録層が好まし い。 [0044] The recording layer is a layer on which information is recorded and reproduced by a laser beam used for recording and reproduction. In particular, code information (code information) such as digital information is recorded. The recording layer may be a dye recording layer or a phase change recording layer, but a dye recording layer is preferred.
[0045] 上記記録層に含有される色素の具体例としては、シァニン色素、ォキソノール色素 、ァゾ色素、フタロシアニン色素、トリァゾール化合物(ベンゾトリアゾール化合物を含 む)、トリアジンィ匕合物、メロシア-ンィ匕合物、アミノブタジェンィ匕合物、桂皮酸化合物 、ベンゾォキサゾールイ匕合物、ピロメテンィ匕合物、スクァリリウム化合物等が挙げられ る。なお、これらは配位中心に金属原子を持っていてもよい。 Specific examples of the dye contained in the recording layer include cyanine dyes, oxonol dyes, azo dyes, phthalocyanine dyes, triazole compounds (including benzotriazole compounds), triazine compounds, merocyanine compounds. Examples thereof include compounds, aminobutadiene compounds, cinnamic acid compounds, benzoxazole compounds, pyromethene compounds, squarylium compounds, and the like. In addition, these may have a metal atom in the coordination center.
[0046] また、特開平 4— 74690号公報、特開平 8— 127174号公報、同 11 53758号公 報、同 11— 334204号公報、同 11— 334205号公報、同 11— 334206号公報、同 11— 334207号公報、特開 2000— 43423号公報、同 2000— 108513号公報、及 び同 2000— 158818号公報等に記載されている色素を用いることも可能である。 [0046] Further, JP-A-4-74690, JP-A-8-127174, JP1153758, JP11-334204, JP11-334205, JP11-334206, It is also possible to use the dyes described in JP-A Nos. 11-334207, 2000-43423, 2000-108513, 2000-158818, and the like.
[0047] 上記化合物の中では、シァニン色素、ォキソノール色素、ァゾ色素(Ni、 Co錯体を 含む)、ピロメテンィ匕合物が好ましい。 [0047] Among the above compounds, cyanine dyes, oxonol dyes, azo dyes (including Ni and Co complexes), and pyromethene compounds are preferable.
本発明の光情報記録媒体の記録層のうち、少なくとも第 1の記録層に含有される色 素として、ォキソノール色素を使用することが好ましい。ォキソノール色素を使用する ことで、高い耐光性と耐久性を示し、より良好な記録特性を発揮することができる。 Of the recording layers of the optical information recording medium of the present invention, it is preferable to use an oxonol dye as a dye contained in at least the first recording layer. By using an oxonol dye, high light resistance and durability can be exhibited, and better recording characteristics can be exhibited.
[0048] ォキソノール色素の具体例としては、 F. M. Harmer著、 Heterocyclic Compou nds― Cyanme Dyes and Related Compounds^ John&Wiley&Sons^ Ne w York, London, 1964年刊に記載のもの等が挙げられる。このようなォキソノー ル色素の中でも、本発明にお 、ては下記一般式(1)で表される構造のものが好まし い。 [0048] Specific examples of the oxonol dye include those described in F. M. Harmer, Heterocyclic Compounds-Cyanme Dyes and Related Compounds, John & Wiley & Sons New York, London, 1964. Among such oxonol dyes, those having a structure represented by the following general formula (1) are preferred in the present invention.
[0049] [化 6]
〇 [0049] [Chemical 6] Yes
…一般式 (1)
一般式(1)中、 Za1及び Za2は各々独立に酸性核を形成する原子群を表わし、 Ma1 、 Ma2、及び Ma3は各々独立に、置換または無置換のメチン基を表わし、 kaは 0から 3までの整数を表わし、 Qは電荷を中和するイオンを表わし、 yは電荷の中和に必要 な Qの数を表わす。 ... General formula (1) In general formula (1), Za 1 and Za 2 each independently represent an atomic group that forms an acidic nucleus, and Ma 1 , Ma 2 , and Ma 3 each independently represent a substituted or unsubstituted methine group, ka represents an integer from 0 to 3, Q represents an ion that neutralizes the charge, and y represents the number of Q necessary for neutralizing the charge.
[0050] Za2の具体例は、「James編、 The Theory of the Photographic Proc ess,第 4版、マクミラン社、 1977年、第 198頁」により定義される。より具体的には、ピ ラゾール一 5—オン、ビラゾリジン一 3, 5—ジオン、イミダゾリン一 5—オン、ヒダントイ ン、 2または 4 チォヒダントイン、 2—ィミノォキサゾリジン 4 オン、 2 ォキサゾリ ンー5 オン、 2 チォォキサゾリン 2, 4 ジオン、イソローダニン、ローダニン、 5, 6員の炭素環(例えばインダン 1 , 3 ジオン)、チォフェン 3 オン、チォフェン 3 オン 1 , 1 ジォキシド、インドリンー2 オン、インドリンー3 オン、 2—ォキ ソインダゾリゥム、 5, 7 ジォキソ 6, 7 ジヒドロチアゾロ〔3, 2— a〕ピリミジン、 3, 4 —ジヒドロイソキノリン一 4—オン、 1 , 3 ジォキサン一 4, 6 ジオン(例えば、メルド ラム酸)、バルビツール酸、 2 チォバルビツール酸、クマリン一 2, 4 ジオン、インダ ゾリンー 2 オン、ピリド [ 1 , 2— a]ピリミジン 1 , 3 ジオン、ピラゾ口〔1 , 5— b〕キナ ゾロン、ピラゾ口ピリドン、 3—ジシァノメチリデュル一 3—フエ-ルプロピオ-トリル、メ ルドラム酸などの核が挙げられ、好ましくは、ピラゾールー 5—オン、バルビツール酸 、 2 チォバルビツール酸、 1 , 3 ジォキサン 4, 6 ジオンである。 [0050] A specific example of Za 2 is defined by “James, The Theory of the Photographic Procedure, 4th edition, Macmillan, 1977, p. 198”. More specifically, pyrazole-1-5-one, virazolidine-1,3,5-dione, imidazoline-5-one, hydantoin, 2 or 4 thiohydantoin, 2-iminooxazolidine 4one, 2 oxazoline 5 on, 2 thoxazoline 2, 4 dione, isorhodanine, rhodanine, 5, 6 membered carbocycle (eg indan 1, 3 dione), thiophen 3 on, thiophen 3 on 1, 1 dioxide, indoline 2 on, indoline 3 on, 2-oxosoindazolium, 5,7 dioxo6,7 dihydrothiazolo [3,2-a] pyrimidine, 3,4-dihydroisoquinolinone-4-one, 1,3 dioxane-1,4,6 dione (for example, melt ram Acid), barbituric acid, 2 thiobarbituric acid, coumarin mono 2,4 dione, indazoline 2-one, pyrido [1,2-a] pyrimidine 1,3 dione , Pyrazomouth [1, 5-b] quinazolone, pyrazomouth pyridone, 3-disyanometiliduryl 3-phenolpropio-tolyl, meldrum acid, etc., preferably pyrazol-5-one , Barbituric acid, 2 thiobarbituric acid, 1,3 dioxane 4,6 dione.
[0051] Ma2、及び Ma3は各々独立に、置換または無置換のメチン基を表わす。 Ma1 、 Ma2、及び Ma3における置換基は、置換または無置換のアルキル基、置換または 無置換のアルコキシ基、置換または無置換のァリール基、置換または無置換のァリ ールォキシ基、置換または無置換のへテロ環基、ハロゲン原子、カルボキシル基、置 換または無置換のアルコキシカルボ-ル基、シァノ基、置換または無置換のァシル
基、置換または無置換の力ルバモイル基、アミノ基、置換アミノ基、スルホ基、ヒドロキ シル基、ニトロ基、置換または無置換のスルホニルァミノ基、置換または無置換のアミ ノカルボ-ルァミノ基、置換または無置換のアルキルスルホ-ル基、置換または無置 換のァリールスルホ-ル基、置換または無置換のスルフィエル基および置換または 無置換のスルファモイル基を表す。 [0051] Ma 2 and Ma 3 each independently represents a substituted or unsubstituted methine group. Substituents in Ma 1 , Ma 2 and Ma 3 are substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, substituted or unsubstituted aryloxy groups, substituted or Unsubstituted heterocyclic group, halogen atom, carboxyl group, substituted or unsubstituted alkoxycarbo group, cyano group, substituted or unsubstituted acyl Group, substituted or unsubstituted force rubamoyl group, amino group, substituted amino group, sulfo group, hydroxyl group, nitro group, substituted or unsubstituted sulfonylamino group, substituted or unsubstituted aminocarbo-lamino group, substituted Or an unsubstituted alkylsulfol group, a substituted or unsubstituted arylol group, a substituted or unsubstituted sulfiel group and a substituted or unsubstituted sulfamoyl group;
[0052] 上記置換基として好ましくは、置換または無置換の炭素数 1〜20のアルキル基、置 換または無置換の炭素数 2〜20のへテロ環基、置換または無置換の炭素数 1〜20 のアルコキシ基、置換または無置換の炭素数 6〜20のァリール基、ハロゲン原子で あり、更に好ましくは、置換または無置換の炭素数 1〜: LOのアルキル基、置換または 無置換の炭素数 1〜10のアルコキシ基、置換または無置換の炭素数 2〜 10のへテ 口環基、ハロゲン原子が好ましぐ最も好ましくは無置換の炭素数 1〜5のアルキル基 、無置換の炭素数 1〜5のアルコキシ基、置換または無置換の炭素数 2〜6のへテロ 環基およびハロゲン原子である。 [0052] Preferably, the substituent is 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 group having 1 to 2 carbon atoms. 20 alkoxy groups, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, and halogen atoms, more preferably substituted or unsubstituted carbon atoms 1 to: LO alkyl group, substituted or unsubstituted carbon numbers An alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon ring group having 2 to 10 carbon atoms, a halogen atom is most preferred, and an unsubstituted alkyl group having 1 to 5 carbon atoms and an unsubstituted carbon number An alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 6 carbon atoms and a halogen atom;
[0053]
及び Ma3は、より好ましくは、無置換のメチン基、または無置換の炭素 数 1〜5のアルキル基、無置換の炭素数 1〜5のアルコキシ基、置換または無置換の 炭素数 2〜6のへテロ環基およびハロゲン原子で置換されたメチン基である。 [0053] And Ma 3 is more preferably an unsubstituted methine group, an unsubstituted alkyl group having 1 to 5 carbon atoms, an unsubstituted alkoxy group having 1 to 5 carbon atoms, or a substituted or unsubstituted carbon number 2 to 6 And a methine group substituted with a halogen atom.
[0054] kaは 0から 3までの整数を表わし、より好ましくは 1または 2の整数を表す。 kaが 2以 上のとき、複数存在する Ma1 Ma2は同じでも異なってもよい。 Ka represents an integer of 0 to 3, more preferably an integer of 1 or 2. When ka is 2 or more, multiple Ma 1 Ma 2 may be the same or different.
[0055] ある化合物が陽イオン、陰イオンであるか、あるいは正味のイオン電荷を有するか 否かは、その化合物の置換基に依存する。一般式(1)において Qで表されるイオン は、 ££± ^色素分子の電荷に応じて、陽イオンを表す場合と、陰イオンを表す場合 があり、また、色素分子が無電荷の場合には、 Qは存在しない。 Qとして表されるィォ ンには特に制限は無ぐ無機化合物よりなるイオンであっても、有機化合物よりなるィ オンであっても構わない。また、 Qとして表されるイオンの電荷は 1価であっても多価 であっても構わない。 [0055] Whether a compound is a cation, an anion, or has a net ionic charge depends on the substituent of the compound. Depending on the charge of the dye molecule, the ion represented by Q in the general formula (1) may represent a cation or an anion, and the dye molecule may be uncharged. There is no Q. The ion represented by Q is not particularly limited and may be an ion composed of an inorganic compound or an ion composed of an organic compound. In addition, the charge of the ion represented as Q may be monovalent or polyvalent.
[0056] Qで表される陽イオンとしては、例えば、ナトリウムイオン、カリウムイオンのような金 属イオン、 4級アンモ-ゥムイオン、ォキソ -ゥムイオン、スルホ -ゥムイオン、ホスホ- ゥムイオン、セレノ -ゥムイオン、ョードニゥムイオンなどのォ-ゥムイオンが挙げられ
[0057] 一方、 Qで表される陰イオンとしては、例えば塩ィ匕物イオン、臭化物イオン、フツイ匕 物イオンのようなハロゲン陰イオン、硫酸イオン、リン酸イオン、リン酸水素イオンなど のへテロポリ酸イオン、琥珀酸イオン、マレイン酸イオン、フマル酸イオン、芳香族ジ スルホン酸イオンのような有機多価陰イオン、四フッ化ホウ酸イオン、六フッ化リン酸ィ オンが挙げられる。 [0056] Examples of the cation represented by Q include metal ions such as sodium ion and potassium ion, quaternary ammonium ion, oxo-um ion, sulfo-mu ion, phospho-mu ion, seleno-mu ion, and cation. For example, ion ions such as dawn ion. [0057] On the other hand, examples of the anion represented by Q include halogen anions such as salt chloride ions, bromide ions, and fluoride ions, sulfate ions, phosphate ions, hydrogen phosphate ions, and the like. Examples thereof include organic polyvalent anions such as telopolyacid ion, oxalate ion, maleate ion, fumarate ion and aromatic disulfonate ion, tetrafluoroborate ion and hexafluorophosphate ion.
[0058] Qで表される陽イオンとして好ましくは、ォニゥムイオンであり、更に好ましくは 4級ァ ンモニゥムイオンである。 4級アンモニゥムイオンの中でも特に好ましくは、特開 2000 - 52658号公報の一般式 (1—4)で表される 4, 4 '—ビビリジ-ゥム陽イオンおよび特 開 2002— 59652号公報に開示されて!ヽる 4, 4 '—ビビリジ-ゥム陽イオンである。 [0058] The cation represented by Q is preferably an ion, and more preferably a quaternary ammonium ion. Among the quaternary ammonium ions, the 4, 4′-bibilidium cation represented by the general formula (1-4) of JP 2000-52658 A and JP 2002-59652 A are particularly preferable. Disclosed! Speak 4, 4 '—Bibilium-cation.
[0059] 前記一般式(1)で表される色素の中でも、 Qで表されるイオンは下記一般式(2)で 表される構造であるものが好まし 、。 [0059] Among the dyes represented by the general formula (1), the ion represented by Q preferably has a structure represented by the following general formula (2).
[0060] [化 7] [0060] [Chemical 7]
一般式(2)中、 RU、 R12、 RW、 R15、 R16、 R17、 R19、及び R2°は、各々独立に水素原子 または、 1価の置換基を表し、 R13及び R18は、各々独立に、 1価の置換基を表す。 In the general formula (2), R U , R 12 , R W , R 15 , R 16 , R 17 , R 19 , and R 2 ° each independently represent a hydrogen atom or a monovalent substituent, R 13 and R 18 each independently represents a monovalent substituent.
[0061] 1価の置換基としては、ハロゲン原子、アルキル基(シクロアルキル基、ビシクロアル キル基を含む)、ァルケ-ル基(シクロアルケ-ル基、ビシクロアルケ-ル基を含む)、 アルキ-ル基、ァリール基、ヘテロ環基、シァノ基、ヒドロキシル基、ニトロ基、カルボ キシル基、アルコキシ基、ァリールォキシ基、シリルォキシ基、ヘテロ環ォキシ基、ァ シルォキシ基、力ルバモイルォキシ基、アルコキシカルボ-ルォキシ基、ァリールォ キシカルボニルォキシ、アミノ基 (ァ-リノ基を含む)、ァシルァミノ基、ァミノカルボ- ルァミノ基、アルコキシカルボ-ルァミノ基、ァリールォキシカルボ-ルァミノ基、スル ファモイルァミノ基、アルキル及びァリールスルホ -ルァミノ基、メルカプト基、アルキ
ルチオ基、ァリールチオ基、ヘテロ環チォ基、スルファモイル基、スルホ基、アルキル 及びァリールスルフィエル基、アルキル及びァリールスルホ-ル基、ァシル基、ァリー ルォキシカルボ-ル基、アルコキシカルボ-ル基、力ルバモイル基、ァリール及びへ テロ環ァゾ基、イミド基、ホスフイノ基、ホスフィエル基、ホスフィエルォキシ基、ホスフィ -ルァミノ基、シリル基が例として挙げられる。 [0061] Examples of the monovalent substituent include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), a alkenyl group (including a cycloalkyl group and a bicycloalkenyl group), an alkyl group. Group, aryl group, heterocyclic group, cyan group, hydroxyl group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic group, acyloxy group, rubamoyloxy group, alkoxycarbo-loxy group, Aryloxycarbonyloxy, amino group (including arlino group), acylamino group, aminocarbolamino group, alkoxycarbolamamino group, aryloxycarbolamamino group, sulfamoylamino group, alkyl and arylsulfolamino group , Mercapto group, alkyl Ruthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and aryl sulfier group, alkyl and arylsulfol group, acyl group, aryloxycarbonyl group, alkoxycarbole group, strong rubamoyl group And aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphier groups, phosphieroxy groups, phosphi-lamino groups, and silyl groups.
さらに詳しくは、 Ru、 R12、 R14、 R15、 R16、 R17、 R19、及び R2°は、各々独立に、ハロゲ ン原子 (例えば、塩素原子、臭素原子、ヨウ素原子)、アルキル基〔直鎖、分岐、環状 の置換もしくは無置換のアルキル基、を表す。これらは、具体的には、アルキル基 (好 ましくは炭素数 1から 30のアルキル基、例えばメチル、ェチル、 n—プロピル、イソプロ ピル、 tーブチル、 n—ォクチル、エイコシル、 2—クロロェチル、 2—シァノエチル、 2 —ェチルへキシル)、シクロアルキル基 (好ましくは、炭素数 3から 30の置換または無 置換のシクロアルキル基、例えば、シクロへキシル、シクロペンチル、 4— n—ドデシル シクロへキシル)、ビシクロアルキル基 (好ましくは、炭素数 5から 30の置換もしくは無 置換のビシクロアルキル基、つまり、炭素数 5から 30のビシクロアルカン力も水素原子 を一個取り去った一価の基である。例えば、ビシクロ [1, 2, 2]ヘプタンー2—ィル、 ビシクロ [2, 2, 2]オクタンー3 ィル)、更に環構造が多いトリシクロ構造なども包含 するものである。以下に説明する置換基の中のアルキル基 (例えばアルキルチオ基 のアルキル基)もこのような概念のアルキル基を表す。 ]、 More specifically, R u , R 12 , R 14 , R 15 , R 16 , R 17 , R 19 , and R 2 ° are each independently a halogen atom (for example, chlorine atom, bromine atom, iodine atom) And an alkyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. These are specifically alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2 —Cyanoethyl, 2 —ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), Bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a bicycloalkane force having 5 to 30 carbon atoms is a monovalent group in which one hydrogen atom is removed. For example, bicyclo [ 1, 2, 2] heptane-2-yl, bicyclo [2, 2, 2] octane-3 yl), and tricyclo structures with more ring structures A. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ],
ァルケ-ル基 [直鎖、分岐、環状の置換もしくは無置換のァルケ-ル基を表す。これ らは、ァルケ-ル基 (好ましくは炭素数 2から 30の置換または無置換のアルケニル基 、例えば、ビュル、ァリル、プレニル、ゲラ -ル、ォレイル)、シクロアルケ-ル基(好ま しくは、炭素数 3から 30の置換もしくは無置換のシクロアルケニル基、つまり、炭素数 3から 30のシクロアルケンの水素原子を一個取り去った一価の基である。例えば、 2 —シクロペンテン一 1—ィル、 2—シクロへキセン一 1—ィル)、ビシクロアルケ-ル基( 置換もしくは無置換のビシクロアルケ-ル基、好ましくは、炭素数 5から 30の置換もし くは無置換のビシクロアルケ-ル基、つまり二重結合を一個持つビシクロアルケンの 水素原子を一個取り去った一価の基である。例えば、ビシクロ [2, 2, 1]ヘプトー 2— ェン 1 ィル、ビシクロ [2, 2, 2]オタトー 2 ェンー4 ィル)を包含するものである
。 ]、 Alkenyl group [Represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. These include an alkyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as bur, aryl, prenyl, galle, oleyl), a cycloalkenyl group (preferably a carbon A substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms has been removed, such as 2 -cyclopentene 1-yl, 2 —Cyclohexene 1-yl), bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, In other words, it is a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed, for example, bicyclo [2, 2, 1] hepto-2-yl, bicyclo [2, 2, 2]. Otato 2 4 It is intended to cover the . ],
アルキ-ル基 (好ましくは、炭素数 2から 30の置換または無置換のアルキ-ル基、例 えば、ェチュル、プロパルギル、トリメチルシリルェチュル)、ァリール基 (好ましくは炭 素数 6から 30の置換もしくは無置換のァリール基、例えばフエ-ル、 p トリル、ナフ チル、 m—クロ口フエ-ル、 o へキサデカノィルァミノフエ-ル)、ヘテロ環基(好まし くは 5または 6員の置換もしくは無置換の、芳香族もしくは非芳香族のへテロ環化合 物から一個の水素原子を取り除いた一価の基であり、更に好ましくは、炭素数 3から 3 0の 5もしくは 6員の芳香族のへテロ環基である。例えば、 2 フリル、 2 チェ-ル、 2 —ピリミジ -ル、 2—ベンゾチアゾリル)、シァノ基、ヒドロキシル基、ニトロ基、カルボキ シル基、アルコキシ基 (好ましくは、炭素数 1から 30の置換もしくは無置換のアルコキ シ基、例えば、メトキシ、エトキシ、イソプロポキシ、 t ブトキシ、 n—ォクチルォキシ、 2—メトキシェトキシ)、ァリールォキシ基 (好ましくは、炭素数 6から 30の置換もしくは 無置換のァリールォキシ基、例えば、フエノキシ、 2—メチルフエノキシ、 4—tーブチ ルフエノキシ、 3 -トロフエノキシ、 2—テトラデカノィルァミノフエノキシ)、シリルォキ シ基 (好ましくは、炭素数 3から 20のシリルォキシ基、例えば、トリメチルシリルォキシ、 t—プチルジメチルシリルォキシ)、ヘテロ環ォキシ基 (好ましくは、炭素数 2から 30の 置換もしくは無置換のへテロ環ォキシ基、 1 フエ-ルテトラゾールー 5—ォキシ、 2 ーテトラヒドロビラ-ルォキシ)、ァシルォキシ基 (好ましくはホルミルォキシ基、炭素数 2から 30の置換もしくは無置換のアルキルカルボ-ルォキシ基、炭素数 6から 30の置 換もしくは無置換のァリールカルボ-ルォキシ基、例えば、ホルミルォキシ、ァセチル ォキシ、ビバロイルォキシ、ステアロイルォキシ、ベンゾィルォキシ、 p—メトキシフエ二 ルカルボ-ルォキシ)、 An alkyl group (preferably a substituted or unsubstituted alkyl group having 2 to 30 carbon atoms, such as ethul, propargyl, trimethylsilyl ether), an aryl group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms). Substituted aryl groups such as phenyl, p-tolyl, naphthyl, m-chloroform, o-hexadecanolaminophenol, heterocyclic groups (preferably 5- or 6-membered substitution) Or a monovalent group obtained by removing one hydrogen atom from an unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic having 3 to 30 carbon atoms. For example, 2 furyl, 2 chael, 2-pyrimidyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxy group, alkoxy group (preferably carbon number 1 to 30 Substituted or unsubstituted alkoxy groups such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy groups (preferably substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms) Groups such as phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-trophenoxy, 2-tetradecanoylaminophenoxy), silyloxy groups (preferably silyloxy groups having 3 to 20 carbon atoms, for example trimethylsilyl Oxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazole-5-oxy, 2-tetrahydrovira- Ruoxy), acyloxy group (preferably formyloxy group, 2 carbon atoms) 30 substituted or unsubstituted alkylcarboxoxy groups, substituted or unsubstituted aryloxycarboxyl groups having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, bivalyloxy, stearoyloxy, benzoyloxy, p-methoxyphenyl Luco-Luoxy),
力ルバモイルォキシ基 (好ましくは、炭素数 1から 30の置換もしくは無置換の力ルバ モイルォキシ基、例えば、 N, N ジメチルカルバモイルォキシ、 N, N ジェチルカ ルバモイルォキシ、モルホリノカルボニルォキシ、 N, N ジー n—ォクチルァミノカル ボニルォキシ、 N— n—ォクチルカルバモイルォキシ)、アルコキシカルボニルォキシ 基 (好ましくは、炭素数 2から 30の置換もしくは無置換アルコキシカルボニルォキシ基 、例えばメトキシカルボニルォキシ、エトキシカルボニルォキシ、 t ブトキシカルボ二
ルォキシ、 n—ォクチルカルボ-ルォキシ)、ァリールォキシカルボ-ルォキシ基(好 ましくは、炭素数 7から 30の置換もしくは無置換のァリールォキシカルボ-ルォキシ 基、例えば、フエノキシカルボ-ルォキシ、 p—メトキシフエノキシカルボ-ルォキシ、 p n へキサデシルォキシフエノキシカルボ-ルォキシ)、 Rubamoyloxy group (preferably a substituted or unsubstituted rubamoyloxy group having 1 to 30 carbon atoms, for example, N, N dimethylcarbamoyloxy, N, N jetylcarbamoyloxy, morpholinocarbonyloxy, N, N di n— Octylaminocarbonyloxy, N—n-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms such as methoxycarbonyloxy, ethoxy Carbonyloxy, t-butoxycarbonyl Roxy, n-octylcarbo-loxy), aryloxy-carboxoxy group (preferably substituted or unsubstituted aryloxycarbo-loxy group having 7 to 30 carbon atoms, such as phenoxycarbo-loxy, p —Methoxyphenoxycarboxoxy, pn hexadecyloxyphenoxycarboxoxy),
アミノ基 (好ましくは、アミノ基、炭素数 1から 30の置換もしくは無置換のアルキルアミ ノ基、炭素数 6から 30の置換もしくは無置換のァリールアミノ基、例えば、アミ入メチ ルァミノ、ジメチルアミ入ァニリノ、 N—メチル一ァニリ入ジフエニルァミノ)、ァシルァ ミノ基 (好ましくは、ホルミルアミノ基、炭素数 1から 30の置換もしくは無置換のアルキ ルカルボ-ルァミノ基、炭素数 6から 30の置換もしくは無置換のァリールカルボ-ル アミノ基、例えば、ホルミルァミノ、ァセチルアミ入ビバロイルアミ入ラウロイルァミノ、 ベンゾィルアミ入 3, 4, 5—トリー n—ォクチルォキシフエニルカルボニルァミノ)、アミ ノカルボ-ルァミノ基 (好ましくは、炭素数 1から 30の置換もしくは無置換のァミノカル ボ-ルァミノ、例えば、力ルバモイルアミ入 N, N ジメチルァミノカルボ-ルアミ入 N, N ジェチルァミノカルボ-ルアミ入モルホリノカルボ-ルァミノ)、 An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, such as amino-containing methylamino, dimethylamino-anilino, N —Methylaniline-containing diphenylamino), an acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbolumino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcoyl group having 6 to 30 carbon atoms) Amino group such as formylamino, acetylamino-containing bivaloylamino-containing lauroylamino, benzoylami-containing 3, 4, 5-tree n-octyloxyphenylcarbonylamino, aminocarbo-lamino group (preferably having 1 to 1 carbon atoms) 30 substituted or unsubstituted aminoboraminos, for example force rumomoire N, N Dimethylaminocarboleamino, N, N Jetylaminocarbole morpholinocarbolamino),
アルコキシカルボ-ルァミノ基 (好ましくは炭素数 2から 30の置換もしくは無置換アル コキシカルボ-ルァミノ基、例えば、メトキシカルボ-ルアミ入エトキシカルボ-ルアミ 入 t ブトキシカルボニルァミノ、 n—ォクタデシルォキシカルボニルアミ入 N—メチ ルーメトキシカルボ-ルァミノ)、ァリールォキシカルボ-ルァミノ基 (好ましくは、炭素 数 7から 30の置換もしくは無置換のァリールォキシカルボ-ルァミノ基、例えば、フエ ノキシカルボニルァミノ、 p クロ口フエノキシカルボニルァミノ、 m— n—ォクチルォキ シフエノキシカルボ-ルァミノ)、スルファモイルァミノ基 (好ましくは、炭素数 0から 30 の置換もしくは無置換のスルファモイルァミノ基、例えば、スルファモイルアミ入 N, N ージメチルアミノスルホニルァミノ、 N— n—ォクチルアミノスルホニルァミノ)、アルキ ル及びァリールスルホニルァミノ基 (好ましくは炭素数 1から 30の置換もしくは無置換 のアルキルスルホ -ルァミノ、炭素数 6から 30の置換もしくは無置換のァリールスルホ -ルアミ入例えば、メチルスルホ -ルアミ入ブチルスルホ -ルアミ入フエ-ルスルホ ニルアミ入 2, 3, 5 トリクロ口フエニルスルホニルアミ入 p メチルフエニルスルホニ ルァミノ)、
メルカプト基、アルキルチオ基 (好ましくは、炭素数 1から 30の置換もしくは無置換の アルキルチオ基、例えばメチルチオ、ェチルチオ、 n—へキサデシルチオ)、ァリール チォ基 (好ましくは炭素数 6から 30の置換もしくは無置換のァリールチオ、例えば、フ ェ-ルチオ、 p—クロ口フエ-ルチオ、 m—メトキシフエ-ルチオ)、ヘテロ環チォ基(好 ましくは炭素数 2から 30の置換または無置換のへテロ環チォ基、例えば、 2 ベンゾ チアゾリルチオ、 1 フエ-ルテトラゾールー 5—ィルチオ)、スルファモイル基(好まし くは炭素数 0から 30の置換もしくは無置換のスルファモイル基、例えば、 N ェチル スルファモイル、 N— (3—ドデシルォキシプロピル)スルファモイル、 N, N ジメチル スルファモイル、 N ァセチルスルファモイル、 N ベンゾィルスルファモイル、 N— ( スルホ基、アルキル及びァリールスルフィエル基 (好ましくは、炭素数 1から 30の置換 または無置換のアルキルスルフィエル基、 6から 30の置換または無置換のァリールス ルフィ-ル基、例えば、メチルスルフィ -ル、ェチルスルフィ -ル、フエ-ルスルフィ- ル、 ρ—メチルフヱ-ルスルフィ -ル)、アルキル及びァリールスルホ -ル基(好ましく は、炭素数 1から 30の置換または無置換のアルキルスルホ-ル基、 6から 30の置換 または無置換のァリールスルホ-ル基、例えば、メチルスルホ -ル、ェチルスルホ- ル、フエ-ルスルホ -ル、 p メチルフエ-ルスルホ-ル)、ァシル基(好ましくはホルミ ル基、炭素数 2から 30の置換または無置換のアルキルカルボニル基、炭素数 7から 3 0の置換もしくは無置換のァリールカルボニル基、炭素数 4から 30の置換もしくは無 置換の炭素原子でカルボ-ル基と結合しているへテロ環カルボ-ル基、例えば、ァ セチル、ピバロィル、 2—クロロアセチル、ステアロイル、ベンゾィル、 p—n—ォクチル ォキシフ ニルカルボニル、 2—ピリジルカルボニル、 2—フリルカルボニル)、 ァリールォキシカルボ-ル基 (好ましくは、炭素数 7から 30の置換もしくは無置換のァ リールォキシカルボ-ル基、例えば、フエノキシカルボ-ル、 o クロロフエノキシカル ボニル、 m—二トロフエノキシカルボニル、 p—t—ブチルフエノキシカルボニル)、アル コキシカルボニル基 (好ましくは、炭素数 2から 30の置換もしくは無置換アルコキシ力 ルボニル基、例えば、メトキシカルボ-ル、エトキシカルボ-ル、 t—ブトキシカルボ- ル、 n—ォクタデシルォキシカルボ-ル)、力ルバモイル基 (好ましくは、炭素数 1から
30の置換もしくは無置換の力ルバモイル、例えば、力ルバモイル、 N—メチルカルバ モイル、 N, N—ジメチルカルバモイル、 N, N—ジー n—ォクチルカルバモイル、 N— (メチルスルホ -ル)力ルバモイル)、 Alkoxycarbolamino group (preferably a substituted or unsubstituted alkoxycarbolamino group having 2 to 30 carbon atoms, for example, methoxycarbolami-containing ethoxycarbolami-in t-butoxycarbonylamino, n-octadecyloxycarbonyl Amino-containing N-methylmethoxycarbolamino), aryloxycarbolamino group (preferably a substituted or unsubstituted aryloxycarbolamino group having 7 to 30 carbon atoms, for example, phenylcarbonyl Amino, p-cyclophenoxycarbonylamino, m-n-octyloxyphenoxycarbolamino), sulfamoylamino group (preferably substituted or unsubstituted sulfamoyl having 0 to 30 carbon atoms) Amino groups such as N, N-dimethylaminosulfonylamino, N-n-oxy (Luminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfo-lumino having 1 to 30 carbon atoms, substituted or unsubstituted aryloylsulfo-amino having 6 to 30 carbon atoms) For example, methylsulfuramine-containing butylsulfuramide-containing phenylsulfonylamide-containing 2, 3, 5 triclonal phenylsulfonylamino-containing p-methylphenylsulfonylamino), Mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), arylthio group (preferably substituted or unsubstituted group having 6 to 30 carbon atoms) Arylthio, for example, ferthio, p-chlorophenol, m-methoxyphenol, heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms) For example, 2 benzothiazolylthio, 1-phenyltetrazol-5-ylthio), sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethyl sulfamoyl, N- (3-dodecylthio) Xypropyl) sulfamoyl, N, N dimethyl sulfamoyl, N-acetyl sulfamoyl, N benzoyl Sulfamoyl, N— (sulfo group, alkyl and aryl sulfier group (preferably a substituted or unsubstituted alkyl sulfier group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfur group having 6 to 30 carbon atoms, For example, methylsulfuryl, ethylsulfuryl, phenylsulfur, ρ-methylphenylsulfuryl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfols having 1 to 30 carbon atoms) Groups, 6 to 30 substituted or unsubstituted arylsulfonyl groups, eg methylsulfol, ethylsulfol, phenolsulfol, pmethylphenolsulfol), acyl groups (preferably formyl groups, carbon A substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylylcarbonyl group having 7 to 30 carbon atoms A heterocyclic carbocyclic group bonded to a carbocyclic group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, such as acetyl, pivalol, 2-chloroacetyl, stearoyl, benzoyl, p- n-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), aryloxycarbonyl group (preferably, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, For example, phenoxycarbon, o chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-t-butylphenoxycarbonyl), alkoxycarbonyl group (preferably substituted or unsubstituted having 2 to 30 carbon atoms) Alkoxy group carbonyl group, for example, methoxy carbonyl, ethoxy carbonyl, t-butoxy carboyl, n-octadecyloxy Carbo), rubamoyl group (preferably from 1 carbon atom) 30 substituted or non-substituted rubamoyl, for example, rubamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfol) force rubamoyl),
ァリール及びへテロ環ァゾ基 (好ましくは炭素数 6から 30の置換もしくは無置換のァリ 一ルァゾ基、炭素数 3から 30の置換もしくは無置換のへテロ環ァゾ基、例えば、フエ ニルァゾ、 ρ—クロ口フエニルァゾ、 5—ェチルチオ—1, 3, 4ーチアジアゾールー 2— ィルァゾ)、イミド基 (好ましくは、 N—スクシンイミド、 N—フタルイミド)、ホスフイノ基( 好ましくは、炭素数 2から 30の置換もしくは無置換のホスフイノ基、例えば、ジメチル ホスフィ入ジフエ-ルホスフィ入メチルフエノキシホスフイノ)、ホスフィエル基(好まし くは、炭素数 2から 30の置換もしくは無置換のホスフィエル基、例えば、ホスフィニル 、ジォクチルォキシホスフィエル、ジエトキシホスフィエル)、ホスフィエルォキシ基(好 ましくは、炭素数 2から 30の置換もしくは無置換のホスフィエルォキシ基、例えば、ジ フエノキシホスフィエルォキシ、ジォクチルォキシホスフィエルォキシ)、ホスフィエルァ ミノ基 (好ましくは、炭素数 2から 30の置換もしくは無置換のホスフィニルァミノ基、例 えば、ジメトキシホスフィエルアミ入ジメチルァミノホスフィエルアミノ)、シリル基(好ま しくは、炭素数 3から 30の置換もしくは無置換のシリル基、例えば、トリメチルシリル、 t ーブチルジメチルシリル、フエ-ルジメチルシリル)を表す。 Aryl and heterocyclic azo groups (preferably substituted or unsubstituted aryl azo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo , Ρ-black mouth phenylazo, 5-ethylthio-1,3,4-thiadiazole-2-ylazo), imide group (preferably N-succinimide, N-phthalimide), phosphino group (preferably 2 to 30 carbon atoms) Substituted or unsubstituted phosphino groups such as dimethyl phosphite-containing diphenylphosphite-containing methylphenoxyphosphino, phosphier groups (preferably 2 to 30 carbon atoms substituted or unsubstituted phosphier groups such as Phosphinyl, dioctyloxyphosphier, diethoxyphosphier), phosphieroxy group (preferably substituted with 2 to 30 carbon atoms) Or an unsubstituted phosphieroxy group, such as diphenoxyphosphieroxy, dioctyloxyphosphieroxy group, or a phosphieramino group (preferably a substituted or unsubstituted group having 2 to 30 carbon atoms) Phosphinylamino groups such as dimethoxyphosphieramino-containing dimethylaminophosphieramino, silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms such as trimethylsilyl, t- Butyldimethylsilyl, and phenyldimethylsilyl).
[0063] 上記の官能基の中で、水素原子を有するものは更に上記の基で置換されていても 良い。そのような官能基の例としては、アルキルカルボ-ルアミノスルホ -ル基、ァリ ールカルボ-ルアミノスルホ -ル基、アルキルスルホ -ルァミノカルボ-ル基、ァリー ルスルホ -ルァミノカルボ-ル基が挙げられる。その例としては、メチルスルホ -ルァ ミノカルボニル、 p—メチルフエ-ルスルホ -ルァミノカルボ-ル、ァセチルアミノスル ホ -ル、ベンゾィルアミノスルホ -ル基が挙げられる。 [0063] Among the above functional groups, those having a hydrogen atom may be further substituted with the above groups. Examples of such a functional group include an alkyl carbo- aminosulfol group, an aryl carbo-amino amino group, an alkyl sulfonylamino group, and an aryl sulfonylamino group. Examples thereof include methylsulfoaminocarbonyl, p-methylphenylsulfoluminocarbon, acetylaminosulfol, and benzoylaminosulfol groups.
[0064] RU、 R12、 R"、 R15、 R16、 R"、 R19、及び R2°は、好ましくは、全て水素原子である。 R13 及び R18はそれぞれ独立に、置換または無置換のアルキル基、置換または無置換の ァリール基、置換または無置換のへテロ環基が好ましい。その中でも、置換または無 置換のァリール基がより好ましい。更には、置換ァリール基が好ましい。 R13及び R18が 置換ァリール基である場合の置換基は、ヒドロキシル基、置換または無置換のァリー
ル基、置換または無置換のアルキル基、ハロゲン原子が好ましい。 [0064] R U , R 12 , R ", R 15 , R 16 , R", R 19 , and R 2 ° are preferably all hydrogen atoms. R 13 and R 18 are each independently preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Of these, a substituted or unsubstituted aryl group is more preferable. Furthermore, a substituted aryl group is preferable. When R 13 and R 18 are a substituted aryl group, the substituent is a hydroxyl group, a substituted or unsubstituted aryl And a substituted or unsubstituted alkyl group and a halogen atom are preferred.
本発明の光情報記録媒体において、ォキソノール色素の最も好ましい構造は、下 In the optical information recording medium of the present invention, the most preferred structure of the oxonol dye is
…一般式 (3) 一般式(3)中、
及び R4は、各々独立に、置換または無置換のアルキル 基、置換または無置換のァリール基、置換または無置換のへテロ環基を表すか、ま たは R1と R2、及び R3と R4が、互いに結合して、環構造を形成してもよぐ R21、 R22、 R23 、 R24、 R25、 R26、 R27、
R29、及び R3°は、各々独立に、水素原子または、置換基を 表すか、又は R21、 R22、 R23、 R24、 R25、 R26、
及び R3°のうち、隣接する 2 つの置換基が、互いに結合し、環構造を形成してもよい。 ... General formula (3) In general formula (3), And R 4 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or R 1 and R 2 , and R 3 And R 4 may be bonded to each other to form a ring structure R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 29 and R 3 ° each independently represents a hydrogen atom or a substituent, or R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , And R 3 °, two adjacent substituents may be bonded to each other to form a ring structure.
[0067] 置換基の例は、前述の一般式(2)の RU、 R12、 R"、 R15、 R16、 R"、 R19、及び R2。で述 ベたものを挙げることができる。 Examples of the substituent are R U , R 12 , R ″, R 15 , R 16 , R ″, R 19 , and R 2 in the general formula (2). Can be mentioned.
[0068] R21、 R22、 R23、 R24、 R25、 R26、 R27、
及び R3°は、各々独立に、水素原子、ヒ ドロキシル基、シァノ基、ハロゲン原子、置換または無置換のァリール基、置換または 無置換のアルキル基が好まし 、。 [0068] R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , And R 3 ° each independently represents a hydrogen atom, a hydroxyl group, a cyano group, a halogen atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group.
[0069] R21、 R22、 R23、 R24、 R25、 R26、 R27、
及び R3°の好まし 、例は、 R23、 R28がヒド 口キシル基で、かつ、 R22及び R27が置換または無置換のフエ-ル基であり、より好まし い例は更にその他が水素原子であるものである。 [0069] R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , And R 3 ° is preferable, for example, R 23 and R 28 are hydroxy groups, and R 22 and R 27 are substituted or unsubstituted phenol groups, and more preferable examples are further Others are hydrogen atoms.
[0070] 以下に、上記一般式(1) (上記一般式 (3)に相当する構造も含む)で表される化合 物の好ましい具体例(色素 1〜34)を挙げるが、本発明はこれらに限定されるもので
はない。なお、色素 1〜6は下記一般式 (4)の具体例であり、色素 7〜12は下記一般 式(5)の具体例であり、色素 13〜16は下記一般式 (6)の具体例であり、色素 17〜2 1は下記一般式(7)の具体例である。 [0070] Preferred specific examples (pigments 1 to 34) of the compound represented by the above general formula (1) (including the structure corresponding to the above general formula (3)) are shown below. Is limited to There is no. Dye 1-6 is a specific example of the following general formula (4), Dye 7-12 is a specific example of the following general formula (5), Dye 13-16 is a specific example of the following general formula (6) And dyes 17 to 21 are specific examples of the following general formula (7).
[化 9] [Chemical 9]
21 CH, -CH3 21 CH, -CH 3
m^] [9 oo] m ^] [9 oo]
[0077] [化 15]
[0077] [Chemical 15]
[0078] [化 16]
[0078] [Chemical 16]
なお、本発明の光情報記録媒体においては、ォキソノール色素として、他に、以下 に説明するォキソノール系色素 Aおよび Bを使用してもよい。ォキソノール色素 Aとし ては、下記一般式 (8)で表される化合物が好ま U、。 In the optical information recording medium of the present invention, oxonol dyes A and B described below may be used in addition to the oxonol dye. As the oxonol dye A, a compound represented by the following general formula (8) is preferred U.
[化 17]
[Chemical 17]
((m+2)/x)Zx+ 一般式(8)
((m + 2) / x) Z x + General formula (8)
[一般式 (8)中、 RU、 R12、 R13、及び R"はそれぞれ独立に水素原子、置換または無 置換のアルキル基、置換または無置換のァリール基、および置換または無置換のへ テロ環基のいずれかを表し、 R21、 R22、及び R3は水素原子、置換または無置換のアル キル基、置換または無置換のアルコキシ基、置換または無置換のァリール基、置換ま たは無置換のァリールォキシ基、置換または無置換のへテロ環基、ハロゲン原子、力 ルボキシル基、置換または無置換のアルコキシカルボ-ル基、シァノ基、置換または 無置換のァシル基、置換または無置換の力ルバモイル基、アミノ基、置換アミノ基、ス ルホ基、ヒドロキシル基、ニトロ基、置換または無置換のアルキルスルホ -ルァミノ基、 置換または無置換のァリールスルホ -ルァミノ基、置換または無置換の力ルバモイル アミノ基、置換または無置換のアルキルスルホ-ル基、置換または無置換のァリール スホ-ル基、置換または無置換のアルキルスルフィエル基、置換または無置換のァリ 一ルスルフィ-ル基および置換または無置換のスルファモイル基のいずれかを表し、 mは 0以上の整数を表し、 mが 2以上の場合は複数の R3は同じでも異なってもよぐ Zx +は陽イオンを表し、 Xは 1以上の整数を表す。 ] [In the general formula (8), R U , R 12 , R 13 , and R ”each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted helic group. R 21 , R 22 , and R 3 are hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, substituted or unsubstituted Is an unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a halogen atom, a force carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a cyano group, a substituted or unsubstituted acyl group, a substituted or unsubstituted Rubbamoyl group, amino group, substituted amino group, sulfo group, hydroxyl group, nitro group, substituted or unsubstituted alkylsulfo-lumino group, substituted or unsubstituted arylosulfo-lumino group, substituted Or unsubstituted rubamoyl amino group, substituted or unsubstituted alkyl sulfonyl group, substituted or unsubstituted aryl sulfonyl group, substituted or unsubstituted alkyl sulfier group, substituted or unsubstituted aryl Represents a rusulfyl 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.]
一般式 (8)の RU、 R12、 R13、及び R14はそれぞれ独立に水素原子、置換または無置 換のアルキル基、置換または無置換のァリール基、および置換または無置換のへテ 口環基のいずれかを表す。 Ru、 R12、 R13、及び R14で表される置換または無置換のァ ルキル基としては、炭素数が 1〜20のアルキル基(例えば、メチル、ェチル、プロピル 、プチル、 iーブチル、 tーブチル、 iーァミル、シクロプロピル、シクロへキシル、ベンジ ル、フエネチル)が挙げられる。また、 Ru、 R12、 R13、及び R"が各々アルキル基を表す 場合には、それらが互いに連結して炭素環(例えばシクロプロピル、シクロブチル、シ クロペンチノレ、シクロへキシノレ、 2—メチノレシクロへキシノレ、シクロへプチノレ、シクロォ クチルなど)または複素環 (例えばピペリジル、クロマ-ル、モルホリルなど)を形成し ていてもよい。 Ru、 R12、 R13、及び R14で表されるアルキル基として好ましくは、炭素数 1〜8の、鎖状アルキル基または環状アルキル基であり、最も好ましくは炭素数 1〜5 の鎖状 (直鎖状または分岐鎖状)アルキル基、 R11と R12および R13と R"がそれぞれ結 合して環をなした炭素数 1〜8の環状アルキル基 (好ましくはシクロへキシル環)、炭 素数 1〜20の置換アルキル基(例えば、ベンジル、フエネチル)である。
[0080] 一般式 (8)の Ru、 R12、 R13、及び R"で表される置換または無置換のァリール基とし ては、炭素数 6〜20のァリール基(例えば、フエ-ル、ナフチル)が挙げられる。 Ru、 R12、 R13、及び R14で表されるァリール基として好ましくは、炭素数 6〜10のァリール基 である。 R U , R 12 , R 13 , and R 14 in the general formula (8) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heter Represents any of the ring ring groups. Examples of the substituted or unsubstituted alkyl group represented by R u , R 12 , R 13 , and R 14 include an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl, butyl, i-butyl, t-butyl, i-amyl, cyclopropyl, cyclohexyl, benzyl, phenethyl). In addition, when R u , R 12 , R 13 , and R ″ each represents an alkyl group, they are connected to each other to form a carbocyclic ring (for example, cyclopropyl, cyclobutyl, cyclopentinole, cyclohexenole, 2-methinorecycloto An alkyl group represented by R u , R 12 , R 13 , and R 14, which may form a xinole, cycloheptinole, cyclooctyl, etc.) or heterocyclic ring (eg piperidyl, chromal, morpholyl, etc.) Preferably, it is a chain alkyl group or cyclic alkyl group having 1 to 8 carbon atoms, and most preferably a chain (linear or branched) alkyl group having 1 to 5 carbon atoms, R 11 and R 12 And R 13 and R "each bonded to form a cyclic alkyl group having 1 to 8 carbon atoms (preferably a cyclohexyl ring), a substituted alkyl group having 1 to 20 carbon atoms (eg, benzyl, phenethyl). In The [0080] The substituted or unsubstituted aryl group represented by R u , R 12 , R 13 , and R "in the general formula (8) is an aryl group having 6 to 20 carbon atoms (for example, a phenyl group). The aryl group represented by R u , R 12 , R 13 , and R 14 is preferably an aryl group having 6 to 10 carbon atoms.
[0081] 一般式 (8)の Ru、 R12、 R13、及び R14で表される置換または無置換のへテロ環基は 炭素原子、窒素原子、酸素原子、あるいは硫黄原子から構成される 5〜6員環の飽 和又は不飽和のヘテロ環基であり、例えばピリジル基、ピリミジル基、ピリダジル基、 ピペリジル基、トリアジル基、ピロリル基、イミダゾリル基、トリァゾリル基、フラ-ル基、 チォフ ニル基、チアゾリル基、ォキサゾリル基、イソチアゾリル基、イソォキサゾリル 基などが挙げられる。またこれらがベンゾ縮環したもの(例えばキノリル基、ベンゾイミ ダゾリル基、ベンゾチアゾリル基、ベンゾキサゾリル基など)でもよい。 Ru、 R12、 R13、 及び R14で表される置換または無置換のへテロ環基として好ましくは、炭素数 6〜: LO の置換または無置換のへテロ環基である。 [0081] R u of the general formula (8), R 12, heterocyclic group R 13, and substituted or unsubstituted to the represented by R 14 is composed of carbon atoms, nitrogen atom, oxygen atom or sulfur atom, 5- or 6-membered saturated or unsaturated heterocyclic group such as pyridyl group, pyrimidyl group, pyridazyl group, piperidyl group, triazyl group, pyrrolyl group, imidazolyl group, triazolyl group, fulleryl group, Nyl group, thiazolyl group, oxazolyl group, isothiazolyl group, isoxazolyl group and the like. In addition, these may be benzo-fused (for example, quinolyl group, benzoimidazolyl group, benzothiazolyl group, benzoxazolyl group, etc.). The substituted or unsubstituted heterocyclic group represented by R u , R 12 , R 13 , and R 14 is preferably a substituted or unsubstituted heterocyclic group having 6 to carbon atoms: LO.
[0082] 一般式 (8)の Ru、 R12、 R13、及び R"で表される置換または無置換のアルキル基、 置換または無置換のァリール基、および置換または無置換のへテロ環基の置換基と しては後述の置換基群 Sが挙げられる。 [0082] A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocycle represented by R u , R 12 , R 13 , and R "in the general formula (8) Examples of the substituent of the group include the substituent group S described later.
[0083] Sで示される置換基としては、炭素数 1〜20のアルキル基(例えば、メチル、ェチル 、プロピル、カルボキシメチル、エトキシカルボ-ルメチル)、炭素数 7〜20のァラルキ ル基(例えば、ベンジル、フエネチル)、炭素数 1〜8のアルコキシ基(例えば、メトキシ 、エトキシ)、炭業数 6〜20のァリール基(例えば、フ ニル、ナフチル)、炭素数 6〜2 0のァリールォキシ基 (例えば、フエノキシ、ナフトキシ)、ヘテロ環基 (例えば、ピリジ ル、ピリミジル、ピリダジル、ベンゾイミダゾリル、ベンゾチアゾリル、ベンゾォキサゾリル 、 2 ピロリジノン一 1—ィル、 2 ピぺリドン一 1—ィル、 2, 4 ジォキシイミダゾリジン 3 ィル、 2, 4ージォキシォキサゾリジン 3 ィル、スクシンイミド、フタルイミド、 マレイミド)、ハロゲン原子 (例えば、フッ素、塩素、臭素、沃素)、カルボキシル基、炭 素数 2〜10のアルコキシカルボ-ル基(例えば、メトキシカルボ-ル、エトキシカルボ -ル)、シァノ基、炭素教 2〜10のァシル基 (例えば、ァセチル、ビバロイル)、炭素数 1〜10の力ルバモイル(例えば、力ルバモイル、メチルカルバモイル、モルホリノカル
バモイル)、アミノ基、炭素数 1〜20の置換アミノ基 (例えば、ジメチルアミ入ジェチル アミ入ビス(メチルスルホ -ルェチル)アミ入 N—ェチルー N'—スルホェチルァミノ) 、スルホ基、ヒドロキシル基、ニトロ基、炭業数 1〜10のアルキルスルホ -ルァミノ基( 例えば、メチルスルホ -ルァミノ)、炭素数 1〜10の力ルバモイルァミノ基(例えば、力 ルバモイルアミ入メチルカルバモイルァミノ)、炭素数 1〜10のスルホ -ル基(例えば 、メタンスルホ -ル、エタンスルホ -ル)、炭素数 1〜10のスルフィエル基(例えば、メ タンスルフィエル)、および炭素数 0〜10のスルファモイル基(例えば、スルファモイル 、メタンスルファモイル)が含まれる。カルボキシル基およびスルホ基の場合にはそれ らは塩の状態であってもよい。 [0083] Examples of the substituent represented by S include an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl, carboxymethyl, ethoxycarboromethyl), and an aralkyl group having 7 to 20 carbon atoms (for example, Benzyl, phenethyl), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy), an aryl group having 6 to 20 carbons (for example, phenyl, naphthyl), an aryl group having 6 to 20 carbon atoms (for example, , Phenoxy, naphthoxy), heterocyclic groups (eg, pyridyl, pyrimidyl, pyridazyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, 2 pyrrolidinone 1-yl, 2 piperidone 1-yl, 2, 4 Dioxyimidazolidine 3 yl, 2,4-dioxoxazolidine 3 yl, succinimide, phthalimide, maleimide), halogen atoms (eg Nitrogen, chlorine, bromine, iodine), carboxyl group, C2-C10 alkoxy carbo group (e.g., methoxy carbo- yl, ethoxy carbo- yl), cyano group, carbon group 2-10 acyl group ( For example, acetyl, bivaloyl), 1-10 carbon strength rubamoyl (for example, strength rubamoyl, methylcarbamoyl, morpholinocar) Bamoyl), amino group, substituted amino group having 1 to 20 carbon atoms (for example, dimethylamino-containing jetyl, ami-containing bis (methylsulfo-ruethyl) ami-containing N-ethyl-N'-sulfoethylamino), sulfo group, hydroxyl group, Nitro group, charcoal number 1-10 alkylsulfo-lamino group (for example, methylsulfo-lamino), carbon number 1-10 strong ruberamoylamino group (for example, force rubamoylamino-containing methylcarbamoylamino), carbon number 1-10 A sulfo group (for example, methanesulfol, ethanesulfol), a sulfiel group having 1 to 10 carbon atoms (for example, methanesulfiel), and a sulfamoyl group having 0 to 10 carbon atoms (for example, sulfamoyl, methanesulfuryl). Moyl). In the case of a carboxyl group and a sulfo group, they may be in a salt state.
[0084] 一般式 (8)の R21、 R22、及び R3はそれぞれ独立に水素原子、置換または無置換の アルキル基、置換または無置換のアルコキシ基、置換または無置換のァリール基、置 換または無置換のァリールォキシ基、置換または無置換のへテロ環基、ハロゲン原 子、カルボキシル基、置換または無置換のアルコキシカルボ-ル基、シァノ基、置換 または無置換のァシル基、置換または無置換の力ルバモイル基、アミノ基、置換アミ ノ基、スルホ基、ヒドロキシル基、ニトロ基、置換または無置換のアルキルスルホ-ル アミノ基、置換または無置換の力ルバモイルァミノ基、置換または無置換のアルキル スルホ-ル基、置換または無置換のァリールスルホ-ル基、置換または無置換のス ルフィ-ル基および置換または無置換のスルファモイル基のいずれかを表す。 R21、 RIn Formula (8), R 21 , R 22 , and R 3 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 aryloxy group, substituted or unsubstituted heterocyclic group, halogen atom, carboxyl group, substituted or unsubstituted alkoxycarbo yl group, cyano group, substituted or unsubstituted acyl group, substituted or unsubstituted Substitutive force Rubamoyl group, amino group, substituted amino group, sulfo group, hydroxyl group, nitro group, substituted or unsubstituted alkyl sulfol amino group, substituted or unsubstituted force ruberamoylamino group, substituted or unsubstituted alkyl Any of sulfo group, substituted or unsubstituted aryl group, substituted or unsubstituted sulfur group and substituted or unsubstituted sulfamoyl group Represents R 21 , R
2 R3として好ましくは、水素原子、置換または無置換の炭素数 1〜20のアルキル基 、置換または無置換の炭素数 2〜20のへテロ環基、置換または無置換の炭素数 1〜 20のアルコキシ基、置換または無置換の炭素数 6〜20のァリール基、ハロゲン原子 であり、更に好ましくは、水素原子、置換または無置換の炭素数 1〜: L0のアルキル基 、置換または無置換の炭素数 1〜10のアルコキシ基、置換または無置換の炭素数 2 〜 10ヘテロ環基、ハロゲン原子が好ましぐ最も好ましくは水素原子、無置換の炭素 数 1〜5のアルキル基、無置換の炭素数 1〜5のアルコキシ基、置換または無置換の 炭素数 2〜6のへテロ環基およびノヽロゲン原子のいずれかである。 R21、 R22、及び R3 は更に置換基を有しても良ぐ置換基としては前述の置換基群 Sが挙げられる。 2 R 3 is 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 number 1 to 20 An alkoxy group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a halogen atom, more preferably a hydrogen atom, a substituted or unsubstituted carbon atom having 1 to: an L0 alkyl group, a substituted or unsubstituted carbon atom, An alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 10 carbon atoms, and most preferably a halogen atom, a hydrogen atom, an unsubstituted alkyl group having 1 to 5 carbon atoms, an unsubstituted group It is any one of an alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 6 carbon atoms, and a nitrogen atom. Examples of the substituent that R 21 , R 22 , and R 3 may further have a substituent include the substituent group S described above.
[0085] mが 0であり、 R21及び R22が両方とも水素原子であることが好ましい。また、 mが 1で
あり、 R21、 R22、及び R3がいずれも水素原子であることが好ましい。 [0085] It is preferable that m is 0, and R 21 and R 22 are both hydrogen atoms. M is 1 R 21 , R 22 , and R 3 are preferably all hydrogen atoms.
[0086] 一般式(8)の mは 0以上の整数を表し、好ましくは 0〜5 (0以上 5以下)の整数であ り、更に好ましくは 0〜3の整数であり、特に好ましくは 0〜2の整数である。 [0086] m in the general formula (8) 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. It is an integer of ~ 2.
[0087] 一般式 (8)において、上記 mが 2以上の場合、複数の R3は同じでも異なってもよぐ それぞれ独立に水素原子又は前記の置換基を表す。 In the general formula (8), 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.
[0088] 一般式 (8)において Zx+は陽イオンを表し、 Xは 1以上の整数を表す。 [0088] In the general formula (8), Z x + represents a cation, and X represents an integer of 1 or more.
[0089] Zx+で表される陽イオンとして好ましくは、第 4級アンモ-ゥムイオンであり、更に好ま しくは、特開 2000— 52658号公報の一般式 (1—4)で表される 4, 4'—ビビリジ-ゥ ム陽イオンおよび特 2002— 59652号公報に開示されている 4, 4'—ビビリジ-ゥム 陽イオンである。一般式(8)において Xは 1または 2が好ましい。 [0089] The cation represented by Z x + is preferably a quaternary ammonium ion, and more preferably 4, 4 represented by the general formula (1-4) of JP-A-2000-52658. 4'-bibilidium cations and 4,4'-bilibium cations disclosed in JP 2002-59652. In the general formula (8), X is preferably 1 or 2.
[0090] 以下に、前記一般式 (8)で表される化合物の好ましい具体例を挙げるが、本発明 はこれらに限定されるものではない。 [0090] Specific preferred examples of the compound represented by the general formula (8) are shown below, but the present invention is not limited thereto.
[0091] [化 18]
[0091] [Chemical 18]
[ΐ^ ] 600] [ΐ ^] 600]
[0095] [化 22]
[0095] [Chemical 22]
[ZZ^ [9600] [ZZ ^ [9600]
lST0C/900Zdf/X3d ζε Ζ08丽 900Ζ OAV
lST0C / 900Zdf / X3d ζε Ζ08 丽 900Ζ OAV
[0097] [化 24]
[0097] [Chemical 24]
[0098] [化 25]
[0098] [Chemical 25]
[0100] [化 27]
[0100] [Chemical 27]
[0101] [化 28]
[0101] [Chemical 28]
lST0C/900Zdf/X3d Z08丽 900Z OAV
lST0C / 900Zdf / X3d Z08 丽 900Z OAV
[οε^] [εοτο] [οε ^] [εοτο]
lSTOC/900Zdf/X3d Ζ08丽 900Ζ OAV
[τε^ ] [画] lSTOC / 900Zdf / X3d Ζ08 丽 900Ζ OAV [τε ^] [Picture]
βε^ ] [solo] βε ^] [solo]
[εε^ ] [9θΐο] [εε ^] [9θΐο]
(9£) (9 £)
次に、本発明の光情報記録媒体おいて、前記ォキソノール色素 Bとして好適な例を 挙げて説明する。当該ォキソノール色素 Bは、下記一般式 (9)で表される化合物が 好ましい。 Next, in the optical information recording medium of the present invention, a description will be given with an example suitable as the oxonol dye B. The oxonol dye B is preferably a compound represented by the following general formula (9).
[化 34] [Chemical 34]
•Q • Q
一般式 (9)中、 Za25及び Za26は、各々独立に、酸性核を形成する原子群であり、 Ma27, Ma28,及び Ma29は、各々独立に、置換または無置換のメチン基であり、 Ka23 は、 0から 3までの整数を表し、 Qは、電荷を中和する陽イオンを表す。 In general formula (9), Za 25 and Za 26 are each independently an atomic group that forms an acidic nucleus, and Ma 27 , Ma 28 , and Ma 29 are each independently a substituted or unsubstituted methine group. Where Ka 23 represents an integer from 0 to 3, and Q represents a cation that neutralizes the charge.
Za25及び Za26の例としては、 James 編、 The Theory of the Photographic P rocess、第 4版、マクミラン社、 1977年、第 198頁に記載されている。具体的には、 各々、置換されてもいてもよいピラゾール一 5—オン、ビラゾリジン一 3, 5—ジオン、ィ ミダゾリンー5 オン、ヒダントイン、 2または 4 チォヒダントイン、 2—ィミノォキサゾリ ジン 4 オン、 2—ォキサゾリン 5 オン、 2 チォォキサゾリン 2, 4 ジオン、 イソローダニン、ローダニン、チォフェン 3 オン、チォフェン 3 オン 1, 1ージ
ォキシド、インドリンー2 オン、インドリンー3 オン、 2 ォキソインダゾリゥム、 5, 7 ージォキソー 6, 7 ジヒドロチアゾロ〔3, 2— a〕ピリミジン、 3, 4ージヒドロイソキノリン 4 オン、 1, 3 ジォキサン 4, 6 ジオン(例えば、メルドラム酸など)、バルビッ ール酸、 2 チォバルビツール酸、クマリン一 2, 4 ジオン、インダゾリン 2 オン、 ピリド [1 , 2— a]ピリミジン 1, 3 ジオン、ピラゾ口〔1, 5— b〕キナゾロン、ビラゾロピ リドン、 5または 6員の炭素環(例えば、へキサン 1, 3 ジオン、ペンタン 1, 3— ジオン、インダン— 1, 3 ジオン)などの核が挙げられ、好ましくは、ピラゾール— 5— オン、バルビツール酸、 2 チォバルビツール酸、 1, 3 ジォキサン 4, 6 ジオン である。 Examples of Za 25 and Za 26 are described in James, The Theory of the Photographic Process, 4th edition, Macmillan, 1977, page 198. Specifically, pyrazol 5-one, azolidinone 3,5-dione, imidazoline-5-one, hydantoin, 2 or 4 thiohydantoin, 2-iminooxazolidin 4-one, 2— Oxazoline 5 ON, 2 Thioxazoline 2, 4 Dione, Isorhodanine, Rhodanine, Thiophene 3 ON, Thiophene 3 ON 1, 1 Oxide, Indoline-2one, Indoline-3on, 2oxoindazolium, 5,7-dioxo6,7 Dihydrothiazolo [3,2-a] pyrimidine, 3,4-dihydroisoquinoline 4on, 1,3 dioxane 4, 6 diones (eg Meldrum's acid), barbituric acid, 2 thiobarbituric acid, coumarin 1, 2, 4 dione, indazoline 2 on, pyrido [1, 2—a] pyrimidine 1, 3 dione, pyrazo mouth Nuclei such as [1,5-b] quinazolone, virazolopyridone, 5- or 6-membered carbocycles (eg, hexane 1,3 dione, pentane 1,3-dione, indan-1,3 dione), Preferred are pyrazol-5-one, barbituric acid, 2 thiobarbituric acid, 1,3 dioxane 4,6 dione.
[0108] Za25、 Za26は、各々、置換されていてもよい 1, 3 ジォキサン一 4, 6 ジオンが最も 好ましい。 [0108] Za 25 and Za 26 are each most preferably an optionally substituted 1,3 dioxane-1,4,6 dione.
[0109] 酸性核を置換する置換基は、ハロゲン原子、アルキル基 (シクロアルキル基、ビシク 口アルキル基を含む)、ァルケ-ル基(シクロアルケ-ル基、ビシクロアルケ-ル基を 含む)、アルキ-ル基、ァリール基、ヘテロ環基、シァノ基、ヒドロキシル基、ニトロ基、 カルボキシル基、アルコキシ基、ァリールォキシ基、シリルォキシ基、ヘテロ環ォキシ 基、ァシルォキシ基、力ルバモイルォキシ基、アルコキシカルボ-ルォキシ基、ァリー ルォキシカルボ-ルォキシ、アミノ基 (ァ-リノ基を含む)、ァシルァミノ基、ァミノカル ボ-ルァミノ基、アルコキシカルボ-ルァミノ基、ァリールォキシカルボ-ルァミノ基、 スルファモイルァミノ基、アルキル及びァリールスルホ -ルァミノ基、メルカプト基、ァ ルキルチオ基、ァリールチオ基、ヘテロ環チォ基、スルファモイル基、スルホ基、アル キル及びァリールスルフィエル基、アルキル及びァリールスルホ-ル基、ァシル基、 ァリールォキシカルボ-ル基、アルコキシカルボ-ル基、力ルバモイル基、ァリール 及びへテロ環ァゾ基、イミド基、ホスフイノ基、ホスフィエル基、ホスフィエルォキシ基、 ホスフィエルアミノ基、またはシリル基が例として挙げられる。その中でも、炭素数 1か ら 20の置換もしくは無置換のアルキル基、または炭素数 6から 20の置換もしくは無置 換のァリール基が好ま U、。 [0109] Substituents for substituting acidic nuclei include halogen atoms, alkyl groups (including cycloalkyl groups and bicyclic alkyl groups), alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkyls. -L group, aryl group, heterocyclic group, cyan group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic group, acyloxy group, rubermoyloxy group, alkoxycarbo-loxy group, Aryloxycarboxy, amino (including amino), acylamino, aminocarboamino, alkoxycarbolumino, aryloxycarboamino, sulfamoylamino, alkyl and arylsulfo -Luamino group, mercapto group, alkylthio group, arylthio group, heterocycle Thio group, sulfamoyl group, sulfo group, alkyl and aryl sulfier group, alkyl group and aryl sulfonyl group, acyl group, allyloxy carboxylic group, alkoxy carbo yl group, strong rubamoyl group, ar yl and hepar Examples include a telocyclic azo group, an imide group, a phosphino group, a phosphier group, a phosphieroxy group, a phosphieramino group, or a silyl group. Among them, preferred is 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.
[0110] 酸性核は、無置換または、炭素数 1から 20の置換もしくは無置換のアルキル基で置 換されたもの、炭素数 6から 20の置換もしくは無置換のァリール基で置換されたもの
が好ましい。 [0110] The acidic nucleus is 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 Is preferred.
[0111] Za25、 Za26が形成する酸性核は、好ましくは、インダンジオン、ピラゾロン、ピラゾリン ジオン、ベンゾチォフェンオンジォキシドである。その中でも、ピラゾロンが最も好まし い。 [0111] The acidic nucleus formed by Za 25 and Za 26 is preferably indandione, pyrazolone, pyrazoline dione, or benzothiophenone dioxide. Of these, pyrazolone is most preferred.
[0112] Ma27, Ma28,及び Ma29は、各々独立に、置換または無置換のメチン基であり、置換 基として好ましくは、炭素数 1から 20のアルキル基 (例えば、メチル、ェチル、イソプロ ピル)、ハロゲン原子(例えば、塩素、臭素、ヨウ素、フッ素)、炭素数 1から 20のアル コキシ基 (例えば、メトキシ、エトキシ、イソプロピル)、炭素数 6から 26のァリール基( 例えば、フエニル、 2—ナフチル)、炭素数 0から 20のへテロ環基 (例えば、 2—ピリジ ル、 3—ピリジル)、炭素数 6から 20のァリールォキシ基(例えば、フエノキシ、 1—ナフ トキシ、 2—ナフトキシ)、炭素数 1から 20のァシルァミノ基 (例えばァセチルアミ入ベ ンゾィルァミノ)、炭素数 1から 20の力ルバモイル基(例えば N, N—ジメチルカルバモ ィル)、スルホ基、ヒドロキシ基、カルボキシ基、炭素数 1から 20のアルキルチオ基 (例 えばメチルチオ)、シァノ基などが挙げられる。また、他のメチン基と結合して環構造 を形成してもよぐ Za25から Za26で表される原子団と結合して環構造を形成してもよい [0112] Ma 27 , Ma 28 , and Ma 29 are each independently a substituted or unsubstituted methine group, preferably an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, isopropyl). Pyr), halogen atoms (eg, chlorine, bromine, iodine, fluorine), alkoxy groups having 1 to 20 carbon atoms (eg, methoxy, ethoxy, isopropyl), aryl groups having 6 to 26 carbon atoms (eg, phenyl, 2 —Naphthyl), a heterocyclic group having 0 to 20 carbon atoms (eg, 2-pyridyl, 3-pyridyl), an aryloxy group having 6 to 20 carbon atoms (eg, phenoxy, 1-naphthoxy, 2-naphthoxy), C 1-20 acylamine groups (eg acetylamino-containing benzoylamino), C 1-20 strong rubamoyl groups (eg N, N-dimethylcarbamoyl), sulfo groups, hydroxy groups, carboxyl groups Examples thereof include a ruboxy group, an alkylthio group having 1 to 20 carbon atoms (eg, methylthio), and a cyan group. It may be combined with other methine groups to form a ring structure. It may be combined with an atomic group represented by Za 25 to Za 26 to form a ring structure.
[0113] Ma27, Ma28,及び Ma29は、各々独立に、好ましくは無置換、ェチル基、メチル基、 フエニル基で置換されたメチン基のいずれかである。最も好ましくは、無置換のメチン 基である。 [0113] Ma 27 , Ma 28 , and Ma 29 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.
[0114] Ka23は、 0から 3までの整数を表す。 Ka23が 2または 3であるとき、複数存在する Ma27 、 Ma28, Ma29は、同じでも異なっていてもよい。 Ka23は、共に 2であるものが好ましい。 Qは、電荷を中和する陽イオンを表す。 [0114] Ka 23 represents an integer from 0 to 3. When Ka 23 is 2 or 3, a plurality of Ma 27 , Ma 28 and Ma 29 may be the same or different. Ka 23 is preferably both 2. Q represents a cation that neutralizes the charge.
[0115] 一般式 (9)で表される構造の色素のうち、特に、下記一般式(10)、(11)、(12)、 ( 13)で表されるものが好ましい。 Of the dyes having the structure represented by the general formula (9), those represented by the following general formulas (10), (11), (12), and (13) are particularly preferable.
Q Q
•Q • Q
一般式(10)、(11)、 (12)、及び(13)中、1^、1^2、1^3、1^4、1^5、1^6、1^7、1^、1^
R32、 R33 (以上を「R」と表示することあり)は、各 々独立に、水素原子または、置換基を表す。置換基は、ハロゲン原子、置換もしくは 無置換のアルキル基 (シクロアルキル基、ビシクロアルキル基を含む)、置換もしくは 無置換のァルケ-ル基(シクロアルケ-ル基、ビシクロアルケ-ル基を含む)、置換も しくは無置換のアルキニル基、置換もしくは無置換のァリール基、置換もしくは無置 換のヘテロ環基、シァノ基、ヒドロキシル基、ニトロ基、カルボキシル基、置換もしくは 無置換のアルコキシ基、置換もしくは無置換のァリールォキシ基、置換もしくは無置 換のシリルォキシ基、置換もしくは無置換のへテロ環ォキシ基、置換もしくは無置換 のァシルォキシ基、置換もしくは無置換の力ルバモイルォキシ基、置換もしくは無置 換のアルコキシカルボ-ルォキシ基、置換もしくは無置換のァリールォキシカルボ-
ルォキシ、置換もしくは無置換のアミノ基 (ァニリノ基を含む)、置換もしくは無置換の ァシルァミノ基、置換もしくは無置換のァミノカルボ-ルァミノ基、置換もしくは無置換 のアルコキシカルボ-ルァミノ基、置換もしくは無置換のァリールォキシカルボ-ルァ ミノ基、置換もしくは無置換のスルファモイルァミノ基、置換もしくは無置換のアルキル 及びァリールスルホニルァミノ基、置換もしくは無置換のメルカプト基、置換もしくは無 置換のアルキルチオ基、置換もしくは無置換のァリールチオ基、置換または無置換 のへテロ環チォ基、置換または無置換のスルファモイル基、スルホ基、置換もしくは 無置換のアルキル及びァリールスルフィエル基、置換もしくは無置換のアルキル及び ァリールスルホニル基、置換もしくは無置換のァシル基、置換もしくは無置換のァリー ルォキシカルボ-ル基、置換もしくは無置換のアルコキシカルボ-ル基、置換または 無置換の力ルバモイル基、置換または無置換のァリール及びへテロ環ァゾ基、置換 もしくは無置換のイミド基、置換もしくは無置換のホスフイノ基、置換もしくは無置換の ホスフィエル基、置換もしくは無置換のホスフィエルォキシ基、置換もしくは無置換の ホスフィエルアミノ基、または置換もしくは無置換のシリル基が例として挙げられる。 更に詳しくは、 Rは、ハロゲン原子 (例えば、塩素原子、臭素原子、ヨウ素原子)、ァ ルキル基〔直鎖、分岐、環状の置換もしくは無置換のアルキル基を表す。それらは、 アルキル基 (好ましくは炭素数 1から 30のアルキル基、例えばメチル、ェチル、 n—プ 口ピル、イソプロピル、 t—ブチル、 n—ォクチル、エイコシル、 2—クロロェチル、 2— シァノエチル、 2—ェチルへキシル)、シクロアルキル基(好ましくは、炭素数 3から 30 の置換または無置換のシクロアルキル基、例えば、シクロへキシル、シクロペンチル、 4—n—ドデシルシクロへキシル)、ビシクロアルキル基(好ましくは、炭素数 5から 30 の置換もしくは無置換のビシクロアルキル基、つまり、炭素数 5から 30のビシクロアル カン力も水素原子を一個取り去った一価の基である。例えば、ビシクロ [1, 2, 2]ヘプ タン一 2—ィル、ビシクロ [2, 2, 2]オクタン一 3—ィル)、更に環構造が多いトリシクロ 構造なども包含するものである。以下に説明する置換基の中のアルキル基 (例えばァ ルキルチオ基のアルキル基)もこのような概念のアルキル基を表す。 ]、 In general formulas (10), (11), (12), and (13), 1 ^, 1 ^ 2 , 1 ^ 3 , 1 ^ 4 , 1 ^ 5 , 1 ^ 6 , 1 ^ 7 , 1 ^, 1 ^ R 32 and R 33 (the above may be expressed as “R”) each independently represents a hydrogen atom or a substituent. Substituents are halogen atoms, substituted or unsubstituted alkyl groups (including cycloalkyl groups and bicycloalkyl groups), substituted or unsubstituted alkyl groups (including cycloalkenyl groups and bicycloalkenyl groups), Substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, substituted or unsubstituted alkoxy group, substituted or Unsubstituted aryloxy group, substituted or unsubstituted silyloxy group, substituted or unsubstituted heterocyclicoxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted force ruberamoyloxy group, substituted or unsubstituted alkoxy Carboxyoxy group, substituted or unsubstituted aryloxycarbo- Roxy, substituted or unsubstituted amino group (including an anilino group), substituted or unsubstituted acylamino group, substituted or unsubstituted aminocarbolamamino group, substituted or unsubstituted alkoxycarbolamino group, substituted or unsubstituted Aryloxycarboamino groups, substituted or unsubstituted sulfamoylamino groups, substituted or unsubstituted alkyl and arylarylsulfonylamino groups, substituted or unsubstituted mercapto groups, substituted or unsubstituted alkylthio Group, substituted or unsubstituted arylothio group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted sulfamoyl group, sulfo group, substituted or unsubstituted alkyl and arylsulfur group, substituted or unsubstituted Alkyl and arylsulfonyl groups, substituted or unsubstituted An acyl group, a substituted or unsubstituted aryloxycarbon group, a substituted or unsubstituted alkoxycarbo group, a substituted or unsubstituted rubamoyl group, a substituted or unsubstituted aryl and heterocyclic azo group, a substituted or Unsubstituted imide group, substituted or unsubstituted phosphino group, substituted or unsubstituted phosphier group, substituted or unsubstituted phosphieroxy group, substituted or unsubstituted phosphieramino group, or substituted or unsubstituted silyl group Examples are the groups. More specifically, R represents a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanethyl, 2- Ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably Is a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group in which a bicycloalkane force having 5 to 30 carbon atoms is also removed from one hydrogen atom, for example, bicyclo [1, 2, 2 ] Heptane-2-yl, bicyclo [2,2,2] octane-3-yl), and tricyclo structures with many ring structures. An alkyl group (for example, an alkyl group of an alkylthio group) in a substituent described below also represents such an alkyl group. ],
ァルケ-ル基 [直鎖、分岐、環状の置換もしくは無置換のァルケ-ル基を表す。それ らは、ァルケ-ル基 (好ましくは炭素数 2から 30の置換または無置換のアルケニル基
、例えば、ビュル、ァリル、プレニル、ゲラ -ル、ォレイル)、シクロアルケ-ル基(好ま しくは、炭素数 3から 30の置換もしくは無置換のシクロアルケニル基、つまり、炭素数 3から 30のシクロアルケンの水素原子を一個取り去った一価の基である。例えば、 2 —シクロペンテン一 1—ィル、 2—シクロへキセン一 1—ィル)、ビシクロアルケ-ル基( 置換もしくは無置換のビシクロアルケ-ル基、好ましくは、炭素数 5から 30の置換もし くは無置換のビシクロアルケ-ル基、つまり二重結合を一個持つビシクロアルケンの 水素原子を一個取り去った一価の基である。例えば、ビシクロ [2, 2, 1]ヘプトー 2— ェン 1 ィル、ビシクロ [2, 2, 2]オタトー 2 ェンー4 ィル)を包含するものである 。 ]、 Alkenyl group [Represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms). For example, bur, aryl, prenyl, galle, oleyl), cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a cycloalkene having 3 to 30 carbon atoms). Monovalent groups from which one hydrogen atom is removed, for example, 2-cyclopentene-1-yl, 2-cyclohexene-1-yl, bicycloalkenyl groups (substituted or unsubstituted bicycloalkenes). A cycloalkyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed. , Bicyclo [2,2,1] heptoe-2-yl, bicyclo [2,2,2] otatoe2-enil). ],
アルキ-ル基 (好ましくは、炭素数 2から 30の置換または無置換のアルキ-ル基、例 えば、ェチニル、プロパルギル、トリメチルシリルェチュル基)、ァリール基 (好ましくは 炭素数 6から 30の置換もしくは無置換のァリール基、例えばフエ-ル、 p トリル、ナ フチル、 m—クロ口フエ-ル、 o へキサデカノィルァミノフエ-ル)、ヘテロ環基(好ま しくは 5または 6員の置換もしくは無置換の、芳香族もしくは非芳香族のへテロ環化合 物から一個の水素原子を取り除いた一価の基であり、更に好ましくは、炭素数 3から 3 0の 5もしくは 6員の芳香族のへテロ環基である。例えば、 2 フリル、 2 チェ-ル、 2 —ピリミジ -ル、 2—ベンゾチアゾリル)、シァノ基、ヒドロキシル基、ニトロ基、カルボキ シル基、アルコキシ基 (好ましくは、炭素数 1から 30の置換もしくは無置換のアルコキ シ基、例えば、メトキシ、エトキシ、イソプロポキシ、 t ブトキシ、 n—ォクチルォキシ、 2—メトキシェトキシ)、ァリールォキシ基 (好ましくは、炭素数 6から 30の置換もしくは 無置換のァリールォキシ基、例えば、フエノキシ、 2—メチルフエノキシ、 4—tーブチ ルフエノキシ、 3 -トロフエノキシ、 2—テトラデカノィルァミノフエノキシ)、 An alkyl group (preferably a substituted or unsubstituted alkyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, or trimethylsilylethyl group), an aryl group (preferably a substituted or substituted group having 6 to 30 carbon atoms). Unsubstituted aryl groups, such as phenyl, p-tolyl, naphthyl, m-chlorophenol, o-hexadecanolaminophenol, heterocyclic groups (preferably 5- or 6-membered substitutions) Or a monovalent group obtained by removing one hydrogen atom from an unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic having 3 to 30 carbon atoms. For example, 2 furyl, 2 chael, 2-pyrimidyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxy group, alkoxy group (preferably carbon number 1 to 30 Substituted or unsubstituted alkoxy groups such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy groups (preferably substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms) Groups such as phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-trophenoxy, 2-tetradecanoylaminophenoxy),
シリルォキシ基 (好ましくは、炭素数 3から 20のシリルォキシ基、例えば、トリメチルシリ ルォキシ、 t—プチルジメチルシリルォキシ)、ヘテロ環ォキシ基 (好ましくは、炭素数 2から 30の置換もしくは無置換のへテロ環ォキシ基、 1—フエ-ルテトラゾールー 5— ォキシ、 2—テトラヒドロビラ-ルォキシ)、ァシルォキシ基 (好ましくはホルミルォキシ 基、炭素数 2から 30の置換もしくは無置換のアルキルカルボニルォキシ基、炭素数 6 から 30の置換もしくは無置換のァリールカルボ-ルォキシ基、例えば、ホルミルォキ
シ、ァセチルォキシ、ビバロイルォキシ、ステアロイルォキシ、ベンゾィルォキシ、 p— メトキシフエ-ルカルポ-ルォキシ)、力ルバモイルォキシ基 (好ましくは、炭素数 1か ら 30の置換もしくは無置換の力ルバモイルォキシ基、例えば、 N, N ジメチルカル バモイルォキシ、 N, N ジェチルカルバモイルォキシ、モルホリノカルボニルォキシ 、 N, N—ジー n—ォクチルァミノカルボニルォキシ、 N— n—ォクチルカルバモイルォ キシ)、アルコキシカルボニルォキシ基 (好ましくは、炭素数 2から 30の置換もしくは無 置換アルコキシカルボ-ルォキシ基、例えばメトキシカルボ-ルォキシ、エトキシカル ボニルォキシ、 t ブトキシカルボニルォキシ、 n—ォクチルカルボ二ルォキシ)、ァリ ールォキシカルボ-ルォキシ基 (好ましくは、炭素数 7から 30の置換もしくは無置換 のァリールォキシカルボ-ルォキシ基、例えば、フエノキシカルボ-ルォキシ、 p—メト キシフエノキシカルボニルォキシ、 p— n—へキサデシルォキシフエノキシカルボニル ォキシ)、 A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted hexoxy group having 2 to 30 carbon atoms). Terocyclicoxy group, 1-phenyltetrazole-5-oxy, 2-tetrahydroviraroxy, acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, carbon number 6 To 30 substituted or unsubstituted arylocarboxyl groups such as formyloxy Ci, acetyloxy, bivaluloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarboxoxy, rubamoyloxy group (preferably a substituted or unsubstituted C 1-30 rubamoyloxy group such as N, N dimethyl Carbamoyloxy, N, N Jetylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, N-n-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably Is a substituted or unsubstituted alkoxycarboxoxy group having 2 to 30 carbon atoms, for example, methoxycarboxoxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarboxoxy group (preferably, 7 to 30 carbon atoms Substituted or unsubstituted aryloxycarboxoxy groups such as phenoxycarboxoxy, p-methoxyphenoxycarbonyloxy, p-n-hexadecyloxyphenoxycarbonyloxy),
アミノ基 (好ましくは、アミノ基、炭素数 1から 30の置換もしくは無置換のアルキルアミ ノ基、炭素数 6から 30の置換もしくは無置換のァリールアミノ基、例えば、アミ入メチ ルァミノ、ジメチルアミ入ァニリノ、 N—メチル一ァニリ入ジフエニルァミノ)、ァシルァ ミノ基 (好ましくは、ホルミルアミノ基、炭素数 1から 30の置換もしくは無置換のアルキ ルカルボ-ルァミノ基、炭素数 6から 30の置換もしくは無置換のァリールカルボ-ル アミノ基、例えば、ホルミルァミノ、ァセチルアミ入ビバロイルアミ入ラウロイルァミノ、 ベンゾィルアミ入 3, 4, 5—トリー n—ォクチルォキシフエニルカルボニルァミノ)、アミ ノカルボ-ルァミノ基 (好ましくは、炭素数 1から 30の置換もしくは無置換のァミノカル ボ-ルァミノ、例えば、力ルバモイルアミ入 N, N ジメチルァミノカルボ-ルアミ入 N, N ジェチルァミノカルボ-ルァミノ、モルホリノカルボ-ルァミノ)、アルコキシ力 ルポニルァミノ基 (好ましくは炭素数 2から 30の置換もしくは無置換アルコキシカルボ -ルァミノ基、例えば、メトキシカルボ-ルアミ入エトキシカルボ-ルアミ入 tーブトキ シカルボニルァミノ、 n—ォクタデシルォキシカルボニルァミノ、 N—メチルーメトキシ カルボ-ルァミノ)、ァリールォキシカルボ-ルァミノ基 (好ましくは、炭素数 7から 30 の置換もしくは無置換のァリールォキシカルボ-ルァミノ基、例えば、フエノキシカル ボニルァミノ、 p クロ口フエノキシカルボニルァミノ、 m— n—ォクチルォキシフエノキ
シカルボ-ルァミノ)、スルファモイルァミノ基 (好ましくは、炭素数 0から 30の置換もし くは無置換のスルファモイルァミノ基、例えば、スルファモイルアミ入 N, N ジメチル アミノスルホニルアミ入 N— n—ォクチルアミノスルホニルァミノ)、アルキル及びァリ 一ルスルホ -ルァミノ基 (好ましくは炭素数 1から 30の置換もしくは無置換のアルキル スルホニルァミノ、炭素数 6から 30の置換もしくは無置換のァリールスルホ -ルァミノ 、例えば、メチルスルホ -ルァミノ、ブチルスルホ -ルアミ入フエ-ルスルホ -ルァミノ 、 2, 3, 5 トリクロ口フエ-ルスルホ-ルアミ入 p—メチルフエ-ルスルホ -ルァミノ) メルカプト基、アルキルチオ基 (好ましくは、炭素数 1から 30の置換もしくは無置換の アルキルチオ基、例えばメチルチオ、ェチルチオ、 n—へキサデシルチオ)、ァリール チォ基 (好ましくは炭素数 6から 30の置換もしくは無置換のァリールチオ、例えば、フ ェ-ルチオ、 p—クロ口フエ-ルチオ、 m—メトキシフエ-ルチオ)、ヘテロ環チォ基(好 ましくは炭素数 2から 30の置換または無置換のへテロ環チォ基、例えば、 2 ベンゾ チアゾリルチオ、 1 フエ-ルテトラゾールー 5—ィルチオ)、スルファモイル基(好まし くは炭素数 0から 30の置換もしくは無置換のスルファモイル基、例えば、 N ェチル スルファモイル、 N— (3—ドデシルォキシプロピル)スルファモイル、 N, N ジメチル スルファモイル、 N ァセチルスルファモイル、 N ベンゾィルスルファモイル、 N— ( スルホ基、アルキル及びァリールスルフィエル基 (好ましくは、炭素数 1から 30の置換 または無置換のアルキルスルフィエル基、 6から 30の置換または無置換のァリールス ルフィ-ル基、例えば、メチルスルフィ -ル、ェチルスルフィ -ル、フエ-ルスルフィ- ル、 ρ—メチルフヱ-ルスルフィ -ル)、アルキル及びァリールスルホ -ル基(好ましく は、炭素数 1から 30の置換または無置換のアルキルスルホ-ル基、 6から 30の置換 または無置換のァリールスルホ-ル基、例えば、メチルスルホ -ル、ェチルスルホ- ル、フエ-ルスルホ -ル、 p メチルフエ-ルスルホ-ル)、ァシル基(好ましくはホルミ ル基、炭素数 2から 30の置換または無置換のアルキルカルボニル基、炭素数 7から 3 0の置換もしくは無置換のァリールカルボニル基、炭素数 4から 30の置換もしくは無 置換の炭素原子でカルボ-ル基と結合しているへテロ環カルボ-ル基、例えば、ァ
セチル、ピバロィル、 2—クロロアセチル、ステアロイル、ベンゾィル、 p—n—ォクチル ォキシフ ニルカルボニル、 2—ピリジルカルボニル、 2—フリルカルボ二ル)、ァリー ルォキシカルボ-ル基 (好ましくは、炭素数 7から 30の置換もしくは無置換のァリール ォキシカルボ-ル基、例えば、フエノキシカルボ-ル、 o クロロフエノキシカルボ-ル 、 m—二トロフエノキシカルボニル、 p—t—ブチルフエノキシカルボニル)、アルコキシ カルボニル基 (好ましくは、炭素数 2から 30の置換もしくは無置換アルコキシカルボ- ル基、例えば、メトキシカルボ-ル、エトキシカルボ-ル、 t ブトキシカルボ-ル、 n— ォクタデシルォキシカルボ-ル)、力ルバモイル基 (好ましくは、炭素数 1から 30の置 換もしくは無置換の力ルバモイル、例えば、力ルバモイル、 N—メチルカルバモイル、 N, N ジメチルカルバモイル、 N, N ジー n—ォクチルカルバモイル、 N (メチル スノレホニノレ)カノレバモイノレ)、 An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, such as amino-containing methylamino, dimethylamino-anilino, N —Methylaniline-containing diphenylamino), an acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbolumino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcoyl group having 6 to 30 carbon atoms) Amino group such as formylamino, acetylamino-containing bivaloylamino-containing lauroylamino, benzoylami-containing 3, 4, 5-tree n-octyloxyphenylcarbonylamino, aminocarbo-lamino group (preferably having 1 to 1 carbon atoms) 30 substituted or unsubstituted aminoboraminos, for example force rumomoire N, N Dimethylaminocarboamiamino N, N Jetylaminocarbolumino, morpholinocarbolumino), alkoxy group Luponylamino group (preferably a substituted or unsubstituted alkoxycarbolumino having 2 to 30 carbon atoms) Groups, for example, methoxycarbolamylated ethoxycarbolamylated t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbolamamino), aryloxycarbolamino groups (Preferably, a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m-n-octyloxyphenoxy, Cicarbo-amino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino group N, N dimethylaminosulfonylamino group N—n-octylaminosulfonylamino), alkyl and arylsulfo-lumino groups (preferably substituted or unsubstituted alkylsulfonylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted having 6 to 30 carbon atoms) Arylsulfo-lumino, such as methylsulfo-lumino, butylsulfo-amino-containing phenylsulfo-lumino, 2,3,5 trichloro-phenyl sulfo-amino-containing p-methylphenol sulfo-lumino) Mercapto group, preferably alkylthio group A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, ethylthio, n Hexadecylthio), arylothio group (preferably substituted or unsubstituted arylothio having 6 to 30 carbon atoms, for example, ferthio, p-chlorophenol, m-methoxyphenolthio), heterocyclic thio group ( Preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2 benzothiazolylthio, 1-phenoltetrazol-5-ylthio, or a sulfamoyl group (preferably having 0 to 30 carbon atoms). Or an unsubstituted sulfamoyl group such as N-ethyl sulfamoyl, N— (3-dodecyloxypropyl) sulfamoyl, N, N dimethyl sulfamoyl, N-acetyl sulfamoyl, N-benzoylsulfamoyl, N— (sulfo group, Alkyl and arylsulfier groups (preferably substituted or unsubstituted alkyl Alkyl groups, 6 to 30 substituted or unsubstituted arylsulfyl groups such as methylsulfuryl, ethylsulfuryl, phenolsulfuryl, ρ-methylphenylsulfuryl), alkyl and arylsulfol groups ( Preferably, it is a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfol group having 6 to 30 carbon atoms, such as methylsulfol, ethylsulfol, phenylsulfol, p-methylphenol sulfo), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, carbon Heterocyclic carbocyclic groups bonded to carbocyclic groups with 4 to 30 substituted or unsubstituted carbon atoms, for example Cetyl, pivalol, 2-chloroacetyl, stearoyl, benzoyl, p-n-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), aryloxycarboyl groups (preferably 7 to 30 carbon atoms) Or an unsubstituted aryloxycarbonyl group such as phenoxycarbol, o chlorophenoxycarbole, m-nitrophenoxycarbonyl, p-t-butylphenoxycarbonyl), alkoxycarbonyl group (preferably C2-C30 substituted or unsubstituted alkoxycarbon groups such as methoxycarbol, ethoxycarbole, t-butoxycarbole, n-octadecyloxycarboro), rubamoyl group ( Preferably, a substituted or unsubstituted force rumomois having 1 to 30 carbon atoms, such as force rubamoi. , N-methylcarbamoyl, N, N dimethylcarbamoyl, N, N di-n-octylcarbamoyl, N (methyl snorehoninore) canolevamoinole),
ァリール及びへテロ環ァゾ基 (好ましくは炭素数 6から 30の置換もしくは無置換のァリ 一ルァゾ基、炭素数 3から 30の置換もしくは無置換のへテロ環ァゾ基、例えば、フエ ニルァゾ、 ρ—クロ口フエニルァゾ、 5 ェチルチオ—1, 3, 4ーチアジアゾールー 2— ィルァゾ)、イミド基 (好ましくは、 N—スクシンイミド、 N フタルイミド)、ホスフイノ基( 好ましくは、炭素数 2から 30の置換もしくは無置換のホスフイノ基、例えば、ジメチル ホスフィ入ジフエ-ルホスフィ入メチルフエノキシホスフイノ)、ホスフィエル基(好まし くは、炭素数 2から 30の置換もしくは無置換のホスフィエル基、例えば、ホスフィニル 、ジォクチルォキシホスフィエル、ジエトキシホスフィエル)、ホスフィエルォキシ基(好 ましくは、炭素数 2から 30の置換もしくは無置換のホスフィエルォキシ基、例えば、ジ フエノキシホスフィエルォキシ、ジォクチルォキシホスフィエルォキシ)、ホスフィエルァ ミノ基 (好ましくは、炭素数 2から 30の置換もしくは無置換のホスフィニルァミノ基、例 えば、ジメトキシホスフィエルアミ入ジメチルァミノホスフィエルアミノ)、シリル基(好ま しくは、炭素数 3から 30の置換もしくは無置換のシリル基、例えば、トリメチルシリル、 t ーブチルジメチルシリル、フエ二ルジメチルシリル)を表わす。 Aryl and heterocyclic azo groups (preferably substituted or unsubstituted aryl azo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo , Ρ-black mouth phenylazo, 5-ethylthio-1,3,4-thiadiazole-2-ylazo), imide group (preferably N-succinimide, N phthalimide), phosphino group (preferably substituted with 2 to 30 carbon atoms) Or an unsubstituted phosphino group such as dimethyl phosphide-containing diphenylphosphite-containing methylphenoxyphosphino, a phosphier group (preferably a substituted or unsubstituted phosphier group having 2 to 30 carbon atoms such as phosphinyl, Dioctyloxyphosphier, diethoxyphosphier), phosphiroxy group (preferably substituted with 2 to 30 carbon atoms) Or an unsubstituted phosphiroxy group, such as diphenoxyphosphieroxy, dioctyloxyphosphieroxy), a phosphieramino group (preferably a substituted or unsubstituted group having 2 to 30 carbon atoms) Phosphinylamino groups such as dimethoxyphosphieramino-containing dimethylaminophosphieramino, silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms such as trimethylsilyl, t- Butyldimethylsilyl, phenyldimethylsilyl).
[0118] 一般式(10)、及び一般式(11)中、 RU、 R12、 R13、 R14、 R15、 R16、 R17、 R18、 R21、 R22 、 R23、 R24、 R25、 R26、
R28は、水素原子が最も好ましい。 [0118] In general formula (10) and general formula (11), R U , 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 28 is most preferably a hydrogen atom.
[0119] R31、 RM、 R"、 R42、 R43、 R"は、置換基としては前記 Rと同じものが挙げられるが、水
素原子、置換もしくは無置換のアルキル基、または置換もしくは無置換のァリール基 が好ましい。その中でも、置換または無置換のァリール基が更に好ましい。 [0119] R 31 , R M , R ", R 42 , R 43 , R" may be the same as the above R as a substituent, A primary atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group is preferred. Of these, a substituted or unsubstituted aryl group is more preferable.
[0120] Ma27, Ma28, Ma29は、各々独立に、置換または無置換のメチン基である。一般式( 2)の Ma27、
Ma29と同義であり、その具体例及び好ましいものも同様である。 K a23は、各々独立に、 0から 3までの整数を表す。 Qは、電荷を中和する一価の陽ィォ ンを表す。 Ka23が 2または 3であるとき、複数存在する Ma27、 Ma28は、同じでも異なつ ていてもよい。 [0120] Ma 27 , Ma 28 , and Ma 29 are each independently a substituted or unsubstituted methine group. Ma 27 in general formula (2), This is synonymous with Ma 29, and specific examples and preferred ones thereof are also the same. K a 23 each independently represents an integer of 0 to 3. Q represents a monovalent cation that neutralizes the charge. When Ka 23 is 2 or 3, a plurality of Ma 27 and Ma 28 may be the same or different.
[0121] 以下に、一般式(9)で表される化合物の好ましい具体例 (ィ匕合物(9) 1〜(9) - 2 [0121] The following are preferred specific examples of the compound represented by the general formula (9) (Compounds (9) 1 to (9)-2)
5)を挙げるが、本発明はこれらに限定されるものではない。 Although 5) is mentioned, the present invention is not limited to these.
[0122] [化 36]
[0122] [Chemical 36]
[0123] [化 37]
[0123] [Chemical 37]
而 900 OAV lSl0e/900Zdf/13d 1-9 08
900 OAV lSl0e / 900Zdf / 13d 1-9 08
ォキソノール色素は、該当する活性メチレンィ匕合物とメチン源 (メチン染料にメチン 基を導入するために用いられる化合物)との縮合反応によって合成することができる oこの種のィ匕合物についての詳糸田は、特公日召 39— 22069号、同 43— 3504号、同 5 2— 38056号、同 54— 38129号、同 55— 10059号、同 58— 35544号、特開昭 49 — 99620号、同 52— 92716号、同 59— 16834号、同 63— 316853号、同 64— 40
827号各公報、ならびに英国特許第 1133986号、米国特許第 3247127号、同 40 42397号、同 4181225号、同 5213956号、同 5260179号各明細書を参照するこ とができる。また、特開昭 63— 209995号公報、特開平 10— 309871号公報、特開 2002- 249674号公報にも記載されて!、る。 Oxonol dyes can be synthesized by a condensation reaction between the corresponding active methylene compound and a methine source (a compound used to introduce a methine group into a methine dye). O Details about this type of compound Itoda, JPK 39-22069, 43-3504, 52-38056, 54-38129, 55-10059, 58-35544, JP-A 49-99620 52-92716, 59-16834, 63-316853, 64-40 Reference can be made to the publications No. 827 and British Patent Nos. 1133986, 3247127, 40 42397, 4181225, 5213956, and 5260179. Also described in JP-A-63-209995, JP-A-10-309871, and JP-A-2002-249674.
[0127] 上記一般式(1)及び(3)等で示されるォキソノール色素は、単独で用いてもよぐあ るいは二種以上を併用してもよい。また、既述のォキソノール色素とこれ以外の色素 化合物とを併用してもよい。併用する色素は、ァゾ色素 (金属イオンとの錯体ィ匕したも のを含む)、ピロメテン色素、シァニン色素、スクァリリウム色素等が例として挙げられ る。 [0127] The oxonol dyes represented by the above general formulas (1) and (3) may be used alone or in combination of two or more. Further, the aforementioned oxonol dye and other dye compounds may be used in combination. Examples of the dye used in combination include azo dyes (including those complexed with metal ions), pyromethene dyes, cyanine dyes, squarylium dyes, and the like.
[0128] 本発明に用いる色素は、熱分解温度が 100°C〜350°Cの範囲にあるものが好まし 更に ίま、 150oC〜300oCの範囲にあるちの力 S好まし ヽ。更に ίま、 200oC力ら 300 °Cの範囲にあるものが好ましい。 [0128] dyes for use in the present invention, further preferably those thermal decomposition temperature is in the range of 100 ° C~350 ° C ί Also, Chino force S preferably is in the range of 150 o C~300 o Cヽ. Further, it is preferable that the temperature is within a range of 300 ° C, such as 200 ° C force.
[0129] 記録層に用いる色素(「既述のォキソノール色素」または「既述のォキソノール色素 およびこれと併用する色素」 )のアモルファス膜の光学特性上、複素屈折率の係数 n ( 実部:屈性率)、 k (虚部:消衰係数)は、好ましくは、 2. 0≤n≤3. 0、0. 005≤k≤0 . 30である。更に好ましく ίま、 2. 1≤η≤2. 7、 0. 01≤k≤0. 15である。最も好まし くは、 2. 15≤n≤2. 50、 0. 03≤k≤0. 10である。 [0129] The complex refractive index coefficient n (real part: bending) due to the optical properties of the amorphous film of the dye used in the recording layer ("Oxonol dye described above" or "Oxonol dye described above and dye used together with it") (Incidence factor) and k (imaginary part: extinction coefficient) are preferably 2.0≤n≤3.0 and 0.005≤k≤0.30. More preferably, 2. 1≤η≤2.7, 0.01.ltoreq.k≤0.15. Most preferably, 2.15≤n≤2.50, 0.03≤k≤0.10.
[0130] 以下、本発明の光情報記録媒体の層構成について、図面を参照して説明する。本 発明の光情報記録媒体は、少なくとも 2層の記録層を有し、それぞれの記録層が同 種もしくは異種のォキソノール色素を含有し、それぞれの記録層の間に中間層が形 成されている構成であれば、特に限定されるものではない。なお、記録層にはォキソ ノール色素以外のほかの色素が含有されて 、てもよ 、。 2層の記録層を有する場合、 その層構成としては、基板上に、第 1の記録層、反射層、第 2の記録層がこの順に形 成されてなる構成である。 Hereinafter, the layer configuration of the optical information recording medium of the present invention will be described with reference to the drawings. The optical information recording medium of the present invention has at least two recording layers, each recording layer contains the same or different oxonol dye, and an intermediate layer is formed between the recording layers. If it is a structure, it will not specifically limit. The recording layer may contain a dye other than the oxonol dye. In the case of having two recording layers, the layer structure is a structure in which a first recording layer, a reflective layer, and a second recording layer are formed in this order on a substrate.
[0131] 図 1および図 2に、本発明の光情報記録媒体の層構成の一例を示す。まず、図 1に 示す光情報記録媒体は、いわゆる貼り合わせ型の光情報記録媒体である。すなわち 、基板 1上に第 1の記録層 L0と反射層 3とが形成された第 1の積層体と、基板 8上に 反射層 7と第 2の記録層 L1と保護層または色素保護層 5とが形成された第 2の積層
体と力 中間層 4を介してそれぞれの記録層が内層となるようにして貼り合わされた構 成となっている。基板 1側力もレーザーを照射する場合、反射層 3は半透明となって いる。 1 and 2 show an example of the layer structure of the optical information recording medium of the present invention. First, the optical information recording medium shown in FIG. 1 is a so-called bonded optical information recording medium. That is, the first laminate in which the first recording layer L0 and the reflective layer 3 are formed on the substrate 1, and the reflective layer 7, the second recording layer L1, and the protective layer or the dye protective layer 5 on the substrate 8. A second laminate formed with Body and force The structure is such that each recording layer is bonded to the inner layer 4 via the intermediate layer 4. When the substrate 1 side force is also irradiated with a laser, the reflective layer 3 is translucent.
[0132] 一方、図 2に示す光情報記録媒体は、いわゆる積層型の光情報記録媒体である。 On the other hand, the optical information recording medium shown in FIG. 2 is a so-called laminated optical information recording medium.
すなわち、基板 1上に第 1の記録層 L0、反射層 3、中間層 4、第 2の記録層 Ll、反射 層 7、および基板 8がこの順に積層した構成となっている。そして、基板 1側からレー ザ一を照射する場合、反射層 3は半透明となっている。 That is, the first recording layer L0, the reflective layer 3, the intermediate layer 4, the second recording layer Ll, the reflective layer 7, and the substrate 8 are laminated on the substrate 1 in this order. When the laser 1 is irradiated from the substrate 1 side, the reflective layer 3 is translucent.
[0133] 以下、本発明の光情報記録媒体の基板や各層の材料および形成方法を説明する [0133] Hereinafter, the materials and forming methods of the substrate and each layer of the optical information recording medium of the present invention will be described.
(基板) (Board)
基板は、従来の情報記録媒体の基板として用いられて ヽる各種の材料から任意に 選択することができる。基板材料としては、例えば、ガラス;ポリカーボネート;ポリメチ ルメタタリレート等のアクリル榭脂;ポリ塩ィ匕ビュル、塩化ビュル共重合体等の塩化ビ -ル系榭脂;エポキシ榭脂;アモルファスポリオレフインおよびポリエステル等を挙げ ることができ、所望によりそれらを併用してもよい。なお、これらの材料はフィルム状と してまたは剛性のある基板として使うことができる。上記材料の中では、耐湿性、寸法 安定性および価格などの点からポリカーボネートが好ましい。 The substrate can be arbitrarily selected from various materials used as a substrate of a conventional information recording medium. Examples of the substrate material include glass; polycarbonate; acrylic resin such as polymethyl methacrylate; vinyl chloride resin such as poly salt resin and chlorinated copolymer; epoxy resin; amorphous polyolefin and polyester And may be used in combination as desired. These materials can be used as a film or as a rigid substrate. Among the above materials, polycarbonate is preferable from the viewpoints of moisture resistance, dimensional stability and price.
[0134] 基板には、トラッキング用の案内溝またはアドレス信号等の情報を表わす凹凸 (プレ グループ)が形成されている。プリグループのトラックピッチは、 300〜900nmの範囲 とすること好ましく、 400〜800nmとすること力さら〖こ好ましい。また、プリグループの 深さ(溝深さ)の範囲は、積層型と貼り合わせ型とで異なる。積層型では、 100〜200 nmの範囲とすることが好ましぐ 110〜150nmの範囲とすることがより好ましい。 [0134] The substrate is provided with irregularities (pregroups) representing information such as tracking guide grooves or address signals. The track pitch of the pregroup is preferably in the range of 300 to 900 nm, more preferably 400 to 800 nm. Moreover, the range of the depth (groove depth) of the pregroup differs between the stacked type and the bonded type. In the laminated type, the range of 100 to 200 nm is preferable, and the range of 110 to 150 nm is more preferable.
[0135] 一方、貼り合わせ型においては、光入射面に近い基板のプリグループの深さは、 1 00〜200nmの範囲とすることが好ましぐ 110〜150nmの範囲とすることがより好ま しい。また、光入射面に遠い基板のプリグループの深さは、 lOOnm以下が好ましぐ 60nm以下とすることがより好ましぐ 15〜40nmとすることがさらに好ましい。 [0135] On the other hand, in the bonded type, the depth of the pre-group of the substrate close to the light incident surface is preferably in the range of 100 to 200 nm, more preferably in the range of 110 to 150 nm. . The depth of the pre-group of the substrate far from the light incident surface is preferably lOOnm or less, more preferably 60 nm or less, and even more preferably 15 to 40 nm.
[0136] さらに、プリグループの半値幅の好ましい範囲は、積層型と貼り合わせ型とで異なる 。積層型では、 200〜400nmの範囲とすることが好ましぐ 230〜380nmとすること
力 り好ましい。 [0136] Furthermore, the preferable range of the half width of the pre-group differs between the stacked type and the bonded type. In the laminated type, it is preferable that the range is 200 to 400 nm. It is preferable.
[0137] 一方、貼り合わせ型においては、光入射面に近い基板のプリグループの半値幅は 、 200〜400nmの範囲とすることが好ましぐ 230〜380nmの範囲とすることがより 好ましい。また、光入射面に遠い基板のプリグループの凸部における半値幅は、 300 〜550nmの範囲とすることが好ましぐ 400〜520nmとすることがより好ましい。 On the other hand, in the bonded type, the half width of the pre-group of the substrate close to the light incident surface is preferably in the range of 200 to 400 nm, more preferably in the range of 230 to 380 nm. Further, the half width at the convex portion of the pre-group of the substrate far from the light incident surface is preferably in the range of 300 to 550 nm, more preferably 400 to 520 nm.
[0138] 記録層が設けられる側の基板表面には、平面性の改善および接着力の向上およ び記録層の変質防止などの目的で、下塗層が設けられてもよい。下塗層の材料とし ては例えば、ポリメチルメタタリレート、アクリル酸 'メタクリル酸共重合体、スチレン '無 水マレイン酸共重合体、ポリビュルアルコール、 N—メチロールアクリルアミド、スチレ ン 'ビュルトルエン共重合体、クロルスルホン化ポリエチレン、ニトロセルロース、ポリ 塩化ビュル、塩素化ポリオレフイン、ポリエステル、ポリイミド、酢酸ビュル'塩ィ匕ビュル 共重合体、エチレン.酢酸ビュル共重合体、ポリエチレン、ポリプロピレン、ポリカーボ ネート等の高分子物質;およびシランカップリング剤などの表面改質剤をあげることが できる。 [0138] An undercoat layer may be provided on the surface of the substrate on which the recording layer is provided for the purpose of improving flatness, improving adhesive force, and preventing alteration of the recording layer. Examples of the material for the undercoat layer include polymethylmethacrylate, acrylic acid 'methacrylic acid copolymer, styrene' hydrous maleic acid copolymer, polybulal alcohol, N-methylolacrylamide, and styrene 'bulutoluene. Polymers, chlorosulfonated polyethylene, nitrocellulose, polychlorinated butyl, chlorinated polyolefin, polyester, polyimide, butyl acetate salt butyl copolymer, ethylene, butyl acetate copolymer, polyethylene, polypropylene, polycarbonate, etc. And surface modifiers such as polymeric substances; and silane coupling agents.
[0139] 下塗層は、上記物質を適当な溶剤に溶解または分散して塗布液を調製したのち、 この塗布液をスピンコート、ディップコート、エタストルージョンコートなどの塗布法によ り基板表面に塗布することにより形成することができる。 [0139] The undercoat layer is prepared by dissolving or dispersing the above substances in an appropriate solvent to prepare a coating solution, and then applying the coating solution to the substrate surface by a coating method such as spin coating, dip coating, or etching coating. It can form by apply | coating to.
[0140] 既述のように、基板 (または下塗層が設けられた場合は、下塗層)にはトラッキング 用溝またはアドレス信号等の情報を表す凹凸 (プレダループ)が形成されて!、る。こ のプレダループは、ポリカーボネートなどの榭脂材料を射出成形あるいは押出成形 する際に直接基板上に前記のトラックピッチで形成されることが好ましい。また、プレ グループの形成を、プレグルーブ層を設けることにより行ってもよい。プレダループ層 の材料としては、アクリル酸のモノエステル、ジエステル、トリエステルおよびテトラエス テルのうち少なくとも一種のモノマー(またはオリゴマー)と光重合開始剤との混合物 を用いることができる。プレダループ層の形成は、例えば、まず精密に作られた母型( スタンパー)上に上記のアクリル酸エステルおよび重合開始剤からなる混合液を塗布 し、さらにこの塗布液層上に基板を載せたのち、基板または母型を介して紫外線を照 射することにより塗布層を硬化させて基板ど塗布層とを固着させる。次いで、基板を
母型から剥離すること〖こより得ることができる。 [0140] As described above, the substrate (or the subbing layer if a subbing layer is provided) is formed with irregularities (predura loops) representing information such as tracking grooves or address signals! . This pre-loop is preferably formed directly on the substrate at the track pitch when a resin material such as polycarbonate is injection-molded or extruded. In addition, the pre-group may be formed by providing a pre-groove layer. As a material of the pre-dalup layer, a mixture of at least one monomer (or oligomer) of monoester, diester, triester and tetraester of acrylic acid and a photopolymerization initiator can be used. For example, the pre-dloop layer is formed by first applying a liquid mixture comprising the above-described acrylic ester and polymerization initiator on a precisely manufactured master (stamper), and further placing a substrate on this coating liquid layer. Then, the coating layer is cured by irradiating ultraviolet rays through the substrate or the matrix, and the substrate and the coating layer are fixed. Then the substrate It can be obtained from cocoon peeling off from the mother mold.
(記録層) (Recording layer)
基板上 (又は下塗層が設けられた場合は、下塗層)のプレダループが形成されてい る面側には、ォキソノール色素、好ましくは前記一般式(1)で示されるォキソノール色 素を含む記録層が少なくとも 2層設けられる。なお、ォキソノール色素については、既 述の通りである。 A recording containing an oxonol dye, preferably an oxonol dye represented by the general formula (1), on the side of the substrate where the pre-loop is formed (or an undercoat layer if an undercoat layer is provided) At least two layers are provided. The oxonol dye is as described above.
[0141] 記録層には、更に耐光性を向上させるための種々の褪色防止剤を含有することが できる。褪色防止剤の代表例としては、特開平 3— 224793号公報に記載の一般式 ( 111)、(IV)もしくは (V)で表される金属錯体、ジインモ -ゥム塩、アミ-ゥム塩ゃ特開 平 2— 300287号公報ゃ特開平 2— 300288号公報に示されて 、るニトロソ化合物、 特開平 10— 151861号公報に示されている TCNQ誘導体などを挙げることができる [0141] The recording layer may further contain various anti-fading agents for improving light resistance. Representative examples of the anti-fading agent include metal complexes represented by the general formula (111), (IV) or (V) described in JP-A-3-224793, diimum salts, and amylum salts. As disclosed in JP-A-2-300287, JP-A-2-300288, nitroso compounds, and TCNQ derivatives as disclosed in JP-A-10-151861 can be mentioned.
[0142] 記録層の形成は、既述のォキソノール色素、更に所望によりクェンチヤ一、結合剤 などを溶剤に溶解して塗布液を調製し、次 、でこの塗布液を基板表面に塗布して塗 膜を形成したのち乾燥することにより行うことができる。色素記録層形成用の塗布液 の溶剤としては、酢酸ブチル、乳酸ェチル、セロソルブアセテートなどのエステル;メ チルェチルケトン、シクロへキサノン、メチルイソブチルケトンなどのケトン;ジクロルメ タン、 1, 2—ジクロルェタン、クロ口ホルムなどの塩素化炭化水素;ジメチルホルムアミ ドなどのアミド;シクロへキサンなどの炭化水素;テトラヒドロフラン、ェチルエーテル、 ジォキサンなどのエーテル;エタノール、 n—プロパノール、イソプロパノール、 n—ブ タノール、ジアセトンアルコールなどのアルコール; 2, 2, 3, 3—テトラフロロプロパノ ールなどのフッ素系溶剤;エチレングリコールモノメチルエーテル、エチレンングリコ 一ノレモノェチノレエーテノレ、プロピレンングリコーノレモノメチノレエーテノレなどのグリコー ルエーテル類などを挙げることができる。 [0142] The recording layer is formed by preparing a coating solution by dissolving the oxonol dye described above, and further, if necessary, a quencher, a binder, etc. in a solvent, and then applying the coating solution on the substrate surface in the following manner. It can be performed by forming a film and then drying it. Solvents in the coating solution for forming the dye recording layer include esters such as butyl acetate, ethyl lactate, and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone; dichloromethane, 1,2-dichloroethane, and black mouth Chlorinated hydrocarbons such as form; Amides such as dimethylformamide; Hydrocarbons such as cyclohexane; Ethers such as tetrahydrofuran, ethyl ether, dioxane; Ethanol, n-propanol, isopropanol, n-butanol, diacetone alcohol, etc. Fluorine solvents such as 2, 2, 3, 3-tetrafluoropropanol; ethylene glycol monomethyl ether, ethylene glycol monoremonoechinoleatenore, propyleneglycolinoremonomethinoreatenore, etc. No And the like can be mentioned co-ethers.
[0143] 上記溶剤は使用する化合物の溶解性を考慮して単独または二種以上組み合わせ て用いることができる。塗布液中にはさらに酸ィ匕防止剤、 UV吸収剤、可塑剤、潤滑 剤などの各種の添加剤を目的に応じて添加してもよ 、。 [0143] The above solvents may be used alone or in combination of two or more in consideration of the solubility of the compound used. Various additives such as anti-oxidation agents, UV absorbers, plasticizers and lubricants may be added to the coating solution depending on the purpose.
[0144] 結合剤の例としては、例えばゼラチン、セルロース誘導体、デキストラン、ロジン、ゴ
ムなどの天然有機高分子物質;およびポリエチレン、ポリプロピレン、ポリスチレン、ポ リイソブチレン等の炭化水素系榭脂;ポリ塩ィ匕ビュル、ポリ塩ィ匕ビユリデン、ポリ塩ィ匕ビ -ル ·ポリ酢酸ビュル共重合体等のビュル系榭脂;ポリアクリル酸メチル、ポリメタタリ ル酸メチルなどのアクリル榭脂;ポリビュルアルコール、塩素化ポリエチレン、ェポキ シ榭脂、プチラール榭脂、ゴム誘導体、フエノール'ホルムアルデヒド榭脂等の熱硬 化性榭脂の初期縮合物などの合成有機高分子を挙げることができる。 [0144] Examples of the binder include, for example, gelatin, cellulose derivatives, dextran, rosin, and gossip. Natural organic polymer materials such as polyethylene; and hydrocarbon resins such as polyethylene, polypropylene, polystyrene, polyisobutylene; polysalt-bulls, polysalt-vinylidenes, polysalt-vinyls, polyacetate butls Bull resin such as copolymer; Acrylic resin such as poly (methyl acrylate) and poly (methyl methacrylate); Poly (bulb alcohol, chlorinated polyethylene, epoxy resin, petital resin, rubber derivatives, phenol formaldehyde resin And synthetic organic polymers such as an initial condensate of thermosetting rosin.
[0145] 記録層の材料として結合剤を併用する場合に、結合剤の使用量は、既述のォキソ ノール色素を始めとした色素の量に対して一般に 0. 01〜50倍量 (質量比)の範囲 にあり、好ましくは 0. 1〜5倍量 (質量比)の範囲にある。このようにして調製される塗 布液の色素濃度は一般に 0. 01〜10質量%の範囲にあり、好ましくは 0. 1〜5質量 %の範囲にある。 [0145] When a binder is used in combination as the recording layer material, the amount of binder used is generally 0.01 to 50 times the mass of the dye, including the oxonol dye described above (mass ratio). ), Preferably in the range of 0.1 to 5 times the mass (mass ratio). The pigment concentration of the coating solution thus prepared is generally in the range of 0.01 to 10% by mass, preferably in the range of 0.1 to 5% by mass.
[0146] 塗布方法としては、スプレー法、スピンコート法、ディップ法、ロールコート法、ブレ ードコート法、ドクターロール法、スクリーン印刷法などを挙げることができる。記録層 は単層でも重層でもよい。記録層の層厚は一般に 20〜500nmの範囲にあり、好まし くは 50〜300nmの範囲にある。 [0146] Examples of the coating 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 recording layer may be a single layer or a multilayer. The thickness of the recording layer is generally in the range of 20 to 500 nm, preferably in the range of 50 to 300 nm.
(反射層) (Reflective layer)
記録層上には、情報の再生時における反射率の向上の目的で、反射層が設けら れることが好ましい。反射層の材料である光反射性物質はレーザー光に対する反射 率が高い物質であり、その例としては、 Mg、 Se、 Y、 Ti、 Zr、 Hf、 V、 Nb、 Ta、 Cr、 Mo、 W、 Mn、 Re、 Fe、 Co、 Niゝ Ru、 Rh、 Pd、 Ir、 Pt、 Cu、 Ag、 Au、 Zn、 Cd、 Al、 Ga、 In、 Si、 Ge、 Te、 Pb、 Po、 Sn、 Biなどの金属及び半金属あるいはステンレス鋼 を挙げることができる。これらのうちで好ましいものは、 Cr、 Ni、 Pt、 Cu、 Ag、 Au、 Al およびステンレス鋼であり、特に好ましいものは Agである。これらの物質は単独で用 いてもよいし、あるいは二種以上の組み合わせで、または合金として用いてもよい。 反射層は、例えば上記反射性物質を蒸着、スパッタリングまたはイオンプレーティン グすることにより記録層の上に形成することができる。 A reflective layer is preferably provided on the recording layer for the purpose of improving the reflectance during information reproduction. The light-reflective material that is the material of the reflective layer is a material that has a high reflectivity for laser light. Examples include Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W. , Mn, Re, Fe, Co, Ni ゝ Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi And metals such as metal and semi-metal or stainless steel. Of these, Cr, Ni, Pt, Cu, Ag, Au, Al, and stainless steel are preferable, and Ag is particularly preferable. These substances may be used alone or in combination of two or more or as an alloy. The reflective layer can be formed on the recording layer, for example, by vapor deposition, sputtering or ion plating of the reflective material.
[0147] 反射層の層厚は一般には 10〜300nmの範囲にあり、好ましくは 50〜200nmの範 囲である。なお、反射層が半透明の反射層(図 1および図 2における反射層 3)の場
合、その層厚は、 2〜150nmの範囲にあることが好ましい。 [0147] The thickness of the reflective layer is generally in the range of 10 to 300 nm, preferably in the range of 50 to 200 nm. It should be noted that the reflective layer is a semi-transparent reflective layer (reflective layer 3 in FIGS. 1 and 2). In this case, the layer thickness is preferably in the range of 2 to 150 nm.
(色素保護層) (Dye protective layer)
色素保護層の材料については、既述の通りである。色素保護層は、真空蒸着、ス ノ ッタリング、塗布等の方法により設けることができる。色素保護層の層厚は一般に は lnm〜: LO μ mの範囲にある。 The material for the dye protective layer is as described above. The dye protective layer can be provided by a method such as vacuum evaporation, sputtering, or coating. The thickness of the dye protective layer is generally in the range of lnm to: LO μm.
(保護層) (Protective layer)
記録層の上には、記録層などを物理的および化学的に保護する目的で保護層 (バ リア層ともいう)が設けられていてもよい。この保護層は、基板の記録層が設けられて いない側にも耐傷性、耐湿性を高める目的で設けられてもよい。 A protective layer (also referred to as a barrier layer) may be provided on the recording layer for the purpose of physically and chemically protecting the recording layer and the like. This protective layer may be provided on the side of the substrate where the recording layer is not provided for the purpose of enhancing scratch resistance and moisture resistance.
[0148] 保護層に用いられる材料としては、例えば、 SiO、 SiO、 MgF、 SnO、 Si N、 Zn [0148] Examples of materials used for the protective layer include SiO, SiO, MgF, SnO, Si N, and Zn.
2 2 2 3 4 2 2 2 3 4
O-Ga Oなどの無機物質;熱可塑性榭脂、熱硬化性榭脂、 UV硬化性榭脂等の有Inorganic substances such as O-GaO; such as thermoplastic resin, thermosetting resin, UV curable resin
2 3 twenty three
機物質を挙げることができる。 Mention may be made of organic substances.
[0149] 保護層は、真空蒸着、スパッタリング、塗布等の方法により設けることができる。また 、熱可塑性榭脂、熱硬化性榭脂を使用する場合には、これらを適当な溶剤に溶解し た塗布液を調製したのち、この塗布液を塗布し、乾燥すること〖こよっても形成すること ができる。 UV硬化性榭脂の場合には、そのままもしくは適当な溶剤に溶解して塗布 液を調製した後、この塗布液を塗布し、 UV光を照射して硬化させることによつても形 成することができる。これらの塗布液中には、更に帯電防止剤、酸化防止剤、 UV吸 収剤等の各種添加剤を目的に応じて添加してもよい。保護層の層厚は一般には In m〜10 μ mの範囲にある。 [0149] The protective layer can be provided by a method such as vacuum deposition, sputtering, or coating. In addition, when using a thermoplastic resin or a thermosetting resin, prepare a coating solution in which these are dissolved in an appropriate solvent, then apply this coating solution and dry it. can do. In the case of UV curable resin, it can also be formed by preparing the coating solution as it is or by dissolving it in a suitable solvent, and then applying this coating solution and curing it by irradiation with UV light. Can do. In these coating solutions, various additives such as an antistatic agent, an antioxidant and a UV absorber may be added according to the purpose. The thickness of the protective layer is generally in the range of In m to 10 μm.
(中間層) (Middle layer)
当該中間層は、既述のように少なくとも第 1の記録層と第 2の記録層との間に設けら れる。また、本発明の光情報記録媒体が貼り合わせ型の場合は、 2つ積層体を接着 する機能も有するので、 As described above, the intermediate layer is provided at least between the first recording layer and the second recording layer. Further, in the case where the optical information recording medium of the present invention is a bonded type, it also has a function of adhering two laminated bodies.
中間層の材料としては、熱可塑性榭脂、熱硬化性榭脂、電子線硬化性榭脂、紫外 線硬化性榭脂、感圧式両面テープ等や、 Si02等の無機材料等が挙げられる。また 、これらの材料を単独または混合してもよいし、一層だけではなく多層膜にして用い てもよい。このような中間層は、スピンコート法やキャスト法、スパッタ法により形成する
ことができる。中間層の厚みは、 5〜: LOO mであることが好ましぐ 10〜70 mであ ることより好まし ヽ。本明糸田書中には、日本出願 2005— 24961号、 2005— 24962号 及び 2006— 3775号の開示の全てが参照により取り込まれる。 Examples of the material for the intermediate layer include thermoplastic resins, thermosetting resins, electron beam curable resins, ultraviolet ray curable resins, pressure-sensitive double-sided tapes, and inorganic materials such as Si02. These materials may be used alone or in combination, and may be used as a multilayer film as well as a single layer. Such an intermediate layer is formed by spin coating, casting, or sputtering. be able to. The thickness of the intermediate layer is 5 to: 10 to 70 m, more preferably LOO m. All of the disclosures of Japanese applications 2005-24961, 2005-24962 and 2006-3775 are incorporated by reference into this book.
[0150] 本発明の光情報記録媒体の情報記録方法は、例えば、次のように行われる。まず、 情報記録媒体を定線速度または定角速度にて回転させながら、基板側から半導体 レーザー光などの記録用のレーザー光を照射する。この光の照射により、記録層と反 射層との界面に空洞を形成 (空洞の形成は、記録層または反射層の変形、あるいは 両層の変形を伴って形成される)するカゝ、基板が肉盛り変形する、あるいは記録層に 変色、会合状態の変化等により屈折率が変化することにより情報が記録されると考え られる。記録光としては、 600nm〜700nm (好ましくは 620〜680nm、更に好ましく は、 630〜660nm)の範囲の発振波長を有する半導体レーザービームが用いられる [0150] The information recording method of the optical information recording medium of the present invention is performed, for example, as follows. First, a recording laser beam such as a semiconductor laser beam is irradiated from the substrate side while rotating the information recording medium at a constant linear velocity or a constant angular velocity. This light irradiation forms a cavity at the interface between the recording layer and the reflective layer (the formation of the cavity is accompanied by deformation of the recording layer or the reflective layer, or deformation of both layers), substrate It is considered that the information is recorded when the thickness of the material changes, or the refractive index changes due to discoloration, change in association state, etc. in the recording layer. As the recording light, a semiconductor laser beam having an oscillation wavelength in the range of 600 nm to 700 nm (preferably 620 to 680 nm, more preferably 630 to 660 nm) is used.
[0151] 上記のように記録された情報の再生は、情報記録媒体を上記と同一の定線速度で 回転させながら記録時と同じ波長を持つ半導体レーザー光を基板側力 照射して、 その反射光を検出することにより行うことができる。 [0151] The information recorded as described above is reproduced by irradiating a semiconductor laser beam having the same wavelength as that during recording while rotating the information recording medium at the same constant linear velocity as described above, and then reflecting the reflected light. This can be done by detecting light.
実施例 Example
[0152] 以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるも のではない。 [0152] Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.
[実施例 1] [Example 1]
射出成形にて、ポリカーボネート榭脂をスパイラル状のグループ (深さ 120nm、溝 幅 365nm、トラックピッチ 0. 74 m)を有する厚さ 0. 570mm,直径 120mmの基板 に成形し、これを第 1の記録層を形成するための基板とした。下記化学式で表される 「ォキソノール色素 A」l. OOgを 2, 2, 3, 3—テトラフルォロプロパノール 100mlに溶 解し、塗布液を調製した。この塗布液をスピンコート法により上記基板のグループが 形成されている面に塗布して、第 1の記録層(L0)を形成した。 By injection molding, polycarbonate resin is formed into a substrate with a thickness of 0.570 mm and a diameter of 120 mm with a spiral group (depth 120 nm, groove width 365 nm, track pitch 0.74 m). A substrate for forming a recording layer was obtained. “Oxonol dye A” l.OOg represented by the following chemical formula was dissolved in 100 ml of 2,2,3,3-tetrafluoropropanol to prepare a coating solution. This coating solution was applied to the surface on which the group of substrates was formed by spin coating to form the first recording layer (L0).
[0153] [化 41]
[0153] [Chemical 41]
次に、第 1の記録層上に、 AgNdCu合金(ターゲット組成 Ag : 98. 4at%、 Nd: 0. Next, an AgNdCu alloy (target composition Ag: 98.4 at%, Nd: 0.
7at%、 Cu: 0. 9at%)をスパッタして膜厚 14nmの半透過性の反射層を形成した。こ れにより第 1の記録層を有する第 1積層体を得た。 7 at%, Cu: 0.9 at%) was sputtered to form a 14 nm thick translucent reflective layer. Thus, a first laminated body having the first recording layer was obtained.
[0154] 一方、射出成形にて、ポリカーボネート榭脂をスノィラル状のグループ (深さ 25nm[0154] On the other hand, in injection molding, polycarbonate resin is made into a spiral group (depth 25nm).
、基板ランド幅 468nm、トラックピッチ 0. 74 m)を有する厚さ 0. 600mm,直径 12Substrate land width 468nm, track pitch 0.74m), thickness 600mm, diameter 12
Ommの基板を成形し、これを第 2の記録層を形成するための基板とした。 An Omm substrate was formed and used as a substrate for forming the second recording layer.
[0155] 次に、この基板のグループが形成されて 、る面に、 AgNdCu合金(ターゲット組成[0155] Next, a group of the substrates is formed, and an AgNdCu alloy (target composition) is formed on the surface.
Ag : 98. 4at%、Nd: 0. 7at%、 Cu: 0. 9at%)をスパッタして膜厚 120nmの反射層 を形成した。 (Ag: 98.4 at%, Nd: 0.7 at%, Cu: 0.9 at%) was sputtered to form a reflective layer having a thickness of 120 nm.
[0156] 更に、上記「ォキソノール色素 A」 2. 00gを 2, 2, 3, 3—テトラフルォロプロパノール 100mlに溶解し塗布液を調製した。この塗布液をスピンコート法により上記基板のグ ループが形成されている面に塗布して、第 2の記録層(L1)を形成した。 Further, 2.00 g of the above “oxonol dye A” was dissolved in 100 ml of 2,2,3,3-tetrafluoropropanol to prepare a coating solution. This coating solution was applied to the surface of the substrate on which the group was formed by spin coating to form a second recording layer (L1).
[0157] 更に第 2の記録層上に ZnO— Ga O (ターゲット組成 ZnO : Ga O = 30wt% : 70w Furthermore, ZnO—Ga 2 O 3 (target composition ZnO: Ga 2 O = 30 wt%: 70w) on the second recording layer
2 3 2 3 2 3 2 3
t%)をスパッタして、膜厚 5nmの保護層(バリア層)を形成した。これにより第 2の記録 層を有する第 2積層体を得た。 t%) was sputtered to form a protective layer (barrier layer) having a thickness of 5 nm. As a result, a second laminate having a second recording layer was obtained.
[0158] 紫外線硬化榭脂 (ダイキュアクリア SD640 大日本インキ化学工業製)を接着剤と して用いて、第 1積層体と第 2積層体とを記録層が内層となるように貼り合せて、光情 報記録媒体を作製した。なお、中間層の厚さは 55 mであった。 [0158] Using UV curable resin (Dicure Clear SD640 manufactured by Dainippon Ink & Chemicals, Inc.) as an adhesive, the first and second laminates were bonded together so that the recording layer was the inner layer. An optical information recording medium was prepared. The intermediate layer had a thickness of 55 m.
[実施例 1 A] [Example 1 A]
射出成形にて、ポリカーボネート榭脂をスパイラル状のグループ (深さ 120nm、溝
幅 365nm、トラックピッチ 0. 74 m)を有する厚さ 0. 570mm,直径 120mmの基板 に成形し、これを第 1の記録層を形成するための基板とした。下記化学式で表される 「ォキソノール色素 A」l. OOgを 2, 2, 3, 3—テトラフルォロプロパノール 100mlに溶 解し、塗布液を調製した。この塗布液をスピンコート法により上記基板のグループが 形成されている面に塗布して、第 1の記録層(L0)を形成した。 Spiral group of polycarbonate resin by injection molding (depth 120nm, groove A substrate having a width of 365 nm, a track pitch of 0.74 m) and a thickness of 0.570 mm and a diameter of 120 mm was formed, and this was used as a substrate for forming the first recording layer. “Oxonol dye A” l.OOg represented by the following chemical formula was dissolved in 100 ml of 2,2,3,3-tetrafluoropropanol to prepare a coating solution. This coating solution was applied to the surface on which the group of substrates was formed by spin coating to form the first recording layer (L0).
[0159] [化 42] [0159] [Chemical 42]
次に、第 1の記録層上に、 AgNdCu合金(ターゲット組成 Ag : 98. 4at%、 Nd: 0. Next, an AgNdCu alloy (target composition Ag: 98.4 at%, Nd: 0.
7at%、 Cu: 0. 9at%)をスパッタして膜厚 14nmの半透過性の反射層を形成した。こ れにより第 1の記録層を有する積層体を得た。 7 at%, Cu: 0.9 at%) was sputtered to form a 14 nm thick translucent reflective layer. Thus, a laminated body having the first recording layer was obtained.
[0160] 一方、射出成形にて、ポリカーボネート榭脂をスノィラル状のグループ (深さ 25nm[0160] On the other hand, the polycarbonate resin is formed into a snoral group (depth 25nm by injection molding).
、基板ランド幅 468nm、トラックピッチ 0. 74 m)を有する厚さ 0. 600mm,直径 12Substrate land width 468nm, track pitch 0.74m), thickness 600mm, diameter 12
0mmの基板を成形し、これを第 2の記録層を形成するための基板とした。 A 0 mm substrate was molded and used as a substrate for forming the second recording layer.
[0161] 次に、この基板のグループが形成されている面に、 AgNdCu合金(ターゲット組成[0161] Next, an AgNdCu alloy (target composition) is formed on the surface on which the group of substrates is formed.
Ag : 98. 4at%、Nd: 0. 7at%、 Cu: 0. 9at%)をスパッタして膜厚 120nmの反射層 を形成した。 (Ag: 98.4 at%, Nd: 0.7 at%, Cu: 0.9 at%) was sputtered to form a reflective layer having a thickness of 120 nm.
[0162] 更に、上記「ォキソノール色素 A」 2. OOgを 2, 2, 3, 3—テトラフルォロプロパノール 100mlに溶解し塗布液を調製した。この塗布液をスピンコート法により上記基板のグ ループが形成されている面に塗布して、第 2の記録層(L1)を形成した。 Further, the above-mentioned “Oxonol dye A” 2.OOg was dissolved in 100 ml of 2,2,3,3-tetrafluoropropanol to prepare a coating solution. This coating solution was applied to the surface of the substrate on which the group was formed by spin coating to form a second recording layer (L1).
[0163] 更に第 1の記録層上に ZnO— Ga O (ターゲット組成 ZnO : Ga O = 30wt% : 70w [0163] Furthermore, ZnO—Ga 2 O 3 (target composition ZnO: Ga 2 O = 30 wt%: 70w on the first recording layer)
2 3 2 3 2 3 2 3
t%)をスパッタして、膜厚 5nmの色素保護層を形成した。これにより第 1の記録層を
有する積層体を得た。 t%) was sputtered to form a 5 nm thick dye protective layer. As a result, the first recording layer The laminated body which has was obtained.
[0164] 紫外線硬化榭脂 (ダイキュアクリア SD640 大日本インキ化学工業製)を接着剤と して用いて、第 1の記録層が形成されている積層体と第 2の記録層が形成されている 積層体とを記録層が内層となるように貼り合せて、光情報記録媒体を作製した。なお 、接着剤の層(中間層)の厚さは 55 μ mであった。 [0164] Using a UV curable resin (Dicure Clear SD640 manufactured by Dainippon Ink and Chemicals) as an adhesive, a laminate in which the first recording layer is formed and a second recording layer are formed. The laminated body was bonded so that the recording layer was an inner layer, and an optical information recording medium was produced. The thickness of the adhesive layer (intermediate layer) was 55 μm.
[0165] なお、エリプソメーター(ULVAC社製のモデル ESM— 1)〖こより、波長 632nmの 条件で測定した第 2の記録層の屈折率は 2. 2であり、色素保護層の屈折率は 1. 8で あった。また、エリプソメーター(ULVAC社製のモデル ESM— 1)により、波長 632η mの条件で測定した色素保護層の消衰係数は 0. 1以下であった。 [0165] According to the ellipsometer (model ESM-1 manufactured by ULVAC), the refractive index of the second recording layer measured at 632 nm was 2.2, and the refractive index of the dye protective layer was 1 It was eight. Further, the extinction coefficient of the dye protective layer measured by an ellipsometer (model ESM-1 manufactured by ULVAC) under the condition of a wavelength of 632 ηm was 0.1 or less.
[比較例 1] [Comparative Example 1]
色素 Aのかわりに下記比較ィ匕合物(1)を用いた以外は、実施例 1と全く同様な方法 で光情報記録媒体を作製した。 An optical information recording medium was produced in the same manner as in Example 1 except that the following comparative compound (1) was used instead of Dye A.
[0166] [化 43] [0166] [Chemical 43]
[実施例 2] [Example 2]
色素保護層を形成する際に、 ZnO-Ga Oターゲットの代わりに SiNターゲットを When forming the dye protective layer, use a SiN target instead of a ZnO-GaO target.
2 3 twenty three
用い、 SiN力もなる色素保護層(層厚 :48nm)を形成した以外は実施例 1一 Aと同様 にして、光情報記録媒体を作製した。なお、色素保護層の屈折率は 1. 6であり、消 衰係数は 0. 1以下であった。 An optical information recording medium was produced in the same manner as in Example 1 A except that a dye protective layer (layer thickness: 48 nm) having a SiN force was used. The dye protective layer had a refractive index of 1.6 and an extinction coefficient of 0.1 or less.
[実施例 3] [Example 3]
色素保護層を形成する際に、 ZnO-Ga Oターゲットの代わりに Ta Oターゲットを When forming the dye protective layer, Ta O target is used instead of ZnO-Ga O target.
2 3 2 5 用い、酸ィ匕タンタル力もなる色素保護層(層厚: 2. 5nm)を形成した以外は実施例 1 と同様にして、光情報記録媒体を作製した。なお、色素保護層の屈折率は 2. 0であ り、消衰係数は 0. 1以下であった。
[実施例 4] An optical information recording medium was produced in the same manner as in Example 1 except that 2 3 2 5 was used and a dye protective layer (layer thickness: 2.5 nm) having an acid-tantalum power was formed. The refractive index of the dye protective layer was 2.0, and the extinction coefficient was 0.1 or less. [Example 4]
色素保護層を形成する際に、 ZnO-Ga Oターゲットの代わりに Nb O ターゲット Nb O target instead of ZnO-Ga O target when forming dye protection layer
2 3 2 4.83 を用い、酸化ニオブからなる色素保護層(層厚: 5nm)を形成した以外は実施例 1と 同様にして、光情報記録媒体を作製した。なお、色素保護層の屈折率は 2. 3であり 、消衰係数は 0. 1以下であった。 An optical information recording medium was produced in the same manner as in Example 1 except that a dye protective layer (layer thickness: 5 nm) made of niobium oxide was formed using 2 3 2 4.83. The dye protective layer had a refractive index of 2.3 and an extinction coefficient of 0.1 or less.
[比較例 1 A] [Comparative Example 1 A]
色素保護層を形成しな力つた以外は実施例 1— Aと同様にして、光情報記録媒体 を作製した。 An optical information recording medium was produced in the same manner as in Example 1-A, except that a dye protective layer was not formed.
[比較例 2] [Comparative Example 2]
色素保護層を形成する際に、 ZnO— Ga Oターゲットの代わりに AgNdCuターゲッ When forming the dye protective layer, instead of ZnO—GaO target, AgNdCu target
2 3 twenty three
ト(ターゲット組成 Ag : 98. 4at%、Nd: 0. 7at%、Cu: 0. 9at%)を用い、 Ag—Nd —Cu合金カゝらなる色素保護層 (層厚 : 5nm)を形成した以外は実施例 1一 Aと同様 にして、光情報記録媒体を作製した。なお、色素保護層の屈折率は 0. 2であり、消 衰係数は 4.。であった。 (Target composition Ag: 98.4 at%, Nd: 0.7 at%, Cu: 0.9 at%) was used to form a dye protective layer (layer thickness: 5 nm) made of Ag—Nd —Cu alloy. An optical information recording medium was produced in the same manner as Example 1 A except for the above. The refractive index of the dye protective layer is 0.2 and the extinction coefficient is 4. Met.
[比較例 3] [Comparative Example 3]
色素保護層を形成する際に、 ZnO-Ga Oターゲットの代わりに MgFターゲットを When forming the dye protective layer, use MgF target instead of ZnO-Ga 2 O target.
2 3 twenty three
用いて色素保護層を形成した以外は実施例 1 Aと同様にして、光情報記録媒体を 作製した。なお、色素保護層の屈折率は 1. 4であった。 An optical information recording medium was produced in the same manner as in Example 1A except that the dye protective layer was used. The refractive index of the dye protective layer was 1.4.
[比較例 4] [Comparative Example 4]
色素保護層を形成する際に、 ZnO-Ga Oターゲットの代わりに TiOx (酸ィ匕チタン When forming the dye protective layer, instead of the ZnO-Ga 2 O target, TiOx (acid 匕 titanium
2 3 twenty three
)ターゲットを用いて色素保護層を形成した以外は実施例 1— Aと同様にして、光情 報記録媒体を作製した。なお、色素保護層の屈折率は 2. 7であった。 ) An optical information recording medium was produced in the same manner as in Example 1-A, except that a dye protective layer was formed using a target. The refractive index of the dye protective layer was 2.7.
以下、上記の実施例 1、 1 A、 2〜4及び比較例 1、 1—A及び 2〜4力 得られた 光情報記録媒体を用いて、その性能評価にっ 、て説明する。 Hereinafter, performance evaluation will be described using the optical information recording media obtained in Examples 1, 1 A, 2 to 4 and Comparative Examples 1, 1-A and 2 to 4 described above.
(光情報記録媒体の評価) (Evaluation of optical information recording media)
DDU— 1000およびマルチシグナルジェネレータ( 、ずれもパルステック工業社製 、レーザー波長:660nm、対物レンズ開口数: 0. 65)を用いて、線速度を 9. 2m/s として、実施例および比較例の光情報記録媒体に、 8— 16変調信号を記録した。実
施例 1及び比較例 1につレ、て使用したストラテジを下記表 1に示す, Examples and comparative examples using a DDU-1000 and a multi-signal generator (both manufactured by Pulstec Industrial Co., Ltd., laser wavelength: 660 nm, objective lens numerical aperture: 0.65) with a linear velocity of 9.2 m / s 8-16 modulation signals were recorded on the optical information recording medium. Fruit The strategies used in Example 1 and Comparative Example 1 are shown in Table 1 below.
1] 1]
また、 d録した信号は、 DDU— 1000 (パルステック工業社製、レーザー波長:660 nm、対物レンズ開口数 : 0. 60)を用いて、線速度を 3. 8mZsとして、再生を行い再 生信号を上記実施例 1及び比較例 1の光情報記録媒体について評価した。上記実 施例 1及び比較例 1の光情報記録媒体について、最適記録パワー、反射率、変調度 、ジッター、 PIエラーを測定した結果を下記表 2に示す。 D Recorded signals are played back and played back using DDU-1000 (Pulstec Industries, laser wavelength: 660 nm, objective lens numerical aperture: 0.60) at a linear velocity of 3.8 mZs. The signal was evaluated for the optical information recording media of Example 1 and Comparative Example 1 above. Table 2 below shows the results of measuring the optimum recording power, reflectivity, modulation factor, jitter, and PI error for the optical information recording media of Example 1 and Comparative Example 1.
[表 2]
実施例 1 比較例 1 [Table 2] Example 1 Comparative Example 1
L0 し 1 し 0 し 1 L0 then 1 then 0 then 1
最適記録パワー Po [m Optimum recording power Po [m
W] 26. 4 29. 2 30. 0 35. 0 記録後の反射率 [%] 17. 3 18. 1 16. 0 13. 0 変調度 0. 68 0. 76 0. 60 0. 55 ジッター [%] 7. 5 7. 5 12. 0 15. 0 W] 26. 4 29. 2 30. 0 35. 0 Reflectance after recording [%] 17. 3 18. 1 16. 0 13. 0 Modulation depth 0.68 0. 76 0. 60 0. 55 Jitter [ %] 7.5 5 7. 5 12. 0 15. 0
PIエラー 5 19 290 423 上記の結果より、第 1の記録層 (L0)、第 2の記録層 (L1)とも比較例 1に比べて実 施例 1の最適記録パワーが低く良好であった。また、第 1の記録層(L0)、第 2の記録 層(L1)とも比較例 1に比べて実施例 1の反射率、変調度が高く良好であった。更に は、第 1の記録層 (L0)、第 2の記録層 (L1)とも比較例 1に比べて実施例 1のジッター 、 PIエラーは低ぐ良好であった。 PI error 5 19 290 423 Based on the above results, the first recording layer (L0) and the second recording layer (L1) had good and low optimum recording power in Example 1 compared to Comparative Example 1. Further, both the first recording layer (L0) and the second recording layer (L1) were good in terms of the reflectivity and the degree of modulation in Example 1 as compared with Comparative Example 1. Further, both the first recording layer (L0) and the second recording layer (L1) had good jitter and PI error in Example 1 as compared with Comparative Example 1.
[0170] また、実施例 1— A、 2、 3、及び 4と比較例 1— A及び 2から得られた光情報記録媒 体についても、記録した信号は、 DDU— 1000 (パルステック工業社製、レーザー波 長: 660nm、対物レンズ開口数: 0. 60)を用いて、線速度を 3. 8mZsとして、再生 を行い、ジッターを評価した。結果を下記表 1— Aに示す。 [0170] In addition, the recorded signals of the optical information recording media obtained from Examples 1—A, 2, 3, and 4 and Comparative Example 1—A and 2 were DDU-1000 (Pulstec Industrial Co., Ltd.). Reproduction was performed at a linear velocity of 3.8 mZs using a laser wavelength of 660 nm and an objective lens numerical aperture of 0.60), and jitter was evaluated. The results are shown in Table 1-A below.
使用した記録レーザー発光パターン (記録ストラテジ)は、各ディスクに対して最適化 した。なお、レーザーは、第 1の記録層側から照射した。 The recording laser emission pattern (recording strategy) used was optimized for each disc. The laser was irradiated from the first recording layer side.
[0171] また、実施例 1— A、 2〜4および比較例 2〜4については、 L1層側の記録感度、反 射率および 30mW記録時の PIエラーを測定した。結果を下記表 2— Aに示す。なお 、表 2— A中の「判定」の基準として、「5」は記録感度および反射率がともに特に優れ ていることを示し、「4」は記録感度および反射率がともに優れていることを示し、「3」 は記録感度および反射率がともに普通程度であることを示し、「2」は感度が不十分で あることを示し、「1」は記録感度および反射率がともに不十分であることを示す。 [0171] For Examples 1-A, 2 to 4 and Comparative Examples 2 to 4, the recording sensitivity on the L1 layer side, the reflectivity, and the PI error during 30 mW recording were measured. The results are shown in Table 2-A below. As a criterion for “judgment” in Table 2-A, “5” indicates that both recording sensitivity and reflectance are particularly excellent, and “4” indicates that both recording sensitivity and reflectance are excellent. "3" indicates that both the recording sensitivity and reflectance are normal, "2" indicates that the sensitivity is insufficient, and "1" indicates that both the recording sensitivity and reflectance are insufficient. It shows that.
[0172] [表 1 - A]
ジッタ- [%] [0172] [Table 1-A] Jitter-[%]
L0 し 1 L0 then 1
実施例 1一 7.5 8.5 Example 1 1 7.5 8.5
A A
実施例 2 7.5 8.0 Example 2 7.5 8.0
実施例 3 7.5 9.0 Example 3 7.5 9.0
実施例 4 7.5 9.0 Example 4 7.5 9.0
比較例 1一 7.5 9.5 Comparative Example 1 1 7.5 9.5
A A
比較例 2 7.5 13.8 [表 2-A] Comparative Example 2 7.5 13.8 [Table 2-A]
上記表 1—Aより、第 1の記録層 (LO)に関しては、実施例 1 A、 2〜4および比較 例 1 A及び 2の光情報記録媒体は、いずれも同程度の低いジッターであつが、第 2 の記録層(L1)に関しては、実施例 1 A、 2〜4の光情報記録媒体の方が低いジッ ターであった。すなわち、実施例 1— A、 2〜4の光情報記録媒体は、良好な信号特 性を有することがわ力つた。また、上記表 2— Aより、実施例 1— A、 2〜4では、良好 な記録特性が示されて ヽることが確認できた。 From Table 1-A above, regarding the first recording layer (LO), the optical information recording media of Examples 1A, 2 to 4 and Comparative Example 1 A and 2 all have the same low jitter. As for the second recording layer (L1), the optical information recording media of Examples 1A and 2 to 4 had lower jitter. That is, it was proved that the optical information recording media of Examples 1-A and 2 to 4 have good signal characteristics. Further, from Table 2-A above, it was confirmed that Examples 1-A and 2-4 showed good recording characteristics.
(保存性の評価)
(1)湿熱保存性の評価: (Evaluation of storage stability) (1) Evaluation of wet heat storage stability:
実施例 1および比較例 1のディスクに DDU— 1000およびマルチシグナルジエネレ ータ(いずれもパルステック工業社製、レーザー波長: 660nm、対物レンズ開口数: 0 . 65)を用いて、線速度を 9. 2mZsとして、実施例 1および比較例 1の光情報記録媒 体に、 8— 16変調信号を記録し、その際の PIエラーを測定した。実施例 1および比較 例 1の光情報記録媒体について使用したストラテジは、上記表 1に示したものを用い た。 Using the disk of Example 1 and Comparative Example 1 with DDU-1000 and a multi-signal generator (both manufactured by Pulstec Industrial Co., Ltd., laser wavelength: 660 nm, objective lens numerical aperture: 0.65), the linear velocity was 9. An 8-16 modulated signal was recorded on the optical information recording medium of Example 1 and Comparative Example 1 at 2 mZs, and the PI error at that time was measured. The strategies shown in Table 1 above were used for the optical information recording medium of Example 1 and Comparative Example 1.
[0174] 信号記録後の実施例および比較例の光情報記録媒体を 80°C85%RHの環境下 に 250時間保持した後、再度 PIエラーを測定した。結果を下記表 3に示す。 [0174] After the signal recording, the optical information recording media of Examples and Comparative Examples were kept in an environment of 80 ° C and 85% RH for 250 hours, and then PI error was measured again. The results are shown in Table 3 below.
[0175] [表 3] [0175] [Table 3]
比較例 1の光情報記録媒体では、 PIエラーが増加し、計測不能になっているのに 対し、実施例 1の光情報記録媒体では、第 1の記録層 (LO)、第 2の記録層 (L1)とも PIエラーに顕著な増加はなく、良好な特性を示してレ、た。 In the optical information recording medium of Comparative Example 1, the PI error increases and measurement is impossible, whereas in the optical information recording medium of Example 1, the first recording layer (LO) and the second recording layer In (L1), there was no significant increase in PI error, indicating good characteristics.
[0176] また、実施例 1— A、 2〜4および比較例 1—Aと 2から得られた光情報記録媒体に っ 、ても湿熱保存性の評価を同様に行レ、、信号記録後の光情報記録媒体を 80°C8 5%RHの環境下に 50時間保持した後、再度 PIエラーを測定した。その実施例 1— A 、 2〜4および比較例 1一 Aと 2の光情報記録媒体についての結果を下記表 3— Aに 示す。 [0176] The optical information recording media obtained from Examples 1-A and 2 to 4 and Comparative Examples 1-A and 2 were also evaluated for wet heat storage in the same manner, after signal recording. The optical information recording medium was kept in an environment of 80 ° C8 5% RH for 50 hours, and then PI error was measured again. Results for the optical information recording media of Examples 1-A, 2 to 4 and Comparative Example 1 A and 2 are shown in Table 3-A below.
[0177] [表 3-A]
L0 L1 実施例 80°C85%RH試験前 5 47[0177] [Table 3-A] L0 L1 Example 80 ° C 85% RH Before test 5 47
1一 A 80°C85%RH 50時間試験後 6 50 実施例 2 80°C85% H試験前 1 10 1 A A 80 ° C85% RH After 50 hours test 6 50 Example 2 80 ° C85% H Before test 1 10
80°C85%RH 50時間試験後 2 25 80 ° C 85% RH After 50 hours test 2 25
実施例 3 80°C85%RH試験前 2 13 Example 3 Before 80 ° C 85% RH test 2 13
80°C85%RH 50時間試験後 2 21 80 ° C85% RH After 50 hours test 2 21
実施例 4 80°C85%RH試験前 1 58 Example 4 Before 80 ° C 85% RH test 1 58
80°C85%RH 50時間試験後 2 60 80 ° C85% RH After 50 hours test 2 60
比較例 80°C85%RH試験前 7 36 Comparative Example 80 ° C 85% RH Before test 7 36
1一 A 80で 85%RH 50時間試験後 10 測定不能 1 A 80% 85% RH 50 hours after test 10 Measurement impossible
比較例 2 80で85% 試験前 8 813 Comparative Example 2 80% 85% Before test 8 813
80°C85%RH 50時間試験後 12 測定不能 上記表 3— Aの結果より、比較例 1一 Aの光情報記録媒体で第 2の記録層(L1)の 記録データが消失し、計測不能となった。比較例 2の光情報記録媒体については、 第 2の記録層 (L1)での PIエラーが増加し、計測不能な状態となった。これに対し、実 施例 1一 A、 2〜4の光情報記録媒体では、第 1の記録層(LO)、第 2の記録層(L1)と も PIエラーに顕著な増加はなく、良好な特性を示して V、た。 80 ° C 85% RH After 50 hours test 12 Measurement not possible Based on the results in Table 3-A above, the data recorded in the second recording layer (L1) is lost on the optical information recording medium of Comparative Example 1-1. became. For the optical information recording medium of Comparative Example 2, the PI error in the second recording layer (L1) increased, and measurement was impossible. On the other hand, in the optical information recording media of Example 1 A 1 and 2-4, the PI error does not significantly increase in both the first recording layer (LO) and the second recording layer (L1), which is good. V, which shows the special characteristics.
(2)耐光性の評価: (2) Light resistance evaluation:
実施例 1および比較例 1のディスクに DDU— 1000およびマルチシグナルジエネレ ータ(レ、ずれもパルステック工業社製、レーザー波長: 660nm、対物レンズ開口数: 0 . 65)を用いて、線速度を 9. 2mZsとして、 8— 16変調信号を記録し、その際の PIェ ラーを測定した。使用したストラテジは、上記表 1に示したものを用いた。 Using the disk of Example 1 and Comparative Example 1 with a DDU-1000 and a multi-signal generator (La, pulse is manufactured by Pulstec Industrial Co., Ltd., laser wavelength: 660 nm, objective lens numerical aperture: 0.65) 8-16 modulation signals were recorded at a velocity of 9.2 mZs, and the PI error at that time was measured. The strategy shown in Table 1 above was used.
[0178] 信号記録後の実施例 1および比較例 1の光情報記録媒体を積算照度 4MlX .hの 光を照射後、再度 PIエラーを測定した。結果を下記表 4に示す。 [0178] After the signal recording, the optical information recording media of Example 1 and Comparative Example 1 were irradiated with light having an integrated illuminance of 4 Ml X .h, and then the PI error was measured again. The results are shown in Table 4 below.
[0179] [表 4] [0179] [Table 4]
上記表 4の結果より、比較例 1の光情報記録媒体では、 PIヱラーが増加し、計測不
能になっているのに対し、実施例 1の光情報記録媒体では、第 1記録層(LO)、第 2 記録層 (L1)とも PIエラーに顕著な増加はなぐ良好な特性を示していた。 From the results in Table 4 above, in the optical information recording medium of Comparative Example 1, the PI error increased and measurement was not possible. On the other hand, in the optical information recording medium of Example 1, both the first recording layer (LO) and the second recording layer (L1) showed good characteristics with no significant increase in PI error. .
[実施例 5] [Example 5]
射出成形にて、ポリカーボネート榭脂をスパイラル状のグループ (深さ 120nm、溝 幅 365nm、トラックピッチ 0. 74 m)を有する厚さ 0. 575mm,直径 120mmの基板 に成形し、これを第 1の記録層を形成するための基板とした。下記化学式で表される 「色素 B」l. OOgを 2, 2, 3, 3—テトラフルォロプロパノール 100mlに溶解した塗布 液を調製し、この塗布液をスピンコート法により上記基板のグループが形成されて ヽ る面上に塗布して、第 1の記録層(L0層)を形成した。 By injection molding, polycarbonate resin is formed into a substrate with a thickness of 0.575 mm and a diameter of 120 mm with a spiral group (depth 120 nm, groove width 365 nm, track pitch 0.74 m). A substrate for forming a recording layer was obtained. Prepare a coating solution by dissolving “Dye B” l. OOg represented by the following chemical formula in 100 ml of 2, 2, 3, 3-tetrafluoropropanol. A first recording layer (L0 layer) was formed by coating on the formed surface.
[0180] 次に、第 1の記録層上に AgNdCu合金(ターゲット組成 Ag98. 4at% :NdO. 7at % : CuO. 9at%)をスパッタして膜厚 13nmの半透過反射層を形成した。これにより 第 1の記録層を有する積層体を得た。 Next, an AgNdCu alloy (target composition Ag 98.4 at%: NdO. 7 at%: CuO. 9 at%) was sputtered on the first recording layer to form a transflective layer having a thickness of 13 nm. Thus, a laminated body having the first recording layer was obtained.
[0181] 一方、射出成形にて、ポリカーボネート榭脂をスノィラル状のグループ (深さ 33nm 、基板ランド幅 450nm、トラックピッチ 0. 74 m)を有する厚さ 0. 600mm,直径 12 0mmの基板に成形し、これを第二の記録層を形成するための基板とした。次に基板 のグループが形成されている面上に AgNdCu合金(ターゲット組成 Ag98. 4at% :N d0. 7at% : CuO. 9at%)をスパッタして膜厚 120nmの反射層を形成した。 [0181] On the other hand, polycarbonate resin is molded into a substrate with a thickness of 0.600mm and a diameter of 120mm having a snorted group (depth 33nm, substrate land width 450nm, track pitch 0.74m) by injection molding. This was used as a substrate for forming the second recording layer. Next, an AgNdCu alloy (target composition Ag98.4 at%: Nd0.7 at%: CuO. 9 at%) was sputtered onto the surface on which the substrate group was formed to form a reflective layer having a thickness of 120 nm.
[0182] さらに、「既述のォキソノール色素 A」 2. OOgを 2, 2, 3, 3—テトラフルォロプロパノ ール 100mlに溶解した塗布液を調製し、この塗布液をスピンコート法により上記基板 のグループが形成されている面上に塗布して、第 2の記録層(L1層)を形成した。更 にこの L1層上に色素保護層として、 Ga Oを RFスパッタリングにより、膜厚 3. 4nm [0182] Furthermore, “Oxonol Dye A as described above” 2. A coating solution in which OOg was dissolved in 100 ml of 2, 2, 3, 3-tetrafluoropropanol was prepared, and this coating solution was prepared by spin coating. The second recording layer (L1 layer) was formed by coating on the surface on which the group of substrates was formed. In addition, as a dye protective layer on this L1 layer, Ga O is deposited by RF sputtering to a thickness of 3.4 nm.
2 3 twenty three
の薄膜を形成した。これにより第 2の記録層を有する積層体を得た。なお、第 2の記 録層(L1層)の屈折率は 2. 2であった。また、色素保護層の屈折率は 1. 8であり、消 衰係数は 0. 1以下であった。 A thin film was formed. As a result, a laminate having a second recording layer was obtained. The refractive index of the second recording layer (L1 layer) was 2.2. The refractive index of the dye protective layer was 1.8, and the extinction coefficient was 0.1 or less.
[0183] [化 44]
[0183] [Chemical 44]
色素 B 紫外線硬化榭脂 (ダイキュアクリア SD640 大日本インキ化学工業製)を接着剤と して用いて第 1の記録層を有する積層体と第 2の記録層を有する積層体とを記録層 が内層となるように貼り合せて光情報記録媒体を作製した。なお、接着剤の層(中間 層)の厚さは 50 /z mであった。 Dye B UV curable resin (Dicure Clear SD640, manufactured by Dainippon Ink and Chemicals) is used as an adhesive, and the recording layer is composed of a laminate having the first recording layer and a laminate having the second recording layer. The optical information recording medium was produced by bonding so as to be an inner layer. The thickness of the adhesive layer (intermediate layer) was 50 / zm.
[実施例 6] [Example 6]
色素保護層の層厚を 6. 7nmとした以外は、実施例 5と同様にして光情報記録媒体 を作製した。なお、色素保護層の屈折率は 1. 8であり、消衰係数は 0. 1以下であつ た。 An optical information recording medium was produced in the same manner as in Example 5 except that the thickness of the dye protective layer was changed to 6.7 nm. The dye protective layer had a refractive index of 1.8 and an extinction coefficient of 0.1 or less.
[実施例 7] [Example 7]
色素保護層の層厚を 10. lnmとした以外は、実施例 5と同様にして光情報記録媒 体を作製した。なお、色素保護層の屈折率は 1. 8であり、消衰係数は 0. 1以下であ つ 7こ。 An optical information recording medium was produced in the same manner as in Example 5 except that the thickness of the dye protective layer was 10. lnm. The refractive index of the dye protective layer is 1.8, and the extinction coefficient is 0.1 or less.
[実施例 8] [Example 8]
色素保護層の層厚を 16. 8nmとした以外は、実施例 5と同様にして光情報記録媒 体を作製した。なお、色素保護層の屈折率は 1. 8であり、消衰係数は 0. 1以下であ つ 7こ。 An optical information recording medium was produced in the same manner as in Example 5 except that the thickness of the dye protective layer was 16.8 nm. The refractive index of the dye protective layer is 1.8, and the extinction coefficient is 0.1 or less.
[参考例] [Reference example]
RFスパッタリングにより、 ZnO— Ga O (ターゲット組成 ZnO : Ga O = 30wt% : 7 By RF sputtering, ZnO—GaO (target composition ZnO: GaO = 30wt%: 7
2 3 2 3 2 3 2 3
0wt%)からなる色素保護層(膜厚 5nm)を形成した以外は、実施例 5と同様にして光 情報記録媒体を作製した。なお、色素保護層の屈折率はであり、消衰係数は以下で あった。
[光情報記録媒体の評価] An optical information recording medium was produced in the same manner as in Example 5 except that a dye protective layer (thickness 5 nm) composed of 0 wt% was formed. The refractive index of the dye protective layer was and the extinction coefficient was as follows. [Evaluation of optical information recording media]
DDU— 1000およびマルチシグナルジェネレータ(パルステック社製。レーザー波 長 655. 9nm、対物レンズ開口数 0. 65)を用いて、線速度を 30. 72mZsとして Using DDU-1000 and multi-signal generator (manufactured by Pulstec Corp., laser wavelength 655.9 nm, objective lens numerical aperture 0.65), linear velocity is 30.72 mZs
、 8— 16変調信号を L1のみに記録した。使用した記録レーザー発光パターン (記録 ストラテジ)は、各ディスクに対して最適化した。 8-16 modulation signal was recorded only in L1. The recording laser emission pattern (recording strategy) used was optimized for each disc.
[0184] また、記録した信号は、 DDU— 1000 (パルステック社製。レーザー波長 651. On m、対物レンズ開口数 0. 60)を用いて、線速度を 3. 84mZsとして、 L1の再生を 行い、 L1層の信号特性を評価した。 [0184] Also, the recorded signal was reproduced using the DDU-1000 (manufactured by Pulstec Inc., laser wavelength 651. On m, objective lens numerical aperture 0.60) at a linear velocity of 3.84 mZs. The signal characteristics of the L1 layer were evaluated.
[0185] 下記表 5に実施例 5〜8と参考例との L1層の信号特性評価結果を示す。参考例の[0185] Table 5 below shows the signal characteristic evaluation results of the L1 layer in Examples 5 to 8 and the reference example. Reference example
L1層の反射率は目標値である 16%にほぼ到達しているのに対して、実施例 5〜8に おける L1層の反射率は目標値である 16%以上の良好な値を示している。さらに、実 施例 5〜8における L1層のその他の信号特性についても、 目標値をクリアするレベル であることがわかった。 While the reflectivity of the L1 layer almost reached the target value of 16%, the reflectivity of the L1 layer in Examples 5 to 8 shows a good value of the target value of 16% or more. Yes. In addition, the other signal characteristics of the L1 layer in Examples 5 to 8 were found to be at a level that cleared the target value.
[0186] [表 5]
[0186] [Table 5]
実施 実施 実施 実施 Implementation Implementation Implementation Implementation
例 5 例 6 例 7 例 8 参考例 色素保護層 Example 5 Example 6 Example 7 Example 8 Reference Example Dye Protective Layer
色素保 層の材 Zn0-Ga,03 (30wt Dye retention layer Zn0-Ga, 0 3 (30wt
Ga203 Ga203 Ga203 Ga203 Ga 2 0 3 Ga 2 0 3 Ga 2 0 3 Ga 2 0 3
. % : 70wt. %) 色素保護層の厚 10. 1 %: 70wt.%) Dye protective layer thickness 10. 1
3. 4 6. 7 16. 8 5. 0 3. 4 6. 7 16. 8 5. 0
さ The
記録条件 spec. Recording conditions spec.
Po (DL) [mW] く 30ra 21. 6 22. 4 24. 1 24. 0 20. 6 Po (DL) [mW] <30ra 21. 6 22. 4 24. 1 24. 0 20. 6
測定結果 spec. Measurement result spec.
Reflectivity (DL Reflectivity (DL
16% min 16. 6 16. 6 17. 0 17. 1 15. 8 16% min 16. 6 16. 6 17. 0 17. 1 15. 8
) [%] ) [%]
Jitter [%] 9% max 8. 5 8. 3 8. 6 8. 4 8. 2 Jitter [%] 9% max 8. 5 8. 3 8. 6 8. 4 8. 2
0. 60 mi 0. 75 0. 75 0. 60 mi 0. 75 0. 75
I 14/I 14H 0. 77 0. 71 0. 73 I 14 / I 14H 0. 77 0. 71 0. 73
n n
0. 20 mi 0. 31 0. 30 0. 20 mi 0. 31 0. 30
13/114 0. 30 0. 30 0. 30 13/114 0. 30 0. 30 0. 30
n n
-0. 05 t 0. 11 0. 11 -0. 05 t 0. 11 0. 11
Asymmetry 0. 09 0. 07 0. 10 Asymmetry 0. 09 0. 07 0. 10
o +0. 15 o +0. 15
280/8EC 280 / 8EC
PI error [max] 10 6 2 6 5 PI error [max] 10 6 2 6 5
C max 以上から、本発明の光情報記録媒体は、十分低いジッターと PIエラーを達成し、か つ、各記録層において、高い反射率と高い変調度を示すことが確認できた。すなわ ち、当該光情報記録媒体は、良好な記録特性を発揮することが確認できた。また、光 や熱に対し良好な堅牢性を有することが確認できた。 From above C max, it was confirmed that the optical information recording medium of the present invention achieved sufficiently low jitter and PI error, and showed high reflectivity and high modulation degree in each recording layer. That is, it was confirmed that the optical information recording medium exhibited good recording characteristics. It was also confirmed that it has good fastness to light and heat.
産業上の利用可能性 Industrial applicability
本発明の光情報記録媒体は、ォキソノール色素を含有させることで長期間に渡り安 定した記録再生特性の維持を実現することができ、また、少なくとも、第 1の記録層と 第 2の記録層との間に中間層及び Z又は保護層を形成することで、第 1の記録層に 記録された情報信号と第 2の記録層に記録された情報信号の干渉を防ぎ、両方の層 で良好な記録再生信号を得ることができる。追記型のデジタル'バーサタイル.デイス ク(DVD— R)のようなヒートモード型の光情報記録媒体として利用できる。 The optical information recording medium of the present invention can achieve stable recording / reproduction characteristics over a long period of time by containing an oxonol dye, and at least the first recording layer and the second recording layer. By forming an intermediate layer and a Z or protective layer between them, the information signal recorded on the first recording layer and the information signal recorded on the second recording layer can be prevented from interfering with each other. Recording / reproducing signals can be obtained. It can be used as a heat mode type optical information recording medium such as write-once digital 'versatile' disk (DVD-R).
符号の説明
1, 8· "基板 Explanation of symbols 1, 8 · "Board
LO…第 1の記録層 LO ... 1st recording layer
3···反射層 3 ... Reflective layer
4·· '中間層 4 'Middle layer
5···保護層又は色素保護層 L1…第 2の記録層 5 ..Protective layer or dye protective layer L1 ... second recording layer
7···反射層
7 ... Reflective layer
Claims
請求の範囲 The scope of the claims
[1] 基板上に、色素を含有する記録層が少なくとも 2層形成され、少なくとも 2層ある前 記記録層のうち、第 1の記録層および第 2の記録層に含有される前記色素の少なくと も 1種がォキソノール色素であり、 [1] At least two recording layers containing a dye are formed on a substrate, and among the recording layers having at least two layers, the amount of the dye contained in the first recording layer and the second recording layer is small. One is an oxonol dye,
前記第 1の記録層と第 2の記録層との間に中間層が形成されていることを特徴とす る光情報記録媒体。 An optical information recording medium, wherein an intermediate layer is formed between the first recording layer and the second recording layer.
[2] 前記ォキソノール色素が、下記一般式(1)で表される構造を有することを特徴とす る請求項 1に記載の光情報記録媒体。 [2] The optical information recording medium according to [1], wherein the oxonol dye has a structure represented by the following general formula (1).
[化 1] [Chemical 1]
(一般式(1)中、 Za1及び Za2は各々独立に酸性核を形成する原子群を表わし、 Ma1 、 Ma2及び Ma3は各々独立に、置換または無置換のメチン基を表わし、 kaは 0から 3 の整数を表わし、 kaが 2以上のとき、複数存在する Ma1と Ma2は同じでも異なってもよ ぐ Qは電荷を中和するイオンを表わし、 yは電荷の中和に必要な数を表わす。 )(In the general formula (1), Za 1 and Za 2 each independently represent an atomic group forming an acidic nucleus, Ma 1 , Ma 2 and Ma 3 each independently represent a substituted or unsubstituted methine group, ka represents an integer from 0 to 3, and when ka is 2 or more, multiple Ma 1 and Ma 2 may be the same or different. Q represents an ion that neutralizes charge, and y represents neutralization of charge. Represents the number required for.
[3] 前記基板上に、前記第 1の記録層、反射層、第 2の記録層がこの順に形成されてな ることを特徴とする請求項 1に記載の光情報記録媒体。 [3] The optical information recording medium according to [1], wherein the first recording layer, the reflective layer, and the second recording layer are formed in this order on the substrate.
[4] 前記一般式(1)中の Qで表されるイオンが、下記一般式 (2)で表される構造を有す ることを特徴とする請求項 2に記載の光情報記録媒体。 4. The optical information recording medium according to claim 2, wherein the ion represented by Q in the general formula (1) has a structure represented by the following general formula (2).
[化 2] [Chemical 2]
…一般式 (2)
(一般式(2)中、 RU、 R12、 R"、 R15、 R16、 R"、 R19、 R2°は、各々独立に水素原子また は、 1価の置換基を表し、 R13、 R18は、各々独立に、 1価の置換基を表す。 ) ... General formula (2) (In the general formula (2), R U , R 12 , R ", R 15 , R 16 , R", R 19 , R 2 ° each independently represents a hydrogen atom or a monovalent substituent, R 13 and R 18 each independently represents a monovalent substituent.
前記ォキソノール色素が、下記一般式 (3)で表される構造を有することを特徴とす る請求項 2に記載の光情報記録媒体。 3. The optical information recording medium according to claim 2, wherein the oxonol dye has a structure represented by the following general formula (3).
[化 3] [Chemical 3]
…一般式 (3) ... General formula (3)
(一般式(3)中、
R2、 R3及び R4は、各々独立に、置換または無置換のアルキル基 、置換または無置換のァリール基、又は置換または無置換のへテロ環基を表すか、 または R1と R2、又は R3と R4が、互いに結合して、環構造を形成してもよぐ R21、 R22、 R 23、 R24、 R25、
R29、及び R3°は、各々独立に、水素原子または、置換基を あらわすか、又は R21、 R22、 R23、 R24、 R25、 R26、
及び R3°のうち、隣接す る 2つの置換基が、互いに結合し、環構造を形成してもよい。 ) (In general formula (3), R 2 , R 3 and R 4 each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, or R 1 and R 2 Or R 3 and R 4 may be bonded to each other to form a ring structure R 21 , R 22 , R 2 3 , R 24 , R 25 , R 29 and R 3 ° each independently represents a hydrogen atom or a substituent, or R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , And R 3 °, two adjacent substituents may be bonded to each other to form a ring structure. )
[6] 前記少なくとも一つの記録層に隣接して保護層が設けられていることを特徴とする 請求項 1に記載の光情報記録媒体。 6. The optical information recording medium according to claim 1, wherein a protective layer is provided adjacent to the at least one recording layer.
[7] 前記保護層の材料が、 SiO、 SiO、 MgF、 SnO、 Si N、及び ZnO— Ga Oの無 [7] The protective layer is made of SiO, SiO, MgF, SnO, SiN, and ZnO—GaO.
2 2 2 3 4 2 3 機物質並びに、熱可塑性榭脂、熱硬化性榭脂、及び UV硬化性榭脂の有機物質か らなる群より選ばれる少なくとも 1種であることを特徴とする請求項 6に記載の光情報 記録媒体。 2 2 2 3 4 2 3 The organic substance and at least one selected from the group consisting of thermoplastic, thermosetting, and UV-curable organic substances. 6. The optical information recording medium according to 6.
[8] 前記中間層が熱可塑性榭脂、熱硬化性榭脂、電子線硬化性榭脂、紫外線硬化性 榭脂、感圧式両面テープ及び Si02からなる群より選ばれる少なくとも 1種であること
を特徴とする請求項 1に記載の光情報記録媒体。 [8] The intermediate layer is at least one selected from the group consisting of thermoplastic resin, thermosetting resin, electron beam curable resin, ultraviolet curable resin, pressure sensitive double-sided tape, and Si02. The optical information recording medium according to claim 1, wherein:
[9] 対向する一対の基板と、 [9] a pair of opposing substrates;
前記対向する一対の基板の間に、色素を含有する 2層以上の記録層と、 Between the pair of opposed substrates, two or more recording layers containing a dye,
前記 2層以上の記録層のうち少なくとも 1つの記録層のレーザー光が入射する側に 隣接して形成された色素保護層と A dye protective layer formed adjacent to a laser beam incident side of at least one of the two or more recording layers;
を含んでおり、前記少なくとも 1つの記録層の屈折率 (n )と当該記録層に隣接する前 The refractive index (n) of the at least one recording layer and the adjacent refractive index of the recording layer
1 1
記色素保護層の屈折率 (n )とが、下記式 (1)の条件を満たすことを特徴とする光情 The refractive index (n) of the dye protective layer satisfies the condition of the following formula (1).
2 2
報記録媒体。 Information recording medium.
式(1): n -0. 8<n <n +0. 5 Formula (1): n -0. 8 <n <n +0.5
1 2 1 1 2 1
[10] 前記色素保護層を形成する材料が、無機材料であることを特徴とする請求項 9に記 載の光情報記録媒体。 10. The optical information recording medium according to claim 9, wherein the material forming the dye protective layer is an inorganic material.
[11] 前記無機材料が、金属酸化物であることを特徴とする請求項 10に記載の光情報記 録媒体。 11. The optical information recording medium according to claim 10, wherein the inorganic material is a metal oxide.
[12] 前記金属酸化物が、酸化亜鉛と酸化ガリウムとの複合酸化物、酸ィ匕タンタル、およ び、酸ィ匕ニオブ力 なる群力 選択される少なくとも 1種であることを特徴とする請求 項 11に記載の光情報記録媒体。 [12] The metal oxide is at least one selected from a composite oxide of zinc oxide and gallium oxide, an oxide-tantalum, and a group force of acid-niobium force. The optical information recording medium according to claim 11.
[13] 前記金属酸化物が、酸ィ匕ガリウムであることを特徴とする請求項 11に記載の光情 報記録媒体。 13. The optical information recording medium according to claim 11, wherein the metal oxide is gallium oxide.
[14] 2層方式の追記型デジタルヴアーサタイルディスクであり、 [14] A two-layer write-once digital Versatile disc,
当該ディスクが、レーザー光が入射する側から第 1の記録層、色素保護層および第 2の記録層を有し、 The disc has a first recording layer, a dye protective layer and a second recording layer from the side on which the laser beam is incident,
前記色素保護層と第 2の記録層とが隣接しており、 The dye protective layer and the second recording layer are adjacent to each other;
前記第 2の記録層の屈折率 (n )と当該記録層に隣接する前記色素保護層の屈折 Refractive index (n) of the second recording layer and refraction of the dye protective layer adjacent to the recording layer
1 1
率 (n )とが、前記式 (1)の条件を満たすことを特徴とする請求項 9に記載の光情報記 The optical information recording according to claim 9, wherein the rate (n) satisfies the condition of the formula (1).
2 2
録媒体。 Recording media.
[15] 前記色素が、下記一般式(1)で表されるォキソノールであることを特徴とする請求 項 9に記載の光情報記録媒体。 15. The optical information recording medium according to claim 9, wherein the dye is oxonol represented by the following general formula (1).
[化 4]
Za' ノ …一般式 (1 ) [Chemical 4] Za 'no ... General formula (1)
(一般式(1)中、 Za1及び Za2は各々独立に酸性核を形成する原子群を表わし、 Ma1 、 Ma2及び Ma3は各々独立に、置換または無置換のメチン基を表わし、 kaは 0から 3 までの整数を表わし、 kaが 2以上のとき、
Ma2は同じでも異なって もよぐ Qは電荷を中和するイオンを表わし、 yは電荷の中和に必要な数を表わす。 )(In the general formula (1), Za 1 and Za 2 each independently represent an atomic group forming an acidic nucleus, Ma 1 , Ma 2 and Ma 3 each independently represent a substituted or unsubstituted methine group, ka represents an integer from 0 to 3, and when ka is 2 or more, Ma 2 may be the same or different Q represents the ion that neutralizes the charge, and y represents the number necessary for neutralizing the charge. )
[16] 前記一般式(1)中の Qで表されるイオン力 下記一般式(2)で表されるォキソノー ルであることを特徴とする請求項 15に記載の光情報記録媒体。 16. The optical information recording medium according to claim 15, wherein the ionic force represented by Q in the general formula (1) is an oxonol represented by the following general formula (2).
(一般式(2)中、 RU、 R12、 R"、 R15、 R16、 R"、 R19及び R2°は、各々独立に水素原子ま たは、 1価の置換基を表し、 R13及び R18は、各々独立に、 1価の置換基を表す。 )(In the general formula (2), R U , R 12 , R ", R 15 , R 16 , R", R 19 and R 2 ° each independently represents a hydrogen atom or a monovalent substituent. R 13 and R 18 each independently represent a monovalent substituent.
[17] 基板上に、少なくとも 1種のォキソノールの色素を含有する記録層を少なくとも 2層設 けた光情報記録媒体の製造方法であって、 [17] A method for producing an optical information recording medium, wherein at least two recording layers containing at least one oxonol dye are provided on a substrate.
第 1の基板上に、少なくとも 1種のォキソノールの色素を含有する記録層を少なくとも 1層設けた第 1積層体を作製する工程、 Producing a first laminate in which at least one recording layer containing at least one oxonol dye is provided on a first substrate;
第 2の基板上に、少なくとも 1種のォキソノールの色素を含有する記録層を少なくと も 1層設けた第 2積層体を作製する工程、及び Producing a second laminate in which at least one recording layer containing at least one oxonol dye is provided on the second substrate; and
前記第 1積層体と第 2積層体とを中間層を介して貼り合わせる工程 The step of bonding the first laminate and the second laminate via an intermediate layer
を含んでなる、光情報記録媒体の製造方法。 A method for producing an optical information recording medium, comprising:
[18] 前記第 1積層体及び第 2積層体の少なくとも一つの積層体の上に保護層を設ける 工程を含むことを特徴とする請求項 17に記載の光情報記録媒体の製造方法。
[19] 請求項 17に記載の製造方法により作製されることを特徴とする光情報記録媒体。
18. The method for producing an optical information recording medium according to claim 17, further comprising a step of providing a protective layer on at least one of the first laminate and the second laminate. [19] An optical information recording medium manufactured by the manufacturing method according to [17].
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JP2000311384A (en) * | 1999-04-26 | 2000-11-07 | Fuji Photo Film Co Ltd | Optical information recording medium |
JP2002249674A (en) * | 2001-02-27 | 2002-09-06 | Fuji Photo Film Co Ltd | Oxonol pigment compound, and optical information recording medium using the same, and optical information recording method |
JP2003242684A (en) * | 2002-02-14 | 2003-08-29 | Nikko Materials Co Ltd | Sputtering target essentially consisting of zinc sulfide and optical recording medium formed with phase transition optical disk protective film essentially consisting of zinc sulfide using this target, and method of manufacturing this sputtering target |
JP2004188968A (en) * | 2002-11-29 | 2004-07-08 | Fuji Photo Film Co Ltd | Optical information recording medium and novel oxonol compound |
JP2004346238A (en) * | 2003-05-23 | 2004-12-09 | Fuji Photo Film Co Ltd | Two-photon absorption polymerizable composition and three-dimensional optical recording medium produced by using the same |
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JP2000311384A (en) * | 1999-04-26 | 2000-11-07 | Fuji Photo Film Co Ltd | Optical information recording medium |
JP2002249674A (en) * | 2001-02-27 | 2002-09-06 | Fuji Photo Film Co Ltd | Oxonol pigment compound, and optical information recording medium using the same, and optical information recording method |
JP2003242684A (en) * | 2002-02-14 | 2003-08-29 | Nikko Materials Co Ltd | Sputtering target essentially consisting of zinc sulfide and optical recording medium formed with phase transition optical disk protective film essentially consisting of zinc sulfide using this target, and method of manufacturing this sputtering target |
JP2004188968A (en) * | 2002-11-29 | 2004-07-08 | Fuji Photo Film Co Ltd | Optical information recording medium and novel oxonol compound |
JP2004346238A (en) * | 2003-05-23 | 2004-12-09 | Fuji Photo Film Co Ltd | Two-photon absorption polymerizable composition and three-dimensional optical recording medium produced by using the same |
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