JP2010033667A - Optical information recording medium and method for manufacturing same, and method for recording information - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical information recording medium which has a construction of a Blu-ray Disc, exhibits excellent recording characteristics in recording with short-wavelength laser beam irradiation, and has high strength. <P>SOLUTION: The optical information recording medium 10A has a reflection layer 18, a pigment-containing recording layer 14, a barrier layer 20, and a cover layer 16 in this order on a surface of the substrate having pregrooves, wherein an intermediate layer 22 exists between the barrier layer and the cover layer, which is formed by subjecting an ultraviolet curing composition containing a conjugated diene polymer having at least two (meth)acryloyl groups in a molecule to a curing treatment, and which has a glass transition temperature of -25°C or lower. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an optical information recording medium capable of recording and reproducing information using a short wavelength laser beam and a manufacturing method thereof, and more particularly to a Blu-ray optical information recording medium and a manufacturing method thereof. Is. Furthermore, the present invention relates to a method for recording information on the optical information recording medium.

  Conventionally, a write-once CD (CD-R) and a write-once DVD (DVD-R) are known as optical information recording media capable of recording information only once with a laser beam. Information recording on a CD-R is performed by a near-infrared laser beam (usually a wavelength of about 780 nm), whereas information recording on a DVD-R is performed by a visible laser beam (about 630 to 680 nm). Is called. Since DVD-R uses laser light having a shorter wavelength than CD-R as recording laser light, DVD-R has the advantage that high-density recording is possible compared to CD-R. Therefore, in recent years, DVD-R has secured its position as a large-capacity recording medium to some extent.

  In recent years, networks such as the Internet and high-definition TVs are rapidly spreading. In addition, there is an increasing demand for a large-capacity recording medium for recording image information inexpensively and easily, with the upcoming broadcast of HDTV (High Definition Television). However, it cannot be said that the CD-R and DVD-R have a recording capacity that is large enough to meet future requirements. Therefore, in order to improve the recording density by using a laser beam having a shorter wavelength than that of the DVD-R, development of a large-capacity optical disc capable of recording with a short wavelength laser (for example, a wavelength of 440 nm or less) is in progress. As such an optical disc, for example, an optical recording disc (Blu-ray Disc, hereinafter also referred to as “BD”) called a Blu-ray system using a 405 nm blue laser has been proposed.

  The aforementioned Blu-ray disc generally has a narrower track pitch than a conventional write-once optical disc. Further, a conventional additional note that a reflective layer and a recording layer are provided in this order on a substrate, and a relatively thin light-transmitting layer (generally called a cover layer) is bonded on the recording layer. It has a layer structure different from the type optical disc. In addition, the recording laser light has a shorter wavelength. For this reason, there is a problem in that sufficient recording / reproduction characteristics cannot be obtained on a Blu-ray disc with the dyes used as recording dyes for conventional write-once optical information recording media such as CD-R and DVD-R.

On the other hand, Patent Document 1 discloses an optical information recording medium for recording information by irradiating a short wavelength laser beam like the Blu-ray type optical recording disk, and between a barrier layer and a cover layer. It is proposed to provide a pressure-sensitive adhesive layer containing a polymer having a glass transition temperature Tg of 0 ° C. or lower. Patent Document 2 proposes to provide a deformation promoting layer having a glass transition temperature of 0 ° C. or lower at the recording layer side interface of the cover layer in an optical information recording medium compatible with a blue laser.
JP 2003-217177 A JP 2007-26541 A

  Regarding the reason why the recording characteristics are improved by providing a flexible layer having a low glass transition temperature between the cover layer and the recording layer as described in Patent Documents 1 and 2, the present inventors have described the following. I guess so.

When the recording layer containing the dye is irradiated with laser light, the dye absorbs the laser light and generates heat, and the heat causes the dye skeleton or its substituent to thermally decompose to generate a gas, thereby creating voids in the pits. It is thought that it is formed. In general, in a recording layer containing a dye, the refractive index of a laser light non-irradiated portion is about 1.1 to 1.9, whereas the refractive index of a portion where a void is formed by laser light irradiation is about 1. 0, which is significantly different from the refractive index of the unirradiated part. Thereby, it is considered that a large refractive index difference can be realized, and the recording characteristics can be improved.
However, when the gap is formed in the recording layer by laser light irradiation as described above, the formation of the gap usually involves deformation of the recording layer. It becomes difficult to obtain sufficient recording characteristics. For example, in an optical information recording medium having a light reflecting layer, a recording layer, a barrier layer, an intermediate layer (a layer provided for bonding of a barrier layer and a cover layer) and a cover layer in this order on a substrate, The substrate and the light reflecting layer have higher rigidity than the intermediate layer and the barrier layer. Therefore, when the gap is formed, the recording layer pushes up the barrier layer, and when the intermediate layer located between the barrier layer and the cover layer is moderately flexible, the intermediate layer causes a concave deformation. Thus, when the intermediate layer located between the barrier layer and the cover layer is easily deformed, pits can be formed satisfactorily without preventing the formation of voids in the recording layer. Therefore, if the intermediate layer has a low glass transition temperature and is flexible, the intermediate layer can be easily deformed along with the formation of voids, so that the voids can be formed satisfactorily.

  However, in the optical information recording medium described in Patent Document 1, the intermediate layer is formed from an adhesive. When the intermediate layer is formed from an adhesive, it is necessary to perform a pressure-sensitive adhesive bonding process, and thus productivity is lowered. Therefore, in the technique described in Patent Document 1, improvement in productivity has been a problem.

  In order to improve productivity, it is considered effective to form an intermediate layer using an ultraviolet curable resin as described in the reference example of Patent Document 2. However, Patent Document 2 does not describe any details such as the composition of an acrylic ultraviolet curable resin having a low glass transition temperature used in the reference example.

  Conventionally, ultraviolet curable compositions have been widely used for laminating bonded optical disks such as CD-R and DVD-R. However, these ultraviolet curable compositions for bonded optical disks have not been required to have a low Tg. Therefore, the present inventors have repeatedly studied an ultraviolet curable composition capable of forming an intermediate layer having a low glass transition temperature. However, as a result, it has been clarified that there is a trade-off relationship that when the glass transition temperature is lowered in order to improve the recording performance, the adhesive force between the cover layer and the barrier layer is lowered. It has also been found that, depending on the ultraviolet curable composition, when a large amount of ultraviolet rays is irradiated to promote curing, a new problem arises that the transmittance with respect to the short-wavelength laser light decreases and the recording characteristics deteriorate.

  Accordingly, an object of the present invention is an optical information recording medium having a Blu-ray disc configuration, which can exhibit good recording characteristics during recording by irradiation with a short wavelength laser beam and has high strength. It is to provide.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have a glass transition temperature of −25 ° C. or lower formed from an ultraviolet curable composition as an intermediate layer provided between a barrier layer and a cover layer. By using this layer, it is possible to obtain an optical information recording medium having both high productivity and good recording characteristics. Furthermore, as the ultraviolet curable composition, at least two (meth) acryloyl groups are contained in one molecule. By using an ultraviolet curable composition containing a conjugated diene polymer having an intermediate layer capable of bonding the barrier layer and the cover layer with sufficient strength even at a low glass transition temperature, Furthermore, it discovered that the said ultraviolet curable composition had the high transmittance | permeability with respect to a short wavelength laser beam after hardening, and came to complete this invention.

That is, the above object was achieved by the following means.
[1] An optical information recording medium having a reflective layer, a dye-containing recording layer, a barrier layer, and a cover layer in this order on the surface of the substrate having the pregroove,
-25 formed between the barrier layer and the cover layer by subjecting an ultraviolet curable composition containing a conjugated diene polymer having at least two (meth) acryloyl groups in one molecule to a curing treatment. An optical information recording medium comprising an intermediate layer having a glass transition temperature of 0 ° C. or lower.
[2] The optical information recording medium according to [1], wherein the ultraviolet curable composition contains 10 to 80 parts by mass of the conjugated diene polymer with respect to 100 parts by mass of the ultraviolet curable composition.
[3] The conjugated diene polymer includes polybutadiene having at least two (meth) acryloyl groups in one molecule and / or polyisoprene having at least two (meth) acryloyl groups in one molecule. ] Or the optical information recording medium according to [2].
[4] The light according to any one of [1] to [3], wherein the ultraviolet curable composition contains a monofunctional or polyfunctional (meth) acrylate having a homopolymer glass transition temperature of −90 to 25 ° C. Information recording medium.
[5] The optical information recording medium according to any one of [1] to [4], wherein the dye is a phthalocyanine dye compound.
[6] Any one of [1] to [4], wherein the dye is at least one azo dye compound selected from the group consisting of an azo compound and an azo compound and an azo metal complex compound containing a metal ion or a metal oxide ion. An optical information recording medium described in 1.
[7] The optical information recording medium according to [6], wherein the azo metal complex compound contains a copper ion.
[8] The optical information recording medium according to [6] or [7], wherein the dye has an extinction coefficient in a range of 0.15 to 1.0 at a wavelength of 405 nm.
[9] The optical information recording medium according to any one of [6] to [8], wherein the dye has a refractive index in a range of 1.45 to 1.75 at a wavelength of 405 nm.
[10] The optical information recording medium according to any one of [5] to [9], wherein the thermal decomposition temperature of the dye is in the range of 150 to 400 ° C.
[11] The pre-groove includes a plurality of grooves and lands located between adjacent grooves, and a track pitch is in a range of 50 to 500 nm.
The optical information recording medium according to any one of [1] to [10], wherein the recording layer has a thickness in a range of 1 to 100 nm on a land and a range of 5 to 150 nm on a groove.
[12] The pre-groove includes a plurality of grooves and lands located between adjacent grooves, and a ratio of a thickness of the recording layer on the land to a thickness of the recording layer on the groove [(recording layer on the land The thickness of the recording layer on the groove)] is in the range of 0.1 to 1. The optical information recording medium according to any one of [1] to [11].
[13] The optical information recording medium according to any one of [1] to [12], which is used for recording information by irradiating a laser beam having a wavelength of 390 to 440 nm.
[14] An information recording method for recording information on a recording layer of an optical information recording medium by irradiating the optical information recording medium according to any one of [1] to [13] with a laser beam having a wavelength of 390 to 440 nm .
[15] A method for producing an optical information recording medium comprising a reflective layer, a dye-containing recording layer, a barrier layer, and a cover layer in this order on a surface having a pregroove of a substrate,
By applying an ultraviolet curable composition containing a conjugated diene polymer having at least two (meth) acryloyl groups in one molecule on the barrier layer, and irradiating the composition with ultraviolet rays, An intermediate layer having a glass transition temperature of −25 ° C. or lower is formed between the layer and the cover layer.
[16] The method for producing an optical information recording medium according to [15], wherein the ultraviolet curable composition applied on the barrier layer has a viscosity in the range of 20 to 1000 mPa · s.
[17] The optical information recording medium according to [15] or [16], wherein the ultraviolet curable composition contains 10 to 80 parts by mass of the conjugated diene polymer with respect to 100 parts by mass of the ultraviolet curable composition. Production method.
[18] The conjugated diene polymer includes polybutadiene having at least two (meth) acryloyl groups in one molecule and / or polyisoprene having at least two (meth) acryloyl groups in one molecule [15] ] The manufacturing method of the optical information recording medium in any one of [17].
[19] The light according to any one of [15] to [18], wherein the ultraviolet curable composition contains a monofunctional or polyfunctional (meth) acrylate having a homopolymer glass transition temperature of -90 to 25 ° C. A method for manufacturing an information recording medium.

  According to the present invention, an optical information recording medium excellent in recording characteristics in a short wavelength region can be provided with high productivity.

The present invention relates to an optical information recording medium having a reflective layer, a dye-containing recording layer, a barrier layer, and a cover layer in this order on a surface of a substrate having pregrooves. In the optical information recording medium of the present invention, an ultraviolet curable composition containing a conjugated diene polymer having at least two (meth) acryloyl groups in one molecule between the barrier layer and the cover layer is cured. It has an intermediate layer having a glass transition temperature of −25 ° C. or lower formed by application.
Hereinafter, the optical information recording medium of the present invention will be described in more detail.

Intermediate layer The optical information recording medium of the present invention is a BD-structured optical information recording medium having a reflective layer, a dye-containing recording layer, a barrier layer, and a cover layer in this order on a substrate, between the barrier layer and the cover layer. And an intermediate layer (hereinafter also referred to as “adhesive layer”) having a glass transition temperature (Tg) of −25 ° C. or lower formed by subjecting the ultraviolet curable composition to a curing treatment. As described above, by providing a flexible intermediate layer between the barrier layer and the cover layer, good recording characteristics can be obtained without impeding the formation of voids in the recording layer. If the glass transition temperature of the intermediate layer exceeds −25 ° C., the intermediate layer is not deformed well due to void formation in the recording layer, and it becomes difficult to obtain sufficient recording characteristics. In order to obtain excellent recording characteristics, the glass transition temperature of the intermediate layer is preferably −35 ° C. or lower, more preferably −45 ° C. or lower. Moreover, it is preferable that the glass transition temperature of a contact bonding layer is -125 degreeC or more from the point of coexistence with peeling strength. That is, the glass transition temperature of the adhesive layer used in the present invention is preferably in the range of −25 ° C. to −125 ° C., more preferably −35 ° C. to −100 ° C., and further preferably −45 ° C. to −90 ° C. It is.
In addition, the glass transition temperature (Tg) in this invention is a glass transition temperature calculated | required by differential scanning calorimetry (DSC). The glass transition temperature of the intermediate layer can be controlled by the formulation of the ultraviolet curable composition used for forming the intermediate layer, the type of the ultraviolet curable compound contained in the composition, the curing conditions, and the like.

  In the present invention, the storage elastic modulus can also be used as an indicator of the hardness of the adhesive layer, similarly to the glass transition temperature. The storage elastic modulus G ′ by shear mode of the adhesive layer is preferably 1000 KPa or less, more preferably 500 KPa or less, and further preferably 400 KPa or less at 30 ° C. The storage elastic modulus of the adhesive layer is preferably 1 KPa or more from the viewpoint of storage stability. That is, the storage elastic modulus of the adhesive layer is preferably in the range of 1000 KPa to 1 KPa, more preferably 500 KPa to 10 KPa, and still more preferably 400 KPa to 20 KPa. The storage elastic modulus can be obtained from dynamic viscoelastic behavior obtained by measurement at a frequency of 1 Hz using a dynamic viscoelasticity measuring device (for example, DVA-200 manufactured by IT Measurement Control Co., Ltd.). Further, the loss tangent (tan δ) determined by the dynamic viscoelastic behavior is preferably in the range of 1.0 to 0.003 at 30 ° C., more preferably 0 when measured in a frequency of 1 Hz, tensile mode or shear mode. The range is from .9 to 0.0035, and more preferably from 0.6 to 0.004.

  In the present invention, by forming the intermediate layer from the ultraviolet curable composition, an apparatus for bonding with the cover layer becomes simple, and the bonding time can be shortened, so that low-cost manufacturing is possible. Become. Thereby, productivity can be improved. By using an ultraviolet curable composition containing a conjugated diene polymer having at least two (meth) acryloyl groups in one molecule as the ultraviolet curable composition, the glass transition is maintained while maintaining the adhesive force. An intermediate layer having a low temperature can be formed. In the present invention, by forming an adhesive layer using the ultraviolet curable composition, the barrier layer and the cover layer are strengthened by exhibiting sufficient transmittance for short wavelength laser light even at low Tg. An adhesive layer having sufficient adhesive force that can be attached to each other can be formed. Thus, an optical information recording medium having high strength and good recording characteristics can be obtained.

  In the present invention, “(meth) acryloyl group” includes acryloyl group and methacryloyl group, and “conjugated diene polymer” is obtained by polymerization or copolymerization of at least one conjugated diene. Polymer. Examples of the conjugated diene include conjugated dienes having 4 to 8 carbon atoms such as butadiene, isoprene, pentadiene and 2,3-dimethylbutadiene. Examples of the conjugated diene polymer include polybutadiene, polyisoprene, polypentadiene, butadiene-isoprene copolymer, and the like. Polybutadiene and polyisoprene are preferable from the viewpoint of availability and cost.

  The conjugated diene polymer has at least two (meth) acryloyl groups in one molecule. That is, the conjugated diene polymer is bifunctional or higher. When the number of (meth) acryloyl groups is one in one molecule, the conjugated diene polymer does not participate in the cross-linked structure, and the recording properties and the adhesive force are not compatible. The conjugated diene polymer is preferably bifunctional to pentafunctional, more preferably bifunctional to tetrafunctional, and even more preferably bifunctional to trifunctional.

As the ultraviolet curable composition, it is preferable to use a liquid composition at room temperature to 40 ° C. It is preferable not to use a solvent, and even if it is used, it is preferable to keep it as small as possible. The UV curable composition preferably has a viscosity at a temperature of 25 ° C. of 20 to 1000 mPa · s, more preferably a viscosity of 30 to 700 mPa · s, more preferably a viscosity from the viewpoint of application suitability by a spin coating method. The thing of 40-500 mPa * s is still more preferable.
In order to adjust the viscosity, a monofunctional (meth) acrylic monomer may be added as a diluent. A preferable monofunctional (meth) acryl monomer will be described later. As the thickener, a polymer having a mass average molecular weight of 10,000 or more can be used. In order to obtain a desired viscosity with a small amount of addition, a higher molecular weight polymer, for example, a polymer having a mass average molecular weight of 100,000 or more is preferable, and a polymer having a mass average molecular weight of 1,000,000 or more is more preferable. However, it is of course possible to obtain an ultraviolet curable composition having a suitable viscosity without using a thickener by using a conjugated diene polymer having a molecular weight in the preferred range described below.

  The conjugated diene polymer preferably has a mass average molecular weight of 1000 to 50000, more preferably 1500 to 45000, and still more preferably 2000 to 40000. When the weight average molecular weight is within the above range, an ultraviolet curable composition having the above preferred viscosity can be obtained, and an ultraviolet curable composition having a glass transition temperature after curing in a desired range can be obtained. .

  The conjugated diene polymer having at least two (meth) acryloyl groups in one molecule is, for example, (1) terminal hydroxyl group of conjugated diene polymer via 2,4-tolylene diisocyanate via 2-hydroxyethyl acrylate. (2) Method of esterifying 2-hydroxyethyl acrylate to maleated conjugated diene polymer with maleic anhydride added by ene addition reaction, (3) Carboxyl group of conjugated diene polymer (4) A method by an esterification reaction between an epoxidized conjugated diene polymer obtained by acting an epoxidizing agent on a conjugated diene polymer and acrylic acid, (5) Dehydrochlorination reaction of conjugated diene polymer having hydroxyl group and acrylic acid chloride It can be obtained by a method with. Or it can also obtain as a commercial item. Examples of commercially available products include TE-2000 manufactured by Nippon Soda Co., Ltd., UC-102 manufactured by Kuraray Co., Ltd., UC-203, UC-105, and BAC-45 manufactured by Osaka Organic Chemical Industry Co., Ltd., but the present invention is not limited thereto. Absent.

  The conjugated diene polymer is preferably contained in an amount of 10 to 80 parts by mass in 100 parts by mass of the composition from the viewpoint of the glass transition temperature of the intermediate layer to be formed and the viscosity of the ultraviolet curable composition. It is more preferable that it is contained, and it is still more preferable that 20-70 mass parts is contained. In addition, the said conjugated diene polymer may be used only 1 type, and may be used in combination of 2 or more type.

［一般式（ａ）、（ｂ）中、Ｒ¹¹は置換基を表す。］ The ultraviolet curable composition may contain a polymerizable compound such as a polymerizable monomer such as monofunctional (meth) acrylate or polyfunctional (meth) acrylate, or a polymerizable oligomer, together with the conjugated diene polymer. In the present invention, “(meth) acrylate” includes acrylic ester (acrylate) and methacrylic ester (methacrylate). Each of these can be used alone or in combination of two or more. Examples of the monofunctional (meth) acrylate include acrylates represented by the following general formula (a) and methacrylates represented by the following general formula (b).

[In the general formulas (a) and (b), R ¹¹ represents a substituent. ]

More specifically, examples of the polymerizable monomer that can be used in the present invention include the following. As the monofunctional (meth) acrylate, for example, in the general formulas (a) and (b), the substituent R ¹¹ is a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, a ter-butyl group, a pentyl group, Hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, benzyl, methoxyethyl, butoxyethyl, phenoxyethyl, nonylphenoxyethyl, tetrahydro Furfuryl group, glycidyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-chloro-2-hydroxypropyl group, dimethylaminoethyl group, diethylaminoethyl group, nonylphenoxyethyltetrahydrofurfuryl group, caprolactone-modified tetrahydrofurfur Furyl group, isoborni Group, dicyclopentanyl group, a dicyclopentenyl group, having a substituent such as di-cyclopentenylene b carboxyethyl (meth) acrylate, further, include (meth) acrylic acid.
Preferred substituents R ¹¹ include butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, dodecyl group, and more preferred monomers are butyl acrylate, hexyl acrylate, 2- Examples include ethylhexyl acrylate, octyl acrylate, nonyl acrylate, and dodecyl methacrylate.

Examples of the polyfunctional (meth) acrylate include 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexane. Diacrylates such as diol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, tricyclodecane dimethanol, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, Di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol, Di (meth) acrylate, trimethylolpropane tri (meth) acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of Sphenol A, 3 mol or more of ethylene oxide or propylene per 1 mol of trimethylolpropane Diol or tri (meth) acrylate of triol obtained by adding oxide, di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A, tris (2-hydroxyethyl) ) Tri (meth) acrylate obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of isocyanurate tri (meth) acrylate and tris (2-hydroxyethyl) isocyanurate , Pentaerythritol tri- or tetra (meth) acrylate, tri- or tetra (meth) acrylate obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of pentaerythritol, poly (meth) acrylate of dipentaerythritol , Poly (meth) acrylate obtained by adding 6 mol or more of ethylene oxide or propylene oxide to 1 mol of dipentaerythritol, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, alkyl-modified dipentaerythritol poly ( (Meth) acrylate, caprolactone-modified dipentaerythritol poly (meth) acrylate, hydroxypivalate neopentyl glycol diacrylate, caprolactone-modified hydro Shipibarin acid neopentyl glycol diacrylate, ethylene oxide-modified phosphoric acid (meth) acrylate, ethylene oxide-modified alkylated phosphoric acid (meth) acrylate.
Preferably, obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A, and adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane. Triol di- or tri (meth) acrylate, tri (meth) acrylate obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of tris (2-hydroxyethyl) isocyanurate, 4 mol of 1 mol of pentaerythritol Tri- or tetra (meth) acrylate obtained by adding the above ethylene oxide or propylene oxide, 6 moles or more of ethylene oxide or propylene oxide per mole of dipentaerythritol Poly (meth) acrylate obtained by addition, and more preferably, di (meth) acrylate of diol obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of bisphenol A, 3 moles of 1 mole of trimethylolpropane. Diol or tri (meth) acrylate of triol obtained by adding more than mol of ethylene oxide or propylene oxide, tri or tetra (meth) obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of pentaerythritol Acrylate.

  N-vinyl-2-pyrrolidone, acryloylmorpholine, vinylimidazole, N-vinylcaprolactam, N-vinylformamide, vinyl acetate, (meth) acrylic acid, (meth) acrylamide, N-hydroxymethylacrylamide or N-hydroxyethyl Acrylamide and their alkyl ether compounds can also be used.

  Furthermore, a polymerizable oligomer can also be used as the ultraviolet curable compound. Examples of the polymerizable oligomer include polyester (meth) acrylate, polyether (meth) acrylate, and epoxy (meth) acrylate.

  As described above, the glass transition temperature of the intermediate layer formed from the ultraviolet curable composition is adjusted by the formulation of the ultraviolet curable composition, the type of the ultraviolet curable compound contained in the composition, the curing conditions, and the like. Can do. In particular, in the present invention, as a polymerizable compound used in combination with the conjugated diene polymer in an ultraviolet curable composition in order to form an intermediate layer having a low Tg, it is far more than that used in an ordinary ultraviolet curable composition. It is preferable to use a low-Tg compound, especially a monofunctional or polyfunctional (meth) acrylate having a glass transition temperature of -90 to 25 ° C. According to the present invention, by using the conjugated diene compound, it is possible to achieve high transmittance and high adhesive strength with respect to short wavelength laser light in the adhesive layer, and by using the low Tg polymerizable compound as described above. Low Tg of the adhesive layer can be achieved. The glass transition temperature of the (meth) acrylate homopolymer refers to a value obtained by differential scanning calorimetry (DSC) for the (meth) acrylate homopolymer to be measured.

  When the polymerizable compound is used in combination with the conjugated diene polymer, the content of the polymerizable compound is 90 to 20 parts by mass per 100 parts by mass in total of the conjugated diene polymer and the polymerizable compound. It is preferably 85 to 25 parts by mass, more preferably 80 to 30 parts by mass.

  In general, a photopolymerization initiator is added to the ultraviolet curable composition. The photopolymerization initiator is not particularly limited as long as it can cure an ultraviolet curable compound represented by a polymerizable monomer and / or a polymerizable oligomer to be used. As the photopolymerization initiator, a molecular cleavage type or a hydrogen abstraction type is suitable for the present invention.

As photopolymerization initiators, benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, benzyl, 2,2-dimethoxy-2-phenylacetophenone, 2,4,6-trimethylbenzoyldiphenyl Phosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, etc. Further, other molecular cleavage types such as 1-hydroxycyclohexyl phenyl ketone, benzoyl ethyl ether, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-Isopro Ruphenyl) -2-hydroxy-2-methylpropan-1-one and 2-methyl-4 ′-(methylthio) -2-morpholinopropiophenone may be used in combination, and a hydrogen abstraction type photopolymerization initiator. Benzophenone, 4-phenylbenzophenone, isophthalophenone, 4-benzoyl-4′-methyl-diphenylsulfide and the like can be used in combination.
Preferably, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2 -Methyl-4 '-(methylthio) -2-morpholinopropiophenone and 4-phenylbenzophenone, more preferably 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone 2-methyl-4 ′-(methylthio) -2-morpholinopropiophenone, 4-phenylbenzophenone.

  Further, as a sensitizer for the photopolymerization initiator, for example, triethylamine, methyldiethanolamine, triethanolamine, p-diethylaminoacetophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl, p-dimethylaminobenzoic acid. Amines that do not cause an addition polymerization reaction may be used in combination with the aforementioned polymerizable components, such as isoamyl, N, N-dimethylbenzylamine, and 4,4′-bis (diethylamino) benzophenone. Of course, it is preferable to select and use the photopolymerization initiator and the sensitizer that are excellent in solubility in the curable component and do not inhibit the ultraviolet light transmittance.

  In addition, the ultraviolet curable composition, if necessary, further includes other additives such as thermal polymerization inhibitors, antioxidants typified by hindered phenols, hindered amines, phosphites, plasticizers, and epoxy silanes, Silane coupling agents represented by mercaptosilane, (meth) acrylic silane and the like can be blended for the purpose of improving various properties. It is preferable to select and use those that are excellent in solubility in a curable component and those that do not impair ultraviolet light transmittance.

  The amount of photopolymerization initiator, sensitizer and other additives used in the ultraviolet curable composition can be appropriately set, for example, with respect to the total amount of the polymerizable compound containing the conjugated diene polymer, The amount of photopolymerization initiator used can be 1.0 to 10.0% by mass, the amount of sensitizer used can be 0.5 to 10.0% by mass, and other additives. The total amount of use can be 0.1-5.0 mass%.

  Details of the ultraviolet curable composition used for forming the intermediate layer are as described above. The method for forming the intermediate layer is not particularly limited, but a predetermined amount of an ultraviolet curable composition is applied on the surface (bonded surface) of the barrier layer, and a cover layer is placed thereon, and then adhered by spin coating. After spreading the agent so as to be uniform between the surface to be bonded and the cover layer, the intermediate layer can be formed by irradiating ultraviolet rays from the cover layer side and performing a curing treatment. Alternatively, after applying a predetermined amount of an ultraviolet curable composition on the surface of the barrier layer, the coating surface is irradiated with ultraviolet rays to be cured, and then an ultraviolet curable composition for forming a cover layer is applied thereon to apply ultraviolet rays. The cover layer can also be formed by irradiation and curing.

In any of the above methods, it is preferable that the irradiation amount of the ultraviolet ray irradiated for curing the intermediate layer is more than 200 mJ / cm ² . More preferably, it is the range of 200-2000 mJ / cm < ² >. As a UV lamp used for curing, for example, a metal halide lamp M02-L31 (manufactured by Eye Graphics, with cold mirror, lamp output 120 W / cm), 4.2 inch-SPIRAL LAMP manufactured by Xenon Corporation, or the like can be used. It is preferable to appropriately set the distance between the lamp surface and the sample surface during ultraviolet irradiation.

In order to move the medium coated with the ultraviolet curable composition to the UV irradiation position (for example, move from the spin table to the UV irradiation table), the substrate is held and lifted at the outer peripheral part or inner peripheral part of the medium. It is desirable to move it. If the medium is supported and lifted from above by adsorption or other method, the medium will be deformed because the UV curable composition is uncured, or bubbles may be mixed into the intermediate layer, causing fluctuations in the film thickness of the intermediate layer. And may cause defects. In the case of moving while supporting the outer peripheral portion, it is preferable to periodically clean the support member. In the outer peripheral portion, an uncured ultraviolet curable composition shaken off during spinning may adhere to the outer peripheral edge portion and may adhere to the support member. When the medium is repeatedly moved by the same support member, it may adhere to the medium from the support member and cause a defect.
In addition, at the UV irradiation position (for example, on the UV irradiation table), as a part for supporting the medium, one part or a plurality of parts are supported from among the inner peripheral part, outer peripheral part or middle peripheral part of the substrate (medium). can do. The entire surface may be uniformly supported by a plate-like support member. In the case of supporting a plurality of parts, the support height of each part can be changed. This is because, for example, when only the inner periphery is supported, the unsupported medium outer periphery hangs down under its own weight and is cured in that shape, so that when the medium is warped after curing, the outer periphery also This is a case where warping after curing is suppressed by supporting and suppressing sagging, and the effect of adjusting the media shape after curing by adjusting the height of each supporting member can be expected.

  The thickness of the intermediate layer is preferably in the range of 0.1 to 100 μm, more preferably in the range of 0.5 to 50 μm, still more preferably 1 to 30 μm, from the viewpoint of achieving both good recording characteristics and adhesive strength. Range.

  The ultraviolet curable composition may have a high transmittance for short wavelength laser light even after curing. Since information is recorded on the optical information recording medium having the BD structure from the cover layer side, the intermediate layer located between the cover layer and the recording layer has a high transmittance for short wavelength laser light. From the viewpoint of improving the recording characteristics, it is preferable. According to the ultraviolet curable composition, an intermediate layer having a transmittance of, for example, 100 to 80% can be formed as a value measured by the method described in Examples described later.

  A specific example of the optical information recording medium of the present invention is shown in FIG. A first optical information recording medium 10A shown in FIG. 1 includes a first light reflecting layer 18, a first write-once recording layer 14, a barrier layer 20, an intermediate layer 22, and a cover layer 16 on a first substrate 12. And in this order. Hereinafter, the materials constituting the substrate and other layers used in the optical information recording medium of the present invention will be described in order.

Substrate As the substrate used in the present invention, various materials used as substrate materials for conventional optical information recording media can be arbitrarily selected and used. As the substrate, a transparent disk-shaped substrate is preferably used.
Specifically, glass; acrylic resin such as polycarbonate and polymethyl methacrylate; vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer; epoxy resin; amorphous polyolefin; polyester; metal such as aluminum; These may be used together if desired.
Among the materials, thermoplastic resins such as amorphous polyolefin and polycarbonate are preferable, and polycarbonate is particularly preferable from the viewpoints of moisture resistance, dimensional stability, and low price. When these resins are used, the substrate can be manufactured by injection molding.
The thickness of the substrate is generally in the range of 0.7 to 2 mm, preferably in the range of 0.9 to 1.6 mm, and more preferably 1.0 to 1.3 mm.
An undercoat layer can also be formed on the substrate surface on the side where the light reflecting layer described later is provided for the purpose of improving flatness and adhesion.

  On the surface of the substrate on which the recording layer is formed, pregrooves (guide grooves) composed of a plurality of grooves and lands positioned between adjacent grooves are formed. This pre-groove is provided to achieve a higher recording density than CD-R and DVD-R. For example, the optical information recording medium of the present invention is used as a medium corresponding to a blue-violet laser. It is suitable for use.

  The track pitch of the pregroove is preferably in the range of 50 to 500 nm. The upper limit value is more preferably 420 nm or less, still more preferably 370 nm or less, and even more preferably 330 nm or less. Further, the lower limit is more preferably 100 nm or more, further preferably 200 nm or more, and further preferably 260 nm or more. If the track pitch is 50 nm or more, the pregroove can be formed accurately, and the occurrence of crosstalk can be avoided. If the track pitch is 500 nm or less, high-density recording can be performed.

  The track pitch of the pregroove is preferably 100 nm or more and 420 nm or less, more preferably 200 nm or more and 370 nm or less, and further preferably 260 nm or more and 330 nm or less.

  The groove width (half width) of the pregroove is preferably in the range of 25 to 250 nm. The upper limit is preferably 240 nm or less, more preferably 230 nm or less, and still more preferably 220 nm or less. Further, the lower limit is preferably 50 nm or more, more preferably 80 nm or more, and further preferably 100 nm or more. If the groove width of the pregroove is 25 nm or more, the groove can be sufficiently transferred at the time of molding, and further, an increase in error rate at the time of recording can be suppressed. Furthermore, it is possible to avoid the occurrence of crosstalk due to the spread of pits formed during recording.

  The groove width (half width) of the pregroove is preferably 50 nm or more and 240 nm or less, more preferably 80 nm or more and 230 nm or less, and further preferably 100 nm or more and 220 nm or less.

  The groove depth of the pregroove is preferably in the range of 5 to 150 nm. The upper limit is preferably 85 nm or less, more preferably 80 nm or less, and even more preferably 75 nm or less. Further, the lower limit is preferably 10 nm or more, more preferably 20 nm or more, and further preferably 28 nm or more. If the groove depth of the pregroove is 5 nm or more, a sufficient recording modulation degree can be obtained, and if it is 150 nm or less, a high reflectance can be obtained.

  The groove depth of the pregroove is preferably 10 nm to 85 nm, more preferably 20 nm to 80 nm, and still more preferably 28 nm to 75 nm.

In addition, the groove inclination angle of the pregroove is preferably 80 ° or less, more preferably 75 ° or less, still more preferably 70 ° or less, and particularly preferably 65 ° or less. preferable. Further, the lower limit value is preferably 20 ° or more, more preferably 30 ° or more, and further preferably 40 ° or more.
If the groove inclination angle of the pregroove is 20 ° or more, a sufficient tracking error signal amplitude can be obtained, and if it is 80 ° or less, the moldability is good.

The reflective layer can be formed on the substrate by, for example, vacuum vapor deposition, sputtering, or ion plating with a light reflective material having a high reflectance with respect to laser light.
The thickness of the light reflecting layer is generally in the range of 10 to 300 nm and preferably in the range of 20 to 200 nm.
The reflectance is preferably 70% or more.

  As a light reflective material having a high reflectance, Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd , Ir, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi, and the like, and metal and semi-metal or stainless steel. These light reflecting materials may be used alone, or may be used in combination of two or more kinds or as an alloy. Among these, Cr, Ni, Pt, Cu, Ag, Au, Al, and stainless steel are preferable. Particularly preferred is Au, Ag, Al or an alloy thereof, and most preferred is Au, Ag or an alloy thereof.

Recording Layer The dye compound used in the optical information recording medium of the present invention includes phthalocyanine compounds, azo compounds, and azo metal complex compounds, methine dyes (cyanine compounds, oxonol compounds, styryl dyes, merocyanine dyes), triazine dyes Benzotriazole dyes, benzoxazole dyes, aminobutadiene, azomethine dyes, pyridoporphyrazine dyes, pyradoporphyrazine dyes, porphyrin dyes, porphyrazine dyes, preferably phthalocyanine compounds, azo compounds, and azo metal complexes Compounds, methine dyes (cyanine compounds, oxonol compounds, styryl dyes, merocyanine dyes), triazine dyes, benzotriazole dyes, more preferably phthalocyanine compounds, azo compounds, and Zone metal complex compounds, methine dyes (cyanine compound, an oxonol-based compound, styryl dyes, merocyanine dyes,) and the like.

  In the present invention, in order to satisfactorily form voids in the recording layer and improve the recording characteristics, among the dye compounds represented above, the mass reduction rate in the main weight loss process in thermal mass spectrometry is 10% or more. It is preferable to use a compound having a certain thermal decomposability. When the temperature of the compound is raised in a certain temperature range, mass loss due to thermal decomposition occurs. Depending on the type of compound, there are usually several temperature ranges (mass reduction process) that show a large mass loss. In the present invention, among several mass reduction processes (weight reduction processes), the one with the greatest degree of mass reduction is called the main weight reduction process. The mass reduction rate can be obtained by the following method.

  As shown in FIG. 2, the compound having a mass M0 is heated at 10 ° C./min in a nitrogen atmosphere. As the temperature rises, the mass decreases little by little along a straight line ab, and when reaching a certain temperature, a sudden mass decrease along a substantially straight line cd occurs. When the temperature is further increased, the rapid mass decrease ends, and the mass decrease substantially along the straight line ef occurs. Here, at the intersection of the straight line ab and the straight line cd, the temperature is T1 (° C.), and the residual mass ratio with respect to the initial mass M0 is m1 (%). Further, at the intersection of the straight line cd and the straight line ef, the temperature is T2 (° C.), and the residual mass ratio with respect to the initial mass M0 is m2 (%). That is, in the main weight loss process, the weight loss start temperature is T1, the weight loss end temperature is T2, and the mass reduction rate is represented by (m1-m2) (%).

The decrease in mass under the nitrogen atmosphere is considered to be due to the generation of gas based not on the oxidative decomposition but on the substituent decomposition or skeleton decomposition of the dye. Therefore, it is considered that the higher the mass reduction rate, the more gas is generated due to thermal decomposition, which is advantageous for void formation. It is considered that, among the dye compounds, the recording layer contains a material having a mass reduction rate of 10% or more, so that the amount of gas generated by laser light irradiation is large and pits can be formed satisfactorily. Among the dye compounds, those having a thermal decomposability of 20% or more at a thermal decomposition at 150 ° C. to 400 ° C. are more preferable, and a mass decreasing rate at a thermal decomposition at 200 ° C. to 400 ° C. is 25. Those having a thermal decomposability of at least% are more preferred. The thermal decomposability of the dye can be controlled by the type of substituent introduced into the dye skeleton.
Specifically, for example, Seiko Instruments Inc. Using EXSTAR6000, the mass reduction rate can be obtained by heating at a rate of 10 ° C./min in the range of 30 ° C. to 550 ° C. under an N ₂ air flow (flow rate 200 ml / min).

Furthermore, in order to improve sensitivity, it is preferable to use a compound having good thermal decomposability as the dye compound. As an index of thermal decomposability, the thermal decomposition temperature can be used. In the present invention, it is preferable to use a pigment compound having a thermal decomposition temperature of, for example, 150 to 400 ° C, preferably 200 to 400 ° C, more preferably 200 to 380 ° C. In addition, the thermal decomposition temperature in this invention shall say the value calculated | required by TG / DTA measurement. Specifically, for example, Seiko Instruments Inc. Using EXSTAR6000 manufactured, the temperature was raised at 10 ° C / min in the range of 30 ° C to 550 ° C under an N ₂ stream (flow rate 200 ml / min), and the temperature at which the mass reduction rate reached 10% was the thermal decomposition temperature. Can be requested.

  When the optical information recording medium of the present invention is irradiated with laser light, the temperature of the portion of the recording layer irradiated with the laser light locally rises, and the recording dye is considered to thermally decompose at that portion. In general, organic substances show endothermic heat accompanying state changes before the thermal decomposition temperature. If the calorific value before the pyrolysis temperature is large, a large amount of energy is given to the gas generated at the time of pyrolysis, so that the heat generated at the time of recording pit formation may affect the preceding recording pit and cause deformation of the pit shape. In addition, it may be difficult to control the shape of the formed recording pit. On the other hand, if the calorific value before thermal decomposition is small, the energy given to the gas generated at the time of thermal decomposition becomes small, so the influence on adjacent pits can be reduced. However, if the heat generation amount is too small, pit formation may be difficult. Usually, the main weight loss process is a temperature range immediately before the thermal decomposition temperature, and therefore, as an index of material change during heat mode recording, the total calorific value in the main weight loss process, that is, the decrease start temperature in the main weight loss process (FIG. 2). The total calorific value in the temperature range (T1 to T2) from the inside T1) to the end-of-weight reduction temperature (T2 in FIG. 2) can be used. The total calorific value (hereinafter also referred to as “total calorific value Q”) in the main reduction process of the dye in the recording layer is preferably in the range of −200 to 500 J / g. If the total calorific value Q is within the above range, pits having a desired shape can be formed satisfactorily, and thereby good recording / reproducing characteristics can be obtained. A more preferable range of Q is −180 to 450 J / g, and a more preferable range is −160 to 350 J / g.

  The total calorific value Q is the calorific value in the temperature range from the decrease start temperature (T1 in FIG. 2) to the end temperature of decrease (T2 in FIG. 2) in the main weight loss process in the thermal mass spectrometry, manufactured by Seiko Instruments Inc. It can be determined by using DSC6200R and measuring by DSC (Differential Scanning Calorimetry) method. In general, when an organic substance is thermally decomposed, a gas corresponding to a decrease in mass is volatilized. Since the energy given to this gas is also included in Q, DSC measurement is performed in a sealed atmosphere. Specifically, the DSC measurement can be performed by sealing the sample in a SUS sealed container or the like.

  Specific examples of dye compounds that can realize a large refractive index difference in the short wavelength region and can exhibit excellent recording characteristics especially by irradiation with a short wavelength laser beam when combined with the aforementioned intermediate layer are shown below. The present invention is not limited to the following dye compounds.

Examples of the dye compound contained in the phthalocyanine dye compound recording layer include phthalocyanine dye compounds (phthalocyanine derivatives) represented by the following general formula (I). The phthalocyanine dye compound preferably has the aforementioned preferable dye characteristics.

［一般式（Ｉ）中、Ｒは置換基を表し、ｎは１〜８の範囲の整数を表し、ｎが２以上の整数のとき、複数個のＲは互いに同一でも異なっていてもよく、Ｍは２個の水素原子、２〜４価の金属原子、２〜４価のオキシ金属原子、または配位子を有する２〜４価の金属原子を表す。］

[In General Formula (I), R represents a substituent, n represents an integer in the range of 1 to 8, and when n is an integer of 2 or more, a plurality of R may be the same or different from each other; M represents two hydrogen atoms, a divalent to tetravalent metal atom, a divalent to tetravalent oxymetal atom, or a divalent to tetravalent metal atom having a ligand. ]

  Details of the general formula (I) will be described below.

In general formula (I), R represents a substituent. Details of the substituent represented by R are as described later for R ^{α1 to} R ^α8 and R ^{β1 to} R ^{β8 in} the general formula (II).

  In general formula (I), n represents an integer in the range of 1 to 8, preferably represents an integer in the range of 2 to 7, and more preferably represents an integer in the range of 3 to 6. When n is an integer greater than or equal to 2, several R may mutually be same or different.

M represents two hydrogen atoms, a divalent to tetravalent metal atom, a divalent to tetravalent oxymetal atom, or a divalent to tetravalent metal atom having a ligand.
The divalent to tetravalent metal atom is preferably a copper atom, a zinc atom or a magnesium atom, more preferably a copper atom or a zinc atom, and most preferably a copper atom.
The divalent to tetravalent oxymetal atom is preferably an oxide containing any one of the above metal atoms.
Examples of the ligand include a halogen atom, an aryl group having 6 to 30 carbon atoms, a 5-membered or 6-membered heterocyclic group, a cyano group, and a hydroxyl group.

  The compound represented by the general formula (I) is preferably a compound represented by the following general formula (II).

In the general formula (II), R ^{α1 to} R ^α8 and R ^{β1 to} R ^β8 each independently represent a hydrogen atom, a halogen atom, a nitro group, a formyl group, a carboxyl group, a sulfo group, a C 1-20 substitution or Unsubstituted alkyl group, substituted or unsubstituted aryl group having 6 to 14 carbon atoms, substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, carbon C6-C20 substituted or unsubstituted aryloxy group, C1-C20 substituted or unsubstituted heterocyclic oxy group, C1-C20 substituted or unsubstituted alkylthio group, C6-C20 Substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group having 1 to 20 carbon atoms, substituted or unsubstituted acyl group having 2 to 21 carbon atoms, substituted with 1 to 20 carbon atoms Is an unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group having 6 to 14 carbon atoms, a heterylsulfonyl group having 1 to 10 carbon atoms, a substituted or unsubstituted carbamoyl group having 1 to 25 carbon atoms, a carbon number 0-32 substituted or unsubstituted sulfamoyl group, C2-C20 substituted or unsubstituted alkoxycarbonyl group, C7-C15 substituted or unsubstituted aryloxycarbonyl group, C2-C21 substitution Or an unsubstituted acylamino group, a substituted or unsubstituted sulfonylamino group having 1 to 20 carbon atoms, or a substituted or unsubstituted amino group having 0 to 36 carbon atoms, M ¹ represents two hydrogen atoms, 2 to 2 It represents a tetravalent metal atom, a divalent to tetravalent metal atom having a divalent to tetravalent oxymetal atom or a ligand. The amino group includes an anilino group.
Details of the general formula (II) will be described below.

In the general formula (II), R ^{α1 to} R ^α8 and R ^{β1 to} R ^β8 are each independently, preferably each independently a hydrogen atom, a halogen atom (for example, a fluorine atom or a bromine atom), a carboxyl group, a sulfo group. Group, substituted or unsubstituted alkyl group having 1 to 16 carbon atoms (for example, methyl group, ethyl group, n-propyl group, i-propyl group), substituted or unsubstituted aryl group having 6 to 14 carbon atoms (for example, , Phenyl group, p-methoxyphenyl group, p-octadecylphenyl group), substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms (for example, 5- or 6-membered substituted or unsubstituted, aromatic or A monovalent group obtained by removing one hydrogen atom from a non-aromatic heterocyclic compound, and a 5- or 6-membered aromatic heterocyclic group having 1 to 20 carbon atoms, such as a 2-furyl group. , 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms (eg, methoxy group, ethoxy group, n-octyloxy group), 6 to 6 carbon atoms 20 substituted or unsubstituted aryloxy groups (for example, phenoxy group, p-ethoxyphenoxy group), substituted or unsubstituted heterocyclic oxy groups having 1 to 20 carbon atoms (for example, 1-phenyltetrazole-5-oxy group) 2-tetrahydropyranyloxy group), substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms (for example, methylthio group, ethylthio group, n-hexadecylthio group), substituted or unsubstituted arylthio group having 6 to 20 carbon atoms. (For example, phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group), carbon number 1 to 0 substituted or unsubstituted heterocyclic thio group (for example, 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group), substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms (for example, Methanesulfonyl group, n-propylsulfonyl group, n-octylsulfonyl group), substituted or unsubstituted arylsulfonyl group having 6 to 14 carbon atoms (for example, toluenesulfonyl group, benzenesulfonyl group), substitution having 0 to 20 carbon atoms Or an unsubstituted sulfamoyl group (for example, methylsulfamoyl group, n-butylsulfamoyl group), a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms (for example, methoxycarbonyl group, n-butoxycarbonyl group) ), Substituted or unsubstituted aryloxycarbons having 7 to 15 carbon atoms Group (for example, phenoxycarbonyl group, m-chlorophenylcarbonyl group), substituted or unsubstituted acylamino group having 2 to 21 carbon atoms (for example, acetylamino group, pivaloylamino group, n-hexylamino group), 1 to 18 carbon atoms Sulfonylamino group (for example, methanesulfonylamino group, n-butanesulfonylamino group).

R ^{α1 to} R ^α8 and R ^{β1 to} R ^β8 are each independently more preferably a halogen atom, a carboxyl group, a sulfo group, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, or a C ¹ to 20 carbon atom. A substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, a substituted or unsubstituted hetero group having 1 to 20 carbon atoms A ring oxy group, a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclic thio group having 1 to 20 carbon atoms, a carbon number 1-20 substituted or unsubstituted alkylsulfonyl groups, 6-6 carbon atoms substituted or unsubstituted arylsulfonyl groups, 2-20 carbon atoms substituted or unsubstituted A sulfamoyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted acylamino group having 2 to 21 carbon atoms, sulfonylamino group having 1 to 18 carbon atoms 2 to 13 carbon atoms, more preferably, R ^{[alpha] 1} ~ ^Rα8 each independently represents a hydrogen atom, a halogen atom, a sulfo group, a substituted or unsubstituted alkoxy group having 1 to 16 carbon atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, or 6 carbon atoms. -14 substituted or unsubstituted arylsulfonyl group, C2-20 substituted or unsubstituted sulfamoyl group, C2-21 substituted or unsubstituted acylamino group, C1-18 substituted or unsubstituted a sulfonylamino group, R ^.beta.1 to R ^{beta 8} are each independently more is a hydrogen atom or a halogen atom Layer preferred. Further, R ^{α1 to} R ^α8 are each independently a hydrogen atom, a sulfo group, a substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, A substituted or unsubstituted arylthio group having 6 to 20 carbon atoms, an unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, an unsubstituted arylsulfonyl group having 6 to 14 carbon atoms, and an unsubstituted sulfamoyl group having 7 to 20 carbon atoms It is particularly preferable that R ^{β1 to} R ^β8 are hydrogen atoms.

One of R ^α1 and R ^α2 , one of R ^α3 and R ^α4 , one of R ^α5 and R ^α6 , one of R ^α7 and R ^{α8 in} the compound represented by the general formula (II) These four substituents are preferably not hydrogen atoms at the same time.

In particular, each of the four substituent groups of R ^α1 and R ^α2 , R ^α3 and R ^α4 , R ^α5 and R ^α6 , and R ^α7 and R ^{α8 in} the compound represented by the general formula (II) That one of the substituents is a hydrogen atom, and the other substituent is a substituent other than a hydrogen atom, is suitable for ink formation of the phthalocyanine derivative and the crystal of the recording layer after being coated on the disk This is preferable in view of the difficulty of the formation.
In this case, examples of the substituent other than a hydrogen atom include a sulfo group, a substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, and 6 to 20 carbon atoms. Are preferably substituted or unsubstituted arylthio groups, unsubstituted alkylsulfonyl groups having 1 to 20 carbon atoms, unsubstituted arylsulfonyl groups having 6 to 14 carbon atoms, and unsubstituted sulfamoyl groups having 7 to 20 carbon atoms.

In the general formula (II), R ^{α1 to} R ^α8 and R ^{β1 to} R ^β8 may further have a substituent, and examples of the substituent include those described below.
Halogen atom (for example, chlorine atom, bromine atom, iodine atom), alkyl group [represents 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 group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group), Bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. For example, bicyclo [ 1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl) and a ring structure There tricyclo structure is intended to encompass such. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as vinyl group, allyl group, prenyl group, geranyl group, oleyl group), cycloalkenyl group (preferably having 3 carbon atoms). A substituted or unsubstituted cycloalkenyl group having ˜30, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl, 2-cyclohexene- 1-yl), a bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, one hydrogen atom of a bicycloalkene having one double bond. Monovalent groups removed, such as bicyclo [2,2,1] hept-2-en-1-yl, bisci B [2,2,2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group, a propargyl group, a trimethylsilylethynyl group, an aryl group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms). Aryl groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl groups, heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted, aromatic Alternatively, it is a monovalent group obtained by removing one hydrogen atom from a non-aromatic heterocyclic compound, and more preferably a 5- to 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), cyano group, hydroxyl group, nitro group, carboxyl Group, alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, t-butoxy group, n-octyloxy group, 2-methoxyethoxy group) Group), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as a phenoxy group, a 2-methylphenoxy group, a 4-t-butylphenoxy group, a 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy group, t-butyldimethylsilyloxy group), heterocyclic oxy group (preferably carbon number) 2-30 substituted or unsubstituted heterocyclic oxy groups, 1-phenyltetrazole-5- Xyl group, 2-tetrahydropyranyloxy group), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 6 to 30 carbon atoms) Oxy groups such as formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Carbamoyloxy group, for example, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyl Oxy group), Arco A xoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, an n-octylcarbonyloxy group), an aryl An oxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy Group), an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as an amino group, a methylamino group, Dimethylamino group Anilino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms) Substituted arylcarbonylamino groups such as formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group), aminocarbonylamino group (Preferably, a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group) , Alkoxycal Nylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl Rumethoxycarbonylamino group), aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, m- (N-octyloxy) phenoxycarbonylamino group), sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino group, N, N- Dimethyla Minosulfonylamino group, Nn-octylaminosulfonylamino group), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted groups having 6 to 30 carbon atoms) Substituted arylsulfonylamino groups such as methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group), mercapto group, alkylthio group (Preferably, a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group, or an n-hexadecylthio group), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, For example, An arylthio group, a p-chlorophenylthio group, an m-methoxyphenylthio group, a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as a 2-benzothiazolylthio group, 1 -Phenyltetrazol-5-ylthio group), sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′-phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably Is a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, 6 to 0 substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, p-methylphenylsulfinyl group), alkyl and arylsulfonyl groups (preferably substituted or substituted with 1 to 30 carbon atoms) Unsubstituted alkylsulfonyl group, 6-30 substituted or unsubstituted arylsulfonyl group, for example, methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p-methylphenylsulfonyl group), acyl group (preferably formyl group, Bonded to a carbonyl group by a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, or a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms. A heterocyclic carbonyl group, such as Cetyl group, pivaloyl group, 2-chloroacetyl group, stearoyl group, benzoyl group, pn-octyloxyphenylcarbonyl group, 2-pyridylcarbonyl group, 2-furylcarbonyl group), aryloxycarbonyl group (preferably carbon A substituted or unsubstituted aryloxycarbonyl group of 7 to 30, for example, phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt-butylphenoxycarbonyl group), alkoxycarbonyl group (preferably Is a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, or an n-octadecyloxycarbonyl group), a carbamoyl group (preferably having a carbon number of 1 to 3 0 substituted or unsubstituted carbamoyl group such as carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group) Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo groups and p-chlorophenylazo groups) , 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide group, N-phthalimide group), phosphino group (preferably substituted with 2 to 30 carbon atoms or Unsubstituted phosphino groups such as dimethylphosphino group, diphenylphosphino group, methylphenol Xyphosphino group), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl group, dioctyloxyphosphinyl group, diethoxyphosphinyl group), phosphinyloxy group ( Preferably, it is a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group or a dioctyloxyphosphinyloxy group, or a phosphinylamino group (preferably having a carbon number). 2-30 substituted or unsubstituted phosphinylamino groups such as dimethoxyphosphinylamino group and dimethylaminophosphinylamino group, silyl groups (preferably substituted or unsubstituted 3 to 30 carbon atoms) Silyl groups such as trimethylsilyl group, t-butyldimethylsilyl group, phenyldimethyl It represents a Rushiriru group).

  Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. More specific examples include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

In the general formula (II), a preferable substituent for substituting R ^{α1 to} R ^α8 and R ^{β1 to} R ^β8 is a linear or cyclic substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, carbon number 6 Aryl group having 1 to 14 carbon atoms, alkoxy group having 1 to 16 carbon atoms, halogen atom, carbamoyloxy group having 1 to 20 carbon atoms, alkoxycarbonyloxy group having 1 to 20 carbon atoms, aryloxycarbonyloxy group having 1 to 20 carbon atoms , An aminocarbonylamino group having 1 to 20 carbon atoms, an alkoxycarbonylamino group having 2 to 20 carbon atoms, an aryloxycarbonylamino group having 7 to 20 carbon atoms, a sulfamoyl group having 3 to 20 carbon atoms, and 2 to 20 carbon atoms Alkyl and arylsulfonyl group, aryloxycarbonyl group having 7 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, carbon It is a carbamoyl group having 2 to 20 prime numbers. Among these, preferred are linear or cyclic substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, chlorine atoms, and 1 to 1 carbon atoms. 10 alkoxycarbonyloxy groups, C2-C10 alkoxycarbonylamino groups, C3-C10 sulfamoyl groups, C2-C10 alkyl and arylsulfonyl groups, C2-C10 alkoxycarbonyl groups, carbon It is a carbamoyl group of several 2 to 10. Among them, particularly preferred are linear or cyclic substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, aryl groups having 6 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, and 1 to 8 carbon atoms. Alkoxycarbonyloxy group, alkoxycarbonylamino group having 2 to 8 carbon atoms, sulfamoyl group having 3 to 8 carbon atoms, alkyl and arylsulfonyl group having 2 to 8 carbon atoms, alkoxycarbonyl group having 2 to 8 carbon atoms, carbon number 2 ˜8 carbamoyl groups. The most preferable substituents are an alkylsulfonyl group having 2 to 6 carbon atoms and an alkoxycarbonyl group having 2 to 6 carbon atoms.
It is.

M ¹ in the general formula (II) represents two hydrogen atoms, a divalent to tetravalent metal atom, a divalent to tetravalent oxymetal atom, or a divalent to tetravalent metal atom having a ligand. The details are as described for M in the general formula (I).

  The compound represented by the general formula (I) or (II) may be bonded at an arbitrary position to form a multimer, and in this case, each unit may be the same as or different from each other, and polystyrene, You may couple | bond with polymer chains, such as polymethacrylate, polyvinyl alcohol, and cellulose.

  Furthermore, the compound represented by the general formula (I) or (II) may be used alone as a specific derivative, or a mixture of compounds having different structures may be used. In particular, for the purpose of preventing the crystallization of the recording layer, it is preferable to use a mixture of isomers having different substituent substitution positions.

Preferred specific examples of the compound represented by the general formula (I) or (II) are shown below, but the present invention is not limited thereto.
In Table 1 below, for example, the notation R ^α1 / R ^α2 means either R ^α1 or R ^α2 , and therefore a compound having this notation is a mixture of substitutional isomers. In the case of no substitution, that is, when a hydrogen atom is substituted, the notation is omitted.

  The compounds represented by the general formula (I) described above can be prepared by known methods (for example, Shirai-Kobayashi, published by IPC Co., Ltd. “Phthalocyanine—Chemistry and Function”) (P. 1-62), CC , Leznoff-ABBP Lever, written by VCH, described in “Phthalogicanes-Properties and Applications” (P.1-54), etc., or a similar method), or commercially available Some are available as

Azo dye compound In the optical information recording medium of the present invention, the dye contained in the recording layer includes (i) an azo compound, and (ii) an azo metal complex compound containing an azo compound and a metal ion or a metal oxide ion. Also preferred are at least one azo dye compound selected from the group consisting of: The compound can realize a large refractive index difference in a short wavelength region, and can exhibit excellent recording characteristics particularly by irradiation with a short wavelength laser beam when combined with the aforementioned intermediate layer.

  Preferred dye characteristics of the azo dye compound are as described above. Further, as the azo dye compound, an extinction coefficient (hereinafter referred to as an extinction coefficient) at a wavelength of 405 nm (hereinafter referred to as an extinction coefficient) is used from the viewpoint of improving the recording / reproduction sensitivity when information is recorded / reproduced by irradiating the optical information recording medium having the above-described structure with a short wavelength laser beam. The extinction coefficient at a wavelength of 405 nm is preferably “extinction coefficient k” in the range of 0.15 to 1.0, more preferably in the range of 0.2 to 0.6. If the extinction coefficient k of the azo dye compound contained in the recording layer is too large, the reflectivity may be too low to make it practical to obtain practical recording / reproducing characteristics. On the other hand, if the extinction coefficient k is too small. It may be difficult to obtain a sensitivity suitable for practical use.

  The azo dye compound is a refractive index at a wavelength of 405 nm (hereinafter referred to as a light with a wavelength of 405 nm) in order to obtain good recording / reproduction characteristics by irradiation with a short wavelength laser beam in the optical information recording medium having the above-described configuration. The refractive index with respect to is referred to as “refractive index n”) is preferably in the range of 1.45 to 1.75, more preferably in the range of 1.47 to 1.70. preferable. If the refractive index n is an azo dye compound having a refractive index n of 1.45 or more, good 2T CNR can be obtained in recording by irradiation with a short wavelength laser beam. With an azo dye compound having a refractive index n greater than 1.75, it may be difficult to obtain good tracking aptitude in the optical information recording medium having the above-described configuration.

  The refractive index n and the extinction coefficient k are formed by using a coating solution prepared by dissolving a dye in an appropriate solvent, and the dye film is subjected to, for example, a spectroscopic ellipsometry apparatus (JA Woollam Japan). It shall mean the value calculated | required by carrying out a measurement analysis using a company make, model M-2000). For example, a dye-containing coating solution obtained by dissolving 2 g of a dye in 100 ml of 2,2,2,3-tetrafluoropropanol is spin-coated on a glass plate having a thickness of 1.1 mm by a rotational speed of 500 to 1000 rpm. With respect to the dye film formed by coating under the conditions of 23 ° C. and 50% RH while changing the temperature, the values measured using the measuring device can be the refractive index n and the extinction coefficient k.

  From the viewpoint that the refractive index n, extinction coefficient k, and thermal decomposition temperature of the azo dye compound at 405 nm satisfy all of the CNR, tracking suitability, recording sensitivity, and reproduction durability of the recording signal, 1.45 ≦ n ≦ 1.70, 0.13 ≦ k <0.3, and thermal decomposition temperature of 210 ° C. or higher and 340 ° C. or lower, preferably 1.46 ≦ n ≦ 1.67 and 0.15 ≦ k ≦ More preferably, the thermal decomposition temperature is 0.29, and the thermal decomposition temperature is 220 ° C. or higher and 330 ° C. or lower, 1.47 ≦ n ≦ 1.65, and 0.17 ≦ k ≦ 0.28, and the thermal decomposition temperature is 230 ° C. or higher. More preferably, it is 320 degrees C or less.

  Hereinafter, the azo compound and the azo metal complex compound will be described in more detail.

Azo Compound In the present invention, an azo compound is defined as a compound having an acyclic azo group (—N═N—). As the azo compound, those having an acyclic azo group and capable of functioning as a dye can be used, and the following general formula (A), general formula (B), or general formula ( An azo dye represented by any one of C) is particularly preferably used.

［式中、Ｑ₁₁は含窒素複素環を形成する原子群を表し、Ｑ₁₂は複素環または炭素環を形成する原子群を表し、Ｙ₁₁は解離性水素原子を含有し、かつ金属イオンまたは金属酸化物イオンに結合可能な基を表す。］

[Wherein Q ₁₁ represents an atomic group forming a nitrogen-containing heterocyclic ring, Q ₁₂ represents an atomic group forming a heterocyclic ring or a carbocyclic ring, Y ₁₁ contains a dissociative hydrogen atom, and a metal ion or A group capable of binding to a metal oxide ion is represented. ]

［式中、Ｑ₂₁およびＱ₂₂は、各々独立に、複素環または炭素環を形成する原子群を表し、Ｙ₂₁およびＹ₂₂は、各々独立に、解離性水素原子を含有し、かつ金属イオンまたは金属酸化物イオンに結合可能な基を表す。］

[Wherein, Q ₂₁ and Q ₂₂ each independently represent a group of atoms forming a heterocyclic ring or a carbocyclic ring, Y ₂₁ and Y ₂₂ each independently contain a dissociative hydrogen atom, and a metal ion Or represents a group capable of binding to a metal oxide ion. ]

［式中、Ｑ₃₁は複素環または炭素環を形成する原子群を表し、Ｑ₃₂は含窒素複素環を形成する原子群を表し、Ｙ₃₁は解離性水素原子を含有し、かつ金属イオンまたは金属酸化物イオンに結合可能な基を表し、Ｒ₃₁は水素原子または置換基を表す。］

[Wherein Q ₃₁ represents an atomic group forming a heterocyclic ring or a carbocyclic ring, Q ₃₂ represents an atomic group forming a nitrogen-containing heterocyclic ring, Y ₃₁ contains a dissociative hydrogen atom, and a metal ion or represents a group that can be bonded to a metal oxide ion, R ₃₁ represents a hydrogen atom or a substituent. ]

In the present invention, the “dissociable hydrogen atom” means a hydrogen atom having a low pKa and easily deprotonated, preferably having a pKa value of 5 to 15, more preferably 7.0 to 12.0, More preferably, it exists in the range of 8.0-11.0. The pKa value defined here is a value obtained by an acid-base titration method in a solvent system of THF / water = 6/4. In addition, the hydrogen atom represented by R ³¹ in the general formula (C) can also be a dissociative hydrogen atom, and the substituent represented by R ³¹ can also include a dissociable hydrogen atom.

Below, general formula (A) is demonstrated.
Q ₁₁ represents an atomic group forming a nitrogen-containing heterocyclic ring. The nitrogen-containing heterocyclic ring formed by Q _11, is not particularly limited, for example, a pyrazole ring, a pyrrole ring, an imidazole ring, a thiazole ring, an isothiazole ring, an oxazole ring, an isoxazole ring, a 1,2,4-thiadiazole Ring, 1,3,4-thiadiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring and the like.

Q ₁₂ represents an atomic group forming a heterocyclic ring or a carbocyclic ring. If Q ₁₂ to form a heterocyclic ring, the ring formed by Q ₁₂ includes a carbon atom and hetero atom (oxygen atom, a sulfur atom, a nitrogen atom and the like) may be a heterocyclic ring formed together with, but are not limited to Examples thereof include pyrazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, thiazole ring, isothiazole ring, oxazole ring, isoxazole ring, pyridine ring, pyrazine ring, pyrimidine ring and pyridazine ring. These rings may have a substituent and may be condensed.

の具体例としては、下記部分構造式（Ｃ−１）〜（Ｃ−７）等が挙げられる。下記部分構造式は、一般式（Ａ）中のＹ¹¹がヒドロキシル基である態様である。

In the general formula (A), the following partial structure:

Specific examples of these include the following partial structural formulas (C-1) to (C-7). The following partial structural formula is an embodiment in which Y ¹¹ in the general formula (A) is a hydroxyl group.

In the above, R ³ represents a hydrogen atom or a substituent, and R ³ may be the same or different from each other. R ³ may be bonded to each other via a linking group. R ³ is preferably a substituent. Although it does not specifically limit as a substituent, Preferably it is C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C10, for example, a methyl group, an ethyl group, iso- Propyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), aryl group (preferably having 6 to 30 carbon atoms, More preferably, it has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenyl group, a p-methylphenyl group, a naphthyl group, an anthranyl group, a pyridyl group, a thiazole group, an oxazole group, and a triazole group. And the like.

When the ring formed by Q ₁₂ is a carbocycle, the carbocycle is preferably a benzene ring.

The atomic group represented by Q ₁₁ and Q ₁₂ may have a substituent, and preferably has a substituent from the viewpoint of solubility in a coating solvent. Although it does not specifically limit as a substituent, For example, a halogen atom, an alkyl group (a cycloalkyl group and a bicycloalkyl group are included), an alkenyl group (a cycloalkenyl group and a bicycloalkenyl group are included), an alkynyl group, an aryl group, hetero Ring group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group ( Anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group Arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imido group Examples include phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, and silyl group.
More specifically, 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 is represented. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group), Bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. For example, bicyclo [ 1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl) and a ring structure There tricyclo structure is intended to encompass such. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group), a cycloalkenyl group (preferably a carbon number of 3 A substituted or unsubstituted cycloalkenyl group having ˜30, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl, 2-cyclohexene- 1-yl), bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, one hydrogen atom of a bicycloalkene having one double bond. Monovalent groups removed, such as bicyclo [2,2,1] hept-2-en-1-yl, bicycl [2,2,2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group, a propargyl group, a trimethylsilylethynyl group, an aryl group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms). An aryl group such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an o-hexadecanoylaminophenyl group), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or It is a monovalent group obtained by removing one hydrogen atom from a non-aromatic heterocyclic compound, and more preferably a 5- to 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), cyano group, hydroxyl group, nitro group, carboxyl An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group or a 2-methoxyethoxy group) An aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms such as phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, 3-nitrophenoxy group, 2- A tetradecanoylaminophenoxy group), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as a trimethylsilyloxy group or a t-butyldimethylsilyloxy group), a heterocyclic oxy group (preferably having a carbon number of 2 30 substituted or unsubstituted heterocyclic oxy groups, 1-phenyltetrazol-5-oxy Group, 2-tetrahydropyranyloxy group), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms) Group, for example, formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Carbamoyloxy groups such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy Group), alkoxy A carbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, an n-octylcarbonyloxy group), an aryloxy Carbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group ), An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as an amino group, a methylamino group, and dimethyl) Amino group, a Lino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms) Substituted arylcarbonylamino groups such as formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group), aminocarbonylamino group (Preferably, a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group) , Alkoxycarbonyl Mino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl Rumethoxycarbonylamino group), aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, m- n-octyloxyphenoxycarbonylamino group), sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino group, N, N-dimethylamino Sulfo Nylamino group, Nn-octylaminosulfonylamino group), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted groups having 6 to 30 carbon atoms) Arylsulfonylamino group, for example, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group), mercapto group, alkylthio group (preferably Is a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group, or an n-hexadecylthio group, an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, Phenylti Group, p-chlorophenylthio group, m-methoxyphenylthio group), heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio group, 1 -Phenyltetrazol-5-ylthio group), sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′-phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably Represents a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, 6 to 30 carbon atoms. Or an unsubstituted arylsulfinyl group, for example, a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, a p-methylphenylsulfinyl group), an alkyl and an arylsulfonyl group (preferably a substituted or unsubstituted group having 1 to 30 carbon atoms) Alkylsulfonyl group, 6-30 substituted or unsubstituted arylsulfonyl group such as methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p-methylphenylsulfonyl group), acyl group (preferably formyl group, carbon number 2) A substituted or unsubstituted alkylcarbonyl group having 30 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, and a heterocyclic ring bonded to the carbonyl group at a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms Carbonyl group, for example acetyl , Pivaloyl group, 2-chloroacetyl group, stearoyl group, benzoyl group, pn-octyloxyphenylcarbonyl group, 2-pyridylcarbonyl group, 2-furylcarbonyl group), aryloxycarbonyl group (preferably having 7 carbon atoms) To 30 substituted or unsubstituted aryloxycarbonyl groups such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt-butylphenoxycarbonyl group), alkoxycarbonyl group (preferably, A substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, or an n-octadecyloxycarbonyl group), a carbamoyl group (preferably having 1 to 30 carbon atoms) Replace Or unsubstituted carbamoyl groups such as carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group), aryl and Heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as phenylazo group, p-chlorophenylazo group, 5- Ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide, N-phthalimide), phosphino group (preferably substituted or unsubstituted phosphino group having 2 to 30 carbon atoms) For example, dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphine Group), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl group, dioctyloxyphosphinyl group, diethoxyphosphinyl group), phosphinyloxy group ( Preferably, it is a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group or a dioctyloxyphosphinyloxy group, or a phosphinylamino group (preferably having a carbon number). 2-30 substituted or unsubstituted phosphinylamino groups such as dimethoxyphosphinylamino group and dimethylaminophosphinylamino group, silyl groups (preferably substituted or unsubstituted 3 to 30 carbon atoms) Silyl groups such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl) .
Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

When the atomic group represented by Q ₁₂ has a substituent, from the viewpoint of sensitivity to a blue semiconductor laser, the substituent is a hydroxyl group, an alkyloxy group, an aryloxy group, a thiol group, an alkylthio group, an arylthio group, an amino group. And a substituent that does not correspond to any of the alkylamino group and the anilino group. Examples of the substituent include halogen, nitro group, cyano group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted 2 to 10 carbon atoms, Unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, substituted or unsubstituted aryloxycarbonyl group having 7 to 10 carbon atoms, substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms Group, a substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms, or a substituted or unsubstituted alkoxysulfonyl group having 1 to 10 carbon atoms, preferably a cyano group, a substituted or unsubstituted carbon atom having 1 to 1 carbon atoms. 10 alkyl groups, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, substituted or unsubstituted acyl groups having 2 to 10 carbon atoms It is more preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms. Substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted acyl group having 2 to 10 carbon atoms, substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, substituted or unsubstituted carbon It is more preferable that it is a C1-C10 alkylsulfonyl group.

Y ₁₁ represents a group containing a dissociable hydrogen atom and capable of binding to a metal ion or metal oxide ion. The group represented by Y _11, is not particularly limited, for example, a hydroxyl group, a thiol group, an amino group, a carboxyl group, a sulfonic acid group, and the like.

Y ₁₁ represents a hydroxyl group, an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as an amino group, Methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, carbon A substituted or unsubstituted arylcarbonylamino group of formula 6-30, for example, formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonyl Amino group), aminocarbonylamino group (preferably having 1 to 30 carbon atoms) Substituted or unsubstituted aminocarbonylamino group, for example, carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group), alkoxycarbonylamino group (preferably having carbon number) 2 to 30 substituted or unsubstituted alkoxycarbonylamino groups, for example, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group), Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group) , Mn-octyloxyphenoxycarbonylamino group), sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino group, N, N -Dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, substituted having 6 to 30 carbon atoms) Or an unsubstituted arylsulfonylamino group such as a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, or a p-methylphenylsulfonylamino group). preferable. When Y is an amino group having a substituent, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, a substituted or unsubstituted acylamino group having 2 to 30 carbon atoms, a substituted or unsubstituted group having 6 to 30 carbon atoms Arylcarbonylamino group, substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, substituted or unsubstituted aryl having 7 to 30 carbon atoms Oxycarbonylamino group, substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms It is preferably a sulfonylamino group, a substituted or unsubstituted acylamino group having 2 to 30 carbon atoms, carbon number Substituted or unsubstituted arylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, or 0 to 30 carbon atoms More preferably a substituted or unsubstituted sulfamoylamino group, a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted acylamino group having 2 to 30 carbon atoms, carbon number It is more preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted acylamino group having 2 to 30 carbon atoms, It is a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. It is particularly preferred.

When Y ₁₁ is an amino group having a substituent, the substituent may be bonded to an atomic group formed by Q ¹ to form a ring, and such a case is also preferable. Examples of the ring thus formed include a 5-membered ring containing 1 to 3 nitrogen atoms and a 6-membered ring containing 1 to 4 nitrogen atoms, and a 5-membered ring containing 2 or 3 nitrogen atoms. And a 5-membered ring containing 3 nitrogen atoms is more preferable. As a preferred specific example when a 5-membered ring containing three nitrogen atoms is formed, a condensed ring structure contained in the following exemplified compounds (AZO-1), (AZO-2) and the like can be mentioned.

  Specific examples of the azo compound represented by the general formula (A) are shown below, but the present invention is not limited thereto.

Next, general formula (B) will be described.
In the general formula (B), Q ₂₁ and Q ₂₂ each independently represents an atomic group that forms a heterocyclic ring or a carbocyclic ring. The details of Q ₂₁ and Q ₂₂ are as described for Q ₁₂ in the general formula (A).

Y ₂₁ and Y ₂₂ each independently represent a group containing a dissociable hydrogen atom and capable of binding to a metal ion or a metal oxide ion, the details of which are described above for Y ₁₁ in the general formula (A). That's right.

  Specific examples of the azo compound represented by the general formula (B) are shown below, but the present invention is not limited thereto.

Below, general formula (C) is demonstrated.
Q ₃₁ represents an atomic group forming a heterocyclic ring or a carbocyclic ring, and details thereof are as described for Q ₁₂ in the general formula (A).

Q ₃₂ represents an atomic group forming a nitrogen-containing heterocyclic ring. Nitrogen-containing heterocyclic group formed by Q ₃₂ is preferably a ring represented by the partial structural formula (q-1) ~ (q -4), (q-1), with (q-2) More preferably, it is a ring represented by (q-1).

In the above, * represents a binding position with the -N = N-group, R ₃₁ corresponds to R ₃₁ in the general formula (C), R ₄₁ ~R ₄₆ each independently represents a substituent.

R ₃₁ in the general formula (C) represents a hydrogen atom or a substituent. It Examples of the substituent represented by R _31, but are not limited to, containing a dissociative hydrogen atom, a group capable of being bonded to a metal ion or metal oxide ion, or a substituent having a base Is more preferable, and a group that forms a nitrogen-containing heterocycle is more preferable. Although it does not specifically limit as a nitrogen-containing heterocycle, For example, a pyrazole ring, an imidazole ring, a thiazole ring, an oxazole ring, 4,5-dihydroimidazole, 4,5-dihydrooxazole, 4,5-dihydrothiazole, 1,2 , 4-thiadiazole ring, 1,3,4-thiadiazole ring, 1,2,4-triazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,3,5-triazine ring A ring etc. are mentioned. These rings may further have a substituent and may be condensed.

  The nitrogen-containing heterocyclic group is preferably a thiazole ring, oxazole ring, 1,2,4-thiadiazole ring, 1,3,4-thiadiazole ring, 1,2,4-triazole ring, pyridine ring, pyrazine ring. , Pyrimidine ring, pyridazine ring and triazine ring, more preferably thiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring and triazine ring, more preferably thiazole ring, pyridine ring and pyrazine. A ring and a triazine ring, particularly preferably a thiazole ring and a pyridine ring.

When R ₃₁ is a hydrogen atom, it is preferable that the hydrogen atom is dissociated, and a nitrogen atom and a metal ion bonded to the hydrogen atom are covalently bonded to form an azo metal complex.

R ^{41 to} R ⁴⁶ in the partial structural formulas (q-1) to (q-4) each independently represent a hydrogen atom or a substituent. R ^{41 to} R ⁴⁶ are preferably substituents from the viewpoint of improving solubility. The substituent is not particularly limited, substituents exemplified as a substituent further substituted with atom groups represented by Q ₁₁ and Q ₁₂ and the like.

R ⁴¹ , R ⁴³ and R ⁴⁴ are a substituted or unsubstituted carbocyclic group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 6 to 20 carbon atoms, and a substituted or unsubstituted group having 2 to 10 carbon atoms. Alkyloxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group having 7 to 10 carbon atoms, substituted or unsubstituted alkylaminocarbonyl group having 2 to 10 carbon atoms, substituted or unsubstituted anion having 7 to 10 carbon atoms. It is preferably a group selected from a linocarbonyl group, a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms, and a cyano group. 10 substituted or unsubstituted alkyloxycarbonyl groups, 7 to 10 carbon atoms substituted or unsubstituted aryloxycarbonyl groups, 1 to 10 carbon atoms It is more preferably a group selected from a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms, and a cyano group, and a substituted or unsubstituted alkyloxy group having 2 to 10 carbon atoms. Carbonyl group, substituted or unsubstituted aryloxycarbonyl group having 7 to 10 carbon atoms, substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms, cyano A group selected from groups is more preferable, and a cyano group is particularly preferable.

R ⁴² , R ⁴⁵ and R ⁴⁶ are preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and from the viewpoint of solubility, the number of carbon atoms A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted aryl group having 6 to 10 carbon atoms are more preferable. The alkyl group is preferably a branched alkyl group having 3 to 6 carbon atoms, and more preferably a tertiary alkyl group having 4 to 6 carbon atoms.

Y ₃₁ in the general formula (C) contains a dissociative hydrogen atom, and represents a group capable of being bonded to a metal ion or metal oxide ion, for Y ₁₁ in the general formula (A) to the details previously As stated.

  Specific examples of the azo compound represented by the general formula (C) are shown below, but the present invention is not limited thereto.

  The azo compound described above is contained in the recording layer as a recording dye in a state where it is not complexed with metal ions or metal oxide ions. Thus, it is preferable not to contain metal ions or metal oxide ions from the viewpoint of the influence on the environment and the human body. The azo compound is preferably an azo compound represented by the general formula (C) from the viewpoint of dye film stability and dye film light resistance.

  As the general formulas (A), (B), and (C), only azoforms in the azo-hydrazone tautomeric equilibrium are shown, but corresponding hydrazone forms may be used.

Azo metal complex compound The azo metal complex compound contains an azo compound and a metal ion or metal oxide ion. The azo metal complex compound is a dye formed by a coordinate bond between an azo compound and a metal ion by reacting the azo compound with a metal ion or metal oxide ion.

As the azo metal complex dye, the azo dye represented by any one of the general formula (A), the general formula (B), and the general formula (C) and a metal ion or a metal oxide ion are excellent in recording characteristics. An azo metal complex dye containing is particularly preferably used. However, in the general formula (A), the general formula (B), or the general formula (C) that are ligands of the azo metal complex dye in this case, Y ₁₁ , Y ₁₂ , and Y ₁₃ each have a hydrogen atom. It is preferable that the hydrogen atom dissociates to form an anionic group when forming the azo metal complex dye.

  Examples of the metal ions include Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Ba, Pr, Eu, Yb, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Examples include ions of metals such as Bi and Th. Among them, ions of transition metal atoms are preferable. Examples of the metal oxide ion include the metal oxide ions.

  The transition metal atom is an element having an incomplete d-electron shell, including elements of Group IIIa to Group VIII and Ib of the periodic table. The transition metal atom is not particularly limited, but is preferably Mn, Fe, Co, Ni, Cu, Zn, Cr, more preferably Mn, Fe, Co, Ni, Cu, Zn, Mn, Fe, Co, Ni and Cu are more preferable, Co, Ni and Cu are particularly preferable from the viewpoint of recording / reproducing characteristics, and Mn, Fe and Cu are particularly preferable from the viewpoint of influence on the environment and the human body.

The metal ion is preferably a divalent or trivalent metal atom, and more preferably a divalent metal atom. Examples of the divalent or trivalent metal (represented by metal ions) include, for example, Mn ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Ni ²⁺ , Ni ³⁺ , Cu ²⁺ , Zn ²⁺ , Cr ³⁺ , Ru ²⁺ , Rh ³⁺ , Pd ²⁺ , Ir ³⁺ , Pt ^{2+ and the} like can be mentioned. Mn ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ^{3 +} , Ni ²⁺ , Ni ³⁺ , Cu ²⁺ and Zn ²⁺ are preferable, and Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Co ³⁺ , Ni ²⁺ , Ni ³⁺ and Cu ²⁺ are more preferable. Co ³⁺ , Ni ³⁺ , Mn ²⁺ , Fe ²⁺ and Cu ²⁺ are more preferable.

  The azo metal complex compound particularly preferably contains copper ion, cobalt ion or nickel ion as a central metal ion, and most preferably contains copper ion, from the viewpoint of recording / reproducing characteristics.

  Examples of a general synthesis method of the azo dyes represented by the general formulas (A) to (C) include methods described in JP-A Nos. 61-36362 and 2006-57076. However, the present invention is not limited to this, and other acids and reaction solvents may be used, and the coupling reaction may be performed in the presence of a base (for example, sodium acetate, pyridine, sodium hydroxide, etc.). Specific examples of the synthesis method of the azo compound that can be used in the present invention are shown below. Various azo compounds that can be used in the present invention can be synthesized by the same method.

［一般式（Ｄ）中、Ｑ³³は含窒素へテロ環を形成する原子群を表し、Ｑ³¹、Ｑ³²、Ｙ³¹は一般式（Ｃ）と同義である。］

[In General Formula (D), Q ³³ represents an atomic group forming a nitrogen-containing heterocycle, and Q ³¹ , Q ³² , and Y ³¹ are synonymous with General Formula (C). ]

  As a general method for obtaining a metal azo chelate dye by reacting an azo compound with a metal ion (or metal oxide ion), an azo compound or a metal salt (including a metal complex or metal oxide salt) is organically present in the presence of a base. The method of stirring in a solvent or water, or its liquid mixture is mentioned. However, the type of metal salt, the type of base, the type of organic solvent or a mixture thereof, the reaction temperature, etc. are not limited. An example of a method for synthesizing an azo metal complex dye that can be used in the present invention is shown below.

  A synthesis example of an azo metal complex dye composed of the azo compound and a metal ion (or metal oxide ion) is shown below. In the following, methanol is shown as a reaction solvent, but the reaction solvent is not limited to methanol. The reaction solvent is preferably an alcohol that can dissolve metal ions. In the following, triethylamine is shown as a base, but the base is not limited to triethylamine. Moreover, although the dotted line which connects M and a nitrogen atom represents a coordination bond, it is set as the same compound even if it is in the state which does not have this coordination bond and has not couple | bonded. Various azo metal complex dyes composed of various azo compounds and metal ions (or metal oxide ions) that can be used in the present invention can be synthesized by the same method.

Here, Z represents an oxygen atom, a sulfur atom, or a divalent linking group represented by NR ³⁶ , R ³⁶ represents a hydrogen atom or a substituent, and q represents 1 or 2. n1 represents an integer in the range of 1 to 3, and n3 represents the same number as q. The triethylammonium cation of the azo metal complex dye obtained by this synthesis method can undergo a cation exchange reaction in a solvent.

  In the above synthesis method, the azo metal complex dye can be obtained by reacting Co salt, Ni salt, Mn salt, Fe salt or the like with an azo dye.

  In a similar synthesis method, an azo metal complex represented by the following general formula (5-1 ″) can be synthesized by reacting a Cu salt.

Here, Z is as described above, L2 represents a ligand, and n2 represents an integer in the range of 0 to 3. X ⁻ may be an anion and is not particularly limited. Examples of X ⁻ include halogen ion, CH ₃ COO ⁻ , ClO ₄ ⁻ , SO ₄ ^{2− and the} like. n represents an integer in the range of 0 to 6, and preferably in the range of 0 to 4.

  Moreover, an azo metal complex is compoundable by the same method also about general formula (D). When Y is an —OH group, the reaction proceeds even under conditions where no base is present.

［Y₃₁=ZH、Q³³=含窒素へテロ環を形成する原子群］

[Y ₃₁ = ZH, Q ³³ = atom group forming a nitrogen-containing heterocycle]

  Specific examples of the azo metal complex dye that can be used as the recording dye of the optical information recording medium of the present invention are shown below. However, the present invention is not limited to these.

The general formula (E) is described so that the anion on the azo ligand is on the N atom bonded to M, but the anion is not limited to being present on the N atom, but the skeleton of the azo ligand. The state may be widely delocalized as a whole or may have a tautomeric structure.
Moreover, although it applies also about (M-39)-(M-53), t in general formula (E) may change with the environment where a compound exists. That is, in an environment where a coordinating compound (nitrile compound, amide compound, H ₂ O, alcohol compound, ether compound, ester compound, amine compound, nitrogen-containing heterocyclic compound, etc.) exists, May be incorporated into compounds.
Although the general formula (E) can be changed depending on the environment in which the compound exists, it may be considered that the change changes the valence of the copper ion. For example, it is conceivable that Cu ²⁺ becomes Cu ⁺ in the presence of a solvent, and in that case, the azo metal complex site may be neutral or anionic. In this case, it is assumed that the number of Y ^v− (w in the general formula (E)) is changed, or that Y ^v− is replaced with an arbitrary cation.

  In the recording layer, one or a combination of two or more of the azo dye compounds can be used as the recording layer dye. Further, a dye other than the azo dye compound can be used in combination. As the dye that can be used in combination, for example, those having absorption in a short wavelength region of a wavelength of 440 nm or less are preferable. Examples of such dyes include, but are not limited to, azo dyes, azo metal complex dyes, phthalocyanine dyes, oxonol dyes, and cyanine dyes.

  The usage-amount of the pigment | dye for recording layers is the range of 1-100 mass% with respect to the total mass of a recording layer, for example, Preferably it is 50-100 mass%, More preferably, it is the range of 75-100 mass%. When the azo dye compound and another dye are used in combination as the recording layer dye, the ratio of the azo dye compound to the total amount of the dye is preferably 1% by mass or more, and more preferably 10 to 100% by mass. 50 to 100% by mass is particularly preferable.

Oxonol Dye Compound The optical information recording medium of the present invention can also contain an oxonol dye as a recording dye. The oxonol dye includes an anion compound represented by the following general formula (X), a dye containing a cation capable of neutralizing the charge of the anion compound, and / or a compound represented by the following general formula (X). An anion compound in which two or more (which may be the same or different) are linked to each other via any one of A, B, C and / or D, and a cation capable of neutralizing the charge of the anion compound And a dye (oxonol derivative, hereinafter also referred to as “dye A”). These oxonol dye compounds preferably have the aforementioned preferable dye physical properties.

［一般式（X）中、ＡおよびＢは、AおよびBのハメットのσｐ値の合計が０．６以上となる電子吸引性基であって互いに連結して環を形成してもよく、ＣおよびＤは、ＣおよびＤのハメットのσｐ値の合計が０．６以上となる電子吸引性基であって互いに連結して環を形成してもよく、Ｒはメチン炭素上の置換基を表し、ｍは０〜３の範囲の整数を表し、ｎは０〜（２ｍ＋１）の範囲の整数を表し、ｎが２以上の整数のとき、複数個のＲは互いに同一でも異なっていてもよく、また互いに連結して環を形成していてもよい。］

[In General Formula (X), A and B are electron-withdrawing groups in which the sum of the Hammett σp values of A and B is 0.6 or more and may be linked to each other to form a ring; And D are electron-withdrawing groups in which the sum of the Hammett σp values of C and D is 0.6 or more and may be linked to each other to form a ring, and R represents a substituent on the methine carbon. , M represents an integer in the range of 0 to 3, n represents an integer in the range of 0 to (2m + 1), and when n is an integer of 2 or more, a plurality of Rs may be the same or different from each other, They may be connected to each other to form a ring. ]

  Below, the detail of the said pigment | dye is demonstrated.

  Dye A is an oxonol dye, and is represented by the following formula (X), a dye containing a cation that can neutralize the charge of the anion compound, and / or the following formula (X). Two or more of these compounds (which may be the same or different) neutralize the anion compound linked to each other via any one of A, B, C and / or D and the charge of the anion compound. It is a dye containing the resulting cation. In the present invention, the oxonol dye is defined as a polymethine dye having an anionic dye moiety.

  Details of the general formula (X) will be described below.

  In the general formula (X), A and B are electron-withdrawing groups in which the sum of the Hammett σp values of A and B is 0.6 or more, and may be connected to each other to form a ring. D is an electron-withdrawing group in which the sum of the Hammett σp values of C and D is 0.6 or more and may be linked to each other to form a ring, R represents a substituent on the methine carbon, m represents an integer in the range of 0 to 3, n represents an integer in the range of 0 to (2m + 1), and when n is an integer of 2 or more, a plurality of R may be the same or different from each other, They may be connected to each other to form a ring. The general formula (I) includes a plurality of tautomers due to differences in the notation of the local position of the anion. In particular, any of A, B, C, and D is -CO-E (E is a substituent). In some cases, it is common to describe a localized negative charge on an oxygen atom. For example, when D is -CO-E, the following general formula (XI) is common as the notation, and such notation is also included in the general formula (I).

  The definitions of A, B, C, R, m, and n in the general formula (XI) are the same as those in the general formula (X).

  Hereinafter, the oxonol dye moiety represented by the general formula (X) will be described. In the general formula (I), A, B, C, and D are the sum of Hammett's substituent constants σp values of A and B and the sum of Hammett's substituent constants σp values of C and D are 0.6 or more, respectively. Represents an electron-withdrawing group. A, B, C and D may be the same or different. A and B or C and D may be linked to form a ring. The Hammett substituent constant σp value of the electron-withdrawing group represented by A, B, C and D is preferably independently in the range of 0.30 to 0.85, more preferably 0.35. It is in the range of ~ 0.80.

  Hammett's substituent constant σp value (hereinafter referred to as σp value) is described, for example, in Chem. Rev. 91, 165 (1991) and references cited therein, and those not described can be obtained by the method described in the same document. When A and B (C and D) are linked to form a ring, the σp value of A (C) means the σp value of the group -A-B-H (-C-D-H). , B (D) σp value means the σp value of the group -BAH (-DCH). In this case, both have different σp values because of different coupling directions.

  Preferred examples of the electron-withdrawing group represented by A, B, C and D include a cyano group, a nitro group, an acyl group having 1 to 10 carbon atoms (eg, acetyl group, propionyl group, butyryl group, pivaloyl). Group, benzoyl group), alkoxycarbonyl group having 2 to 12 carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, decyloxycarbonyl group), aryl having 7 to 11 carbon atoms Oxycarbonyl group (eg, phenoxycarbonyl group), carbamoyl group having 1 to 10 carbon atoms (eg, methylcarbamoyl group, ethylcarbamoyl group, phenylcarbamoyl group), alkylsulfonyl group having 1 to 10 carbon atoms (eg, methane) Sulfonyl group), arylsulfonyl groups having 6 to 10 carbon atoms (eg, ben Sulfonyl group), alkoxysulfonyl group having 1 to 10 carbon atoms (eg, methoxysulfonyl group), sulfamoyl group having 1 to 10 carbon atoms (eg, ethylsulfamoyl group, phenylsulfamoyl group), carbon atom An alkylsulfinyl group having 1 to 10 carbon atoms (eg, methanesulfinyl group, ethanesulfinyl group), an arylsulfinyl group having 6 to 10 carbon atoms (eg, benzenesulfinyl group), an alkylsulfenyl group having 1 to 10 carbon atoms ( Example, methanesulfenyl group, ethanesulfenyl group), arylsulfenyl group having 6 to 10 carbon atoms (eg, benzenesulfenyl group), halogen atom, alkynyl group having 2 to 10 carbon atoms (eg, ethynyl group) ), A diacylamino group having 2 to 10 carbon atoms (eg, diacetylamino group), a phosphoryl group, A ruboxyl group, a 5-membered or 6-membered heterocyclic group (for example, 2-benzothiazolyl group, 2-benzoxazolyl group, 3-pyridyl group, 5- (1H) -tetrazolyl group, 4-pyrimidyl group); Preferred examples include a cyano group, an alkoxycarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group.

  In the general formula (X), examples of the substituent on the methine carbon represented by R include those described below. A linear or cyclic alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group), substituted or unsubstituted aryl having 6 to 18 carbon atoms Group (for example, phenyl group, chlorophenyl group, anisyl group, toluyl group, 2,4-di-t-amyl group, 1-naphthyl group), alkenyl group (for example, vinyl group, 2-methylvinyl group), alkynyl group (For example, ethynyl group, 2-methylethynyl group, 2-phenylethynyl group), halogen atom (for example, F, Cl, Br, I), cyano group, hydroxyl group, carboxyl group, acyl group (for example, acetyl group, Benzoyl group, salicyloyl group, pivaloyl group), alkoxy group (for example, methoxy group, butoxy group, cyclohexyloxy group), aryloxy group For example, a phenoxy group, 1-naphthoxy group), an alkylthio group (e.g., methylthio, butylthio, benzylthio, 3-methoxypropylthio group), an arylthio group (e.g., phenylthio group, 4-chlorophenylthio group),

  Alkylsulfonyl group (for example, methanesulfonyl group, butanesulfonyl group), arylsulfonyl group (for example, benzenesulfonyl group, paratoluenesulfonyl group), carbamoyl group having 1 to 10 carbon atoms, amide group having 1 to 10 carbon atoms , An imide group having 2 to 12 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, a heterocyclic group (for example, a pyridyl group, a thienyl group, a furyl group, a thiazolyl group, Aromatic heterocyclic rings such as imidazolyl group and pyrazolyl, pyrrolidine rings, piperidine rings, morpholine rings, pyran rings, thiopyran rings, dioxane rings, dithiolane rings and the like.

  R is preferably a halogen atom, a linear or cyclic alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 6 to 10 carbon atoms. Aryloxy group, heterocyclic group having 3 to 10 carbon atoms, especially chlorine atom, alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, isopropyl group), phenyl group, carbon atom number 1-4 alkoxy groups (e.g., methoxy group, ethoxy group), phenoxy groups, nitrogen-containing heterocyclic groups having 4-8 carbon atoms (e.g., 4-pyridyl group, benzoxazol-2-yl, benzothiazole-2) -Yl) is preferred.

  n represents an integer in the range of 0 to (2m + 1). Note that m will be described later. n is preferably an integer in the range of 0-7. When n is an integer greater than or equal to 2, several R may mutually be same or different, and may mutually connect and may form a ring. At this time, the number of ring members is preferably 4 to 8, particularly preferably 5 or 6, and the constituent atoms of the ring are preferably carbon atoms, oxygen atoms or nitrogen atoms, and particularly preferably carbon atoms.

  A, B, C, D and R may further have a substituent, and examples of the substituent include those mentioned above as examples of the monovalent substituent represented by R in formula (I). The same thing can be mentioned.

  As the dye used as the recording layer dye, A and B or C and D are preferably linked to form a ring from the viewpoint of thermal decomposability. Examples of such a ring include the following. Can be mentioned. In the examples, Ra, Rb and Rc each independently represents a hydrogen atom or a substituent.

  Among the above, preferable rings are D-2, D-8, D-9, D-10, D-13, D-14, D-16, D-17, D-36, D-39, D. -42, D-54, D-57, D-59, D-61, D-65 and D-66. More preferably, D-2, D-9, D-10, D-13, D-17, D-42, D-54, D-57, D-59, D-61, D-65 and D- 66. Most preferred are those represented by D-13, D-17, D-54, D-57, D-59, D-61, D-65 and D-66.

  The substituents represented by Ra, Rb and Rc have the same meanings as those exemplified as the substituent represented by R. Ra, Rb and Rc may be connected to each other to form a carbocyclic or heterocyclic ring. Examples of the carbocycle include saturated or unsaturated 4- to 7-membered carbocycles such as a cyclohexyl ring, a cyclopentyl ring, a cyclohexene ring, and a benzene ring. Examples of the heterocyclic ring include saturated or unsaturated 4- to 7-membered heterocyclic rings such as a piperidine ring, piperazine ring, morpholine ring, tetrahydrofuran ring, furan ring, thiophene ring, pyridine ring, and pyrazine ring. it can. These carbocycles or heterocycles may be further substituted. Further, the group which can be substituted has the same meaning as the substituents represented by R.

  In general formula (X), m is an integer in the range of 0-3. The absorption wavelength of the oxonol dye varies greatly depending on the value of m. A dye having an optimum absorption wavelength should be designed according to the oscillation wavelength of the laser used for recording / reproduction, and in this respect, the selection of the value of m is important. When the central oscillation wavelength of the laser used for recording / reproduction is 440 nm or less (for example, a blue-violet semiconductor laser having a central oscillation wavelength of 405 nm), m is preferably 0 or 1.

  The oxonol chromophore represented by the general formula (X) may be bonded at an arbitrary position to form a multimer. In this case, each unit may be the same as or different from each other. You may couple | bond with polymer chains, such as a methacrylate, polyvinyl alcohol, and a cellulose.

  In addition, two or more of the anionic compounds represented by the general formula (X) may form a multimer linked to each other via any one of A, B, C and / or D. In this case, a plurality of oxonol dye moieties represented by general formula (I) may be the same or different. Specific examples include dimers linked by a linking group in the form of removing any hydrogen atom constituting A, B, C, or D in the general formula (X).

As the dimer of the anion compound represented by the general formula (X), an anion compound having a structure represented by the following general formula (XII) is preferable.

In general formula (XII), Za ⁵ and Za ⁶ are each independently an atomic group forming an acidic nucleus, L ¹¹ represents a divalent linking group, and definitions of A, B, C, and D The details are as described for A, B, C, and D of the general formula (X).
In general formula (XII), R ¹ and R ² each independently represent a substituent on the methine carbon, and the details thereof are as described above for R in general formula (X). R ¹ and R ² may be the same or different.
In general formula (XII), m1 and m2 each independently represent an integer in the range of 0 to 3, and details thereof are as described for m in general formula (X).
In general formula (XII), n1 represents an integer in the range of 0 to (2m1 + 1), and n2 represents an integer in the range of 0 to (2m2 + 1). The details of n1 and n2 are as described above for n in the general formula (X). M1 and m2, and n1 and n2 may be the same or different.

In the general formula (XII), any hydrogen atom constituting Za ⁵ and Za ⁶ can be removed and bonded to the linking group L ¹¹ as a dye residue of the general formula (I).

Za ⁵ and Za ⁶ each represent an atomic group necessary for forming an acidic nucleus, and are defined by James ed., The Theory of the Photographic Process, 4th edition, Macmillan, 1977, p. 198. Specifically, 2-pyrazolone-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline-5 -One, 2-thiooxazoline-2,4-dione, isorhodanine, rhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indoline-2-one, Indoline-3-one, 2-oxoindazolium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, 3,4-dihydroisoquinolin-4-one, 1,3- Dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, coumarin-2,4-dione, indazolin-2-one, pyrido Nuclei such as 1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazolone, pyrazolopyridone, 3-dicyanomethylidenyl-3-phenylpropionitrile, oxathiolanone dioxide, meldrum acid, etc. Preferred are 2-pyrazolone-5-one, barbituric acid, 2-thiobarbituric acid, oxathiolanone dioxide, meldrum acid, and pyrazolidine-3,5-dione.

More specifically, the acidic nucleus formed by Za ⁵ and Za ⁶ includes an oxazole nucleus having 3 to 25 carbon atoms (for example, 2-3 methyloxazolyl, 2-3 ethyloxazolyl, 2- 3,4-diethyloxazolyl, 2-3-methylbenzoxazolyl, 2-3-ethylbenzoxazolyl, 2-3-sulfoethylbenzoxazolyl, 2-3-sulfopropylbenzoxazolyl 2-methylthioethylbenzoxazolyl, 2-methoxyethylbenzoxazolyl, 2-3-sulfobutylbenzoxazolyl, 2-3-methyl-β-naphthoxazolyl, 2-3 -Methyl-α-naphthoxazolyl, 2-3-sulfopropyl-β-naphthoxazolyl, 2-3-sulfopropyl-β-naphthoxazolyl, 2-3- (3-naphthoxyethyl) Benzoxazolyl, 2-3,5-dimethylbenzoxazolyl, 2-6-chloro-3-methylbenzoxazolyl, 2-5-bromo-3-methylbenzoxazolyl, 2-3-ethyl -5-methoxybenzoxazolyl, 2-5-phenyl-3-sulfopropylbenzoxazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzoxazolyl, 2-3-dimethyl- 5,6-dimethylthiobenzoxazolyl), thiazole nucleus having 3 to 25 carbon atoms (for example, 2-3-methylthiazolyl, 2-3-ethylthiazolyl, 2-3-sulfopropylthiazolyl, 2-3-sulfo) Butylthiazolyl, 2-3,4-dimethylthiazolyl, 2-3,4,4-trimethylthiazolyl, 2-3-carboxyethylthiazolyl, 2-3-methylbenzo Azolyl, 2-3-ethylbenzothiazolyl, 2-3-butylbenzothiazolyl, 2-3-sulfopropylbenzothiazolyl, 2-3-sulfobutylbenzothiazolyl, 2-3-methyl- β-naphthothiazolyl, 2-3-sulfopropyl-γ-naphthothiazolyl, 2-3- (1-naphthoxyethyl) benzothiazolyl, 2-3,5-dimethylbenzothiazolyl, 2-6-chloro-3-methylbenzothiazolyl 2-6-iodo-3-ethylbenzothiazolyl, 2-5-bromo-3-methylbenzothiazolyl, 2-3-ethyl-5-methoxybenzothiazolyl, 2-5-phenyl- 3-sulfopropylbenzothiazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzothiazolyl, 2-3-dimethyl-5,6-dimethylthiobenzo Azolyl and the like), imidazole nucleus having 3 to 25 carbon atoms (for example, 2-1,3-diethylimidazolyl, 2-1,3-dimethylimidazolyl, 2-1-methylbenzimidazolyl, 2-1,3,4) -Triethylimidazolyl, 2-1,3-diethylbenzimidazolyl, 2-1,3,5-trimethylbenzimidazolyl, 2-6-chloro-1,3-dimethylbenzimidazolyl, 2-5,6-dichloro-1,3-diethyl Benzoimidazolyl, 2-1,3-disulfopropyl-5-cyano-6-chlorobenzimidazolyl, etc.), an indolenine nucleus having 10 to 30 carbon atoms (for example, 3,3-dimethylindolenine), 9 carbon atoms -25 quinoline nuclei (eg 2-1 methylquinolyl, 2-1 ethylquinolyl, 2-1 6-chloroquinolyl, 2-1,3-diethylquinolyl, 2-1-methyl-6-methylthioquinolyl, 2-1-sulfopropylquinolyl, 4-1-methylquinolyl, 4-1-sulfoethylquinolyl 4-1-methyl-7-chloroquinolyl, 4-1,8-diethylquinolyl, 4-1-methyl-6-methylthioquinolyl, 4-1-sulfopropylquinolyl, etc.), carbon number 3 -25 selenazole nucleus (for example, 2-3methylbenzoselenazolyl and the like), pyridine nucleus having 5 to 25 carbon atoms (for example, 2-pyridyl and the like) and the like. Thiazoline nucleus, oxazoline nucleus, selenazoline nucleus, tellurazoline nucleus, tellurazole nucleus, benzotelrazole nucleus, imidazoline nucleus, imidazo [4,5-quinoxaline] Examples include a nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus. These may be substituted, and as a substituent, for example, an alkyl group (for example, methyl group, ethyl group, propyl group), a halogen atom (for example, chlorine, bromine, iodine, fluorine), a nitro group, an alkoxy group (for example, , Methoxy group, ethoxy group), aryl group (for example, phenyl group), heterocyclic group (for example, 2-pyridyl group, 3-pyridyl group, 1-pyrrolyl group, 2-thienyl group), aryloxy group (for example, phenoxy) Group), acylamino group (for example, acetylamino group, benzoylamino group), carbamoyl group (for example, N, N-dimethylcarbamoyl group), sulfo group, sulfonamide group (for example, methanesulfonamide group), sulfamoyl group (for example, N-methyl group) Sulfamoyl group), hydroxy group, carboxy group, alkylthio group (eg methyl O group) and a cyano group. The acidic nucleus formed by Za ⁵ and Za ⁶ is preferably an oxazole nucleus, an imidazole nucleus, or a thiazole nucleus. These heterocycles may be further condensed. Examples of the condensed ring include a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, and a thiophene ring.

In the general formula (XII), L ¹¹ represents a divalent linking group, and there is no particular limitation except that a π-conjugated system is not formed between the chromophores to which they are bonded. 20, for example, methylene group, ethylene group, propylene group, butylene group, pentylene group), arylene group (having 6 to 26 carbon atoms, such as phenylene group, naphthylene group), alkenylene group (having 2 to 20 carbon atoms, such as ethenylene group, propenylene) Group), alkynylene group (having 2 to 20 carbon atoms, such as ethynylene group, propynylene group), metallocenylene group (for example, ferrocene group), -CO-N (R ¹⁰¹ )-, -CO-O-, -SO ₂ -N ( _{^{R 102) -, - SO 2}} -O -, - N (R 103) -CO-N (R 104) -, - SO 2 -, - SO -, - S -, - O -, - CO -, - N (R ¹⁰⁵⁾ -, Heterire Carbon number formed by combining one or more groups (having 1 to 26 carbon atoms, for example, 6-chloro-1,3,5-triazyl-2,4-diyl group, pyrimidine-2,4-diyl group) 0 to 100, preferably 1 to 20 linking groups are represented. R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , and R ¹⁰⁵ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. One or more linking groups represented by L ¹¹ may be present between two chromophores to which they are linked, and a plurality (preferably two) are bonded to form a ring. Also good. L ¹¹ is preferably one in which two alkylene groups (preferably an ethylene group) are bonded to form a ring. Among them, the case where a 5- or 6-membered ring (preferably cyclohexyl) is formed is more preferable.

  Among the anionic compounds represented by the general formula (X), the anionic compounds represented by the following general formula (XIII) are most preferable.

  In general formula (XIII), the definitions and details of A, B, C, D, R, m, and n are as described for A, B, C, D, R, m, and n in general formula (X). is there.

  The preferred specific examples of the anion compounds represented by the general formulas (X) to (XIII) are shown below, but the present invention is not limited thereto.

  The dye A contains the anion compound and a cation capable of neutralizing the charge of the anion compound. In the following, the cation is not particularly limited, and may be an ion composed of an inorganic compound or an ion composed of an organic compound. The cation charge may be monovalent or multivalent. Examples of the cation include metal ions such as sodium ion and potassium ion, quaternary ammonium ions, oxonium ions, sulfonium ions, phosphonium ions, selenonium ions, onium ions such as iodonium ions. The cation represented by Q is preferably an onium ion, and more preferably a quaternary ammonium ion. Of the quaternary ammonium ions, 4,4′-bipyridinium cation represented by general formula (I-4) in JP-A No. 2000-52658 and JP-A No. 2002-59652 are particularly preferable. 4,4′-bipyridinium cation.

  Although the preferable specific example of the pigment | dye A is given to the following, this invention is not limited to these.

  The above dyes can be synthesized by known methods, and some are available as commercial products.

Cyanine Dye Compound The optical information recording medium of the present invention can also contain a compound (polymethine derivative) represented by the following general formula (XX) as a recording dye. The cyanine dye compound preferably has the aforementioned preferable dye physical properties.

［一般式（XX）中、Ｘ¹およびＸ²は、各々独立に、酸素原子、硫黄原子またはＮ−Ｒを表し、Ｒはアルキル基、アリール基、または複素環基を表し、Ｚａ¹およびＺａ²は、各々独立に、５員または６員の複素環を完成するために必要な原子群を表し、Ｌ¹、Ｌ²およびＬ³は、各々独立に、置換または無置換のメチン基を表し（但し、Ｌ¹〜Ｌ³上に置換基がある場合には互いに連結して環を形成してもよい）、ｊは、０または１を表し、Ｍ₁は電荷均衡対イオンを表し、ｍ１は分子の電荷を中和するために必要な０以上１０以下の数を表す。]

[In General Formula (XX), X ¹ and X ² each independently represent an oxygen atom, a sulfur atom or N—R, R represents an alkyl group, an aryl group, or a heterocyclic group, and Za ¹ and Za ² independently represents a group of atoms necessary to complete a 5-membered or 6-membered heterocyclic ring, and L ¹ , L ² and L ³ each independently represents a substituted or unsubstituted methine group. (However, when there is a substituent on L ^{1 to} L ³ , they may be linked to each other to form a ring), j represents 0 or 1, M ₁ represents a charge balanced counter ion, m 1 Represents a number from 0 to 10 which is necessary for neutralizing the charge of the molecule. ]

  Details of the general formula (XX) will be described below.

［一般式（XX）中、Ｘ¹およびＸ²は、各々独立に、酸素原子、硫黄原子またはＮ−Ｒを表し、Ｒはアルキル基、アリール基、または複素環基を表し、Ｚａ¹およびＺａ²は、各々独立に、５員または６員の複素環を完成するために必要な原子群を表し、Ｌ¹、Ｌ²およびＬ³は、各々独立に、置換または無置換のメチン基を表し（但し、Ｌ¹〜Ｌ³上に置換基がある場合には互いに連結して環を形成してもよい）、ｊは、０または１を表し、Ｍ₁は電荷均衡対イオンを表し、ｍ１は分子の電荷を中和するために必要な０以上１０以下の数を表す。]

[In General Formula (XX), X ¹ and X ² each independently represent an oxygen atom, a sulfur atom or N—R, R represents an alkyl group, an aryl group, or a heterocyclic group, and Za ¹ and Za ² independently represents a group of atoms necessary to complete a 5-membered or 6-membered heterocyclic ring, and L ¹ , L ² and L ³ each independently represents a substituted or unsubstituted methine group. (However, when there is a substituent on L ^{1 to} L ³ , they may be linked to each other to form a ring), j represents 0 or 1, M ₁ represents a charge balanced counter ion, m 1 Represents a number from 0 to 10 which is necessary for neutralizing the charge of the molecule. ]

In general formula (XX), L ₁ , L ₂ and L ₃ each independently represent a substituted or unsubstituted methine group. When there are substituents on L ^{1 to} L ³ , they may be linked to each other to form a ring.

  When the substituent that the methine group may have is V, the substituent represented by V is not particularly limited. For example, a halogen atom (for example, chlorine, bromine, iodine, fluorine), a mercapto group, a cyano group, a carboxyl group , Phosphoric acid group, sulfo group, hydroxy group, carbamoyl group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms (for example, methylcarbamoyl group, ethylcarbamoyl group, morpholinocarbonyl group) A sulfamoyl group having 0 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms (for example, a methylsulfamoyl group, an ethylsulfamoyl group, a piperidinosulfonyl group), a nitro group, An alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (for example, methoxy group, ethoxy group) 2-methoxyethoxy group, 2-phenylethoxy group), an aryloxy group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms (for example, a phenoxy group, a p-methylphenoxy group, p-chlorophenoxy group, naphthoxy group), C1-C20, preferably C2-C12, more preferably C2-C8 acyl group (for example, acetyl group, benzoyl group, trichloroacetyl group), carbon number 1-20, preferably C2-C12, more preferably C2-C8 acyloxy group (for example, acetyloxy group, benzoyloxy group), C1-C20, preferably C2-C12, more preferably Is an acylamino group having 2 to 8 carbon atoms (for example, acetylamino group), 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably Is a sulfonyl group having 1 to 8 carbon atoms (for example, methanesulfonyl group, ethanesulfonyl group, benzenesulfonyl group, etc.), 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably a sulfinyl group having 1 to 8 carbon atoms ( For example, methanesulfinyl group, benzenesulfinyl group), sulfonylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (for example, methanesulfonylamino group, ethanesulfonylamino group, benzenesulfonylamino group) Group), an amino group, a substituted amino group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (for example, a methylamino group, a dimethylamino group, a benzylamino group, an anilino group, Diphenylamino group), 0-15 carbon atoms, preferably 3-10 carbon atoms, more preferred Or a C3-C6 ammonium group (for example, trimethylammonium group or triethylammonium group), C0-C15, preferably C1-C10, more preferably C1-C6 hydrazino group (e.g. trimethylhydra). Dino group), a ureido group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (for example, a ureido group, N, N-dimethylureido group), 1 to 15 carbon atoms, preferably Is an imide group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (for example, a succinimide group), 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably an alkyl or arylthio having 1 to 8 carbon atoms. Group (for example, methylthio group, ethylthio group, carboxyethylthio group, sulfobutylthio group, phenylthio group, etc.) 0, preferably an alkoxycarbonyl group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), 6 to 20 carbon atoms, preferably 6 to 6 carbon atoms 12, more preferably an aryloxycarbonyl group having 6 to 8 carbon atoms (for example, phenoxycarbonyl group), an unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms ( For example, a methyl group, an ethyl group, a propyl group, a butyl group), a substituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms (hydroxymethyl group, trifluoromethyl group). Benzyl group, carboxyethyl group, ethoxycarbonylmethyl group, acetylaminomethyl group, and here An unsaturated hydrocarbon group having 2 to 18 carbon atoms, more preferably 3 to 10 carbon atoms, particularly preferably 3 to 5 carbon atoms (for example, a vinyl group, an ethynyl group, a 1-cyclohexenyl group, a benzylidine group, a benzylidene group). Group) is also included in the substituted alkyl group. ), A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (for example, phenyl group, naphthyl group, p-carboxyphenyl group, p-nitrophenyl). Group, 3,5-dichlorophenyl group, p-cyanophenyl group, m-fluorophenyl group, p-tolyl group), C1-20, preferably C2-10, and more preferably C4-6. Examples thereof include a heterocyclic group which may be substituted (for example, pyridyl group, 5-methylpyridyl group, thienyl group, furyl group, morpholino group, tetrahydrofurfuryl group).

Preferred examples of the substituent include the above-described alkyl group, aryl group, alkoxy group, halogen atom, acyl group, cyano group, sulfonyl group, and benzene ring condensation, and more preferable alkyl group, aryl group, halogen atom, acyl group. And a sulfonyl group. L _{1 to} L ₃ are preferably unsubstituted methine groups.

  j is 0 or 1, and when j is 1, the methine group is repeated but need not be identical.

X ¹ and X ² each independently represents an oxygen atom, a sulfur atom or N—R, and R represents an alkyl group, an aryl group or a heterocyclic group. X ¹ and X ² may be the same or different, but are preferably the same.

As the alkyl group, for example, an unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, particularly preferably 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, A hexyl group, an octyl group, a dodecyl group, an octadecyl group), a substituted alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms {for example, V mentioned as a substituent such as L ₁ described above Examples include substituted alkyl groups. Preferably, an aralkyl group (for example, benzyl group, 2-phenylethyl group), an unsaturated hydrocarbon group (for example, allyl group), a hydroxyalkyl group (for example, 2-hydroxyethyl group, 3-hydroxypropyl group), a carboxyalkyl group ( For example, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, carboxymethyl group), alkoxyalkyl group (for example, 2-methoxyethyl group, 2- (2-methoxyethoxy) ethyl group), aryl Roxyalkyl groups (for example, 2-phenoxyethyl group, 2- (1-naphthoxy) ethyl group), alkoxycarbonylalkyl groups (for example, ethoxycarbonylmethyl group, 2-benzyloxycarbonylethyl group), aryloxycarbonylalkyl groups (for example, 3 -Phenoxycarbonylpropi Group), an acyloxyalkyl group (for example, 2-acetyloxyethyl group), an acylalkyl group (for example, 2-acetylethyl group), a carbamoylalkyl group (for example, 2-morpholinocarbonylethyl group), a sulfamoylalkyl group (for example, N, N-dimethylcarbamoylmethyl group), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2- [3-sulfopropoxy] ethyl group, 2-hydroxy- 3-sulfopropyl group, 3-sulfopropoxyethoxyethyl group), sulfoalkenyl group (for example, sulfopropenyl group), sulfatoalkyl group (for example, 2-sulfatoethyl group, 3-sulfatopropyl group, 4-sulfopropyl group) Fat-butyl group), a heterocyclic-substituted alkyl group (for example, 2- Pyrrolidin-2-one-1-yl) ethyl group, tetrahydrofurfuryl group), alkylsulfonylcarbamoyl methyl group (e.g. methanesulfonyl carbamoylmethyl methyl group)} and the like.

As the aryl group, for example, an unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms (for example, phenyl group, 1-naphthyl group), 6 to 20 carbon atoms, Preferably, it is a substituted aryl group having 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms (for example, an aryl group substituted with V mentioned as a substituent such as L ¹ described above. Specifically, p-methoxy is mentioned. A phenyl group, a p-methylphenyl group, a p-chlorophenyl group, etc.).

Examples of the heterocyclic group include unsubstituted heterocyclic groups having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms (for example, 2-furyl group, 2-thienyl group, 2-pyridyl group). Group, 3-pyrazolyl group, 3-isoxazolyl group, 3-isothiazolyl group, 2-imidazolyl group, 2-oxazolyl group, 2-thiazolyl group, 2-pyridazyl group, 2-pyrimidyl group, 3-pyrazyl group, 2- ( 1,3,5-triazolyl) group, 3- (1,2,4-triazolyl) group, 5-tetrazolyl group), C1-20, preferably C3-10, more preferably C4 8 substituted heterocyclic groups (for example, a heterocyclic group substituted by V mentioned as a substituent such as L ¹ described above, specifically, 5-methyl-2-thienyl group, 4-methoxy-2-pyridyl) Group It is.) And the like.

Za ¹ and Za ² each independently represents an atomic group necessary for completing a 5-membered or 6-membered heterocyclic ring. Za ¹ and Za ² may be the same or different, but are preferably the same.
Examples of the 5-membered or 6-membered heterocyclic ring (nucleus) containing Za ¹ include thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, thiazoline nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, oxazoline nucleus, and selenazole nucleus. , Benzoselenazole nucleus, naphthoselenazole nucleus, selenazoline nucleus, tellurazole nucleus, benzotelrazole nucleus, naphthotelrazole nucleus, tellurazoline nucleus, imidazole nucleus, benzimidazole nucleus, naphthimidazole nucleus, pyridine nucleus, quinoline nucleus, isoquinoline nucleus, Imidazo [4,5-b] quinoxaline nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus, pyrrole nucleus, indolenine nucleus, benzoindolenine nucleus, 1,3-dioxolane nucleus, and 1,3-dithiolane Nuclear It can be mentioned. Among these, thiazole nucleus, thiazoline nucleus, benzothiazole nucleus, oxazole nucleus, oxazoline nucleus, benzoxazole nucleus, imidazole nucleus, benzimidazole nucleus, naphthimidazole nucleus, quinoline nucleus, isoquinoline nucleus, imidazo [4,5-b] A quinoxaline nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus, pyrrole nucleus, indolenine nucleus, benzoindolenine nucleus, 1,3-dioxolane nucleus, and 1,3-dithiolane nucleus are preferred. These rings may be further condensed with a benzene ring, a dioxolane ring, or a naphthoquinone ring.

  The 5-membered or 6-membered nitrogen-containing heterocyclic ring may have a substituent. Examples of preferred substituents (atoms) include halogen atoms, substituted or unsubstituted alkyl groups, aryl groups, alkoxy groups, and alkoxycarbonyl groups. As the halogen atom, a chlorine atom is preferable. The alkyl group is preferably a linear alkyl group having 1 to 6 carbon atoms. Examples of the substituent for the alkyl group include an alkoxy group (eg, methoxy group) and an alkylthio group (eg, methylthio group). As the aryl group, a phenyl group is preferable. As the alkoxy group, a methoxy group is preferable. As the alkoxycarbonyl group, a methoxycarbonyl group is preferable. Particularly preferred examples of the substituent are a halogen atom, an unsubstituted alkyl group, an alkoxy group, and an alkoxycarbonyl group.

M ₁ represents a charge-balanced counter ion and is included in the formula to indicate the presence of a cation or an anion when needed to neutralize the ionic charge of the dye. Typical cations include inorganic cations such as hydrogen ions (H ⁺ ), alkali metal ions (eg, sodium ions, potassium ions, lithium ions), alkaline earth metal ions (eg, calcium ions), ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, pyridinium ion, ethylpyridinium ion). The anion may be either an inorganic anion or an organic anion, such as a halogen anion (eg, fluorine ion, chlorine ion, iodine ion), a substituted aryl sulfonate ion (eg, p-toluenesulfonate ion, p-chloro). Benzene sulfonate ion), aryl disulfonate ion (for example, 1,3-benzene sulfonate ion, 1,5-naphthalene disulfonate ion, 2,6-naphthalene disulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion), Examples thereof include sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, and trifluoromethanesulfonate ion. Furthermore, you may use the ionic polymer or the other pigment | dye which has a charge opposite to a pigment | dye. In the present invention, the sulfo group is expressed as SO ₃ ⁻ , but it can also be expressed as SO ₃ H when it has a hydrogen ion as a counter ion. m1 represents a number from 0 to 10 necessary for neutralizing the charge of the molecule, and is 0 when a salt is formed in the molecule.

  The compound represented by the general formula (XX) is preferably a compound represented by the following general formula (XX-1), the following general formula (XX-2), or the following general formula (XXI).

In the general formulas (XX-1) and (XX-2), Zb represents an atomic group necessary for forming an indolenine nucleus, a benzoindolenine nucleus, a benzimidazole nucleus, a benzoxazole nucleus or a benzothiazole nucleus, Xa represents an oxygen atom, a sulfur atom, C (R ₃ ) (R ₄ ) or N—R ₅ , and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently an alkyl group or aryl And L ₄ represents a substituted or unsubstituted methine group. M ₁ and m1 are synonymous with the definitions in the general formula (I-1), and their preferred ranges are also the same.

  The indolenine nucleus, benzoindolenine nucleus, benzimidazole nucleus, benzoxazole nucleus or benzothiazole nucleus containing Zb may have a substituent. Examples of the substituent (which may be an atom) include the examples of the substituent on the 5-membered or 6-membered heterocyclic ring described above, and the preferred ranges thereof are also the same.

R ₁ and R ₂ represent an alkyl group or an aryl group, and details thereof are as described above for R in the general formula (I-1).

R ₃ , R ₄ and R ₅ represent an alkyl group or an aryl group, preferably an alkyl group, more preferably a linear or branched chain having 1 to 18 carbon atoms which may have a substituent. Or a cyclic alkyl group. The alkyl group represented by R ₃ , R ₄ and R ₅ is particularly preferably a linear unsubstituted alkyl group having 1 to 6 carbon atoms (for example, a methyl group or an ethyl group).

In the general formula (XXI), Xb and Xc each independently represent an oxygen atom, a sulfur atom, or N—R ₁₄ , and R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom, an alkyl group or an aryl group, and L ₅ , L ₆ and L ₇ each independently represents a substituted or unsubstituted methine group. However, when there are substituents on L _{5 to} L ₇ , these substituents may be linked to each other to form a ring. k represents 0 or 1; M ₁ and m1 are synonymous with the definitions in the general formula (I-1), and their preferred ranges are also the same.

Xb and Xc are each an oxygen atom, a sulfur atom, or N—R ₁₄ , or one is an oxygen atom and the other is N—R ₁₄ , or one is a sulfur atom and the other is N—R _14. It is preferable to become a combination of R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a substituent. A good linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. The alkyl groups represented by R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each a linear unsubstituted alkyl having 1 to 6 carbon atoms. A group (for example, a methyl group or an ethyl group) is particularly preferable.

In the general formula (XXI), L ₅ , L ₆ and L ₇ each independently represent a substituted or unsubstituted methine group, and the details thereof are represented by L ₁ , L ₂ and the general formula (XX-1). As described for L ₃ .

  Specific preferred examples of the compound represented by the general formula (XX) (including the compound represented by the general formula (XX-1), the general formula (XX-2), or (XXI)) are given below.

  Examples of the coloring compound include, for example, “The Cyanin Soybean and Related Compounds 5 (Interscience Publishers, NY 1964)” p. 55;・ "Polymethine soy", Saint-Clement Aurizuki University Press, Sofia (Nikolai Tyutyulkov, Jurgen Fabian, Achim Ulehlhorn, Fritz Dietz, Alia Tadjer) St. Kliment Ohridski University Press, Sophia, pp. 23-38; DMSturmer, “Heterocyclic Compounds-Special topics in repeating chemistry) "Chapter 18, Section 14, pp. 482-515, John Wiley & Sons, New York, London, (1977);" Rods Chemistry of Carbon Compounds. " (Rodd's Chemistry of Carbon Compounds), (2nd.Ed.vol.IV, part B, published in 1977), Chapter 15, pages 369-422, (2nd.Ed.vol.IV, part B, published in 1985) , Chapter pp. 267-296, Elsvier Science Public Company Inc., New York, and the like.

  In order to introduce a polyvalent anion as a counter ion, first, a dye having a monovalent counter ion is dissolved in a suitable solvent, and a solution of a polyvalent acid or a salt thereof is added thereto. A method of adding a solvent that hardly dissolves the dye and precipitating a dye crystal having a multivalent ion as a counter ion is the simplest and suitable for a large amount of synthesis. Other methods include a method of exchanging counter ions using an ion exchange resin.

  As described above, the amount of the recording layer dye used is, for example, in the range of 1 to 100% by mass, preferably 50 to 100% by mass, and more preferably 75 to 100% by mass with respect to the total mass of the recording layer. Range. As a recording dye, one kind of dye compound can be used, or two or more kinds can be used in combination.

Next, formation of the recording layer will be described.
The recording layer is prepared by dissolving the dye together with a binder or the like in an appropriate solvent without using a binder, and then coating this coating liquid on a reflective layer described later to form a coating film. After forming, it can be formed by drying. Here, the write-once recording layer may be a single layer or a multilayer. A recording layer having a multilayer structure can be formed by performing the step of applying the coating solution a plurality of times.
The concentration of the dye in the coating solution is generally in the range of 0.01 to 15% by mass, preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 5% by mass, most preferably. It is the range of 0.5-3 mass%.

Solvents used for preparing the coating solution include, for example, esters such as butyl acetate, ethyl lactate and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chloroform. Amides such as dimethylformamide; hydrocarbons such as methylcyclohexane; ethers such as tetrahydrofuran, ethyl ether and dioxane; alcohols such as ethanol, n-propanol, isopropanol and n-butanol diacetone alcohol; 2,2,3,3- Fluorinated solvents such as tetrafluoro-1-propanol; glycol agents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether And the like can be given; le compound.
Solvents can be used alone or in combination of two or more in consideration of the solubility of the dye used. In the coating solution, various additives such as a binder, an antioxidant, a UV absorber, a plasticizer, and a lubricant may be added according to the purpose.

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.
During coating, the temperature of the coating solution is preferably in the range of 23 to 50 ° C, more preferably in the range of 23 to 40 ° C, and particularly preferably in the range of 23 to 38 ° C.

  The thickness of the write-once recording layer is preferably in the range of 1 to 100 nm on the land, and preferably in the range of 5 to 150 nm on the groove. The thickness on the land (the convex portion in the substrate) is preferably 70 nm or less, more preferably 50 nm or less, and still more preferably 30 nm or less. The lower limit is preferably 5 nm or more, and more preferably 15 nm or more.

Further, the thickness of the write-once recording layer is preferably 100 nm or less, more preferably 50 nm or less on the groove (the concave portion in the substrate). The lower limit is preferably 10 nm or more, and more preferably 20 nm or more.
Further, the ratio of the thickness of the write-once recording layer on the land and the thickness of the write-once recording layer on the groove [(thickness of recording layer on land) / (thickness of recording layer on groove)] is 0. Is preferably 0.13 or more, more preferably 0.13 or more, further preferably 0.15 or more, and particularly preferably 0.17 or more. The upper limit is preferably 1 or less, more preferably 0.9 or less, still more preferably 0.85 or less, and particularly preferably 0.8 or less.

  Further, the recording layer can contain various anti-fading agents in order to improve the light resistance of the recording layer. Examples of the antifading agent include organic oxidants and singlet oxygen quenchers. As the organic oxidizing agent used as an anti-fading agent, compounds described in JP-A-10-151861 are preferable. As the singlet oxygen quencher, those described in publications such as known patent specifications can be used. Specific examples thereof include JP-A Nos. 58-175893, 59-81194, 60-18387, 60-19586, 60-19586, 60-35054, 60-36190, 60-36191, 60-44554, 60-44555, 60-44389, 60-44390, 60-54892, 60-47069, 63-20995, JP Listed in publications such as Nos. 4-25492, 1-38680, and 6-26028, German Patent No. 350399, and the Chemical Society of Japan, October 1992, page 1141 Can do. Examples of preferable singlet oxygen quenchers include compounds represented by the following general formula (A).

In the general formula (A), R ²¹ represents an alkyl group which may have a substituent, and Q ⁻ represents an anion.

In the general formula (A), R ²¹ is an optionally substituted alkyl group having 1 to 8 carbon atoms, and an unsubstituted alkyl group having 1 to 6 carbon atoms is preferable. Examples of the substituent of the alkyl group include halogen atoms (eg, F, Cl), alkoxy groups (eg, methoxy group, ethoxy group), alkylthio groups (eg, methylthio group, ethylthio group), acyl groups (eg, acetyl group, Propionyl group), acyloxy group (eg, acetoxy group, propionyloxy group), hydroxy group, alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group), alkenyl group (eg, vinyl group), aryl group (eg, phenyl) Group, naphthyl group). Among these, a halogen atom, an alkoxy group, an alkylthio group, and an alkoxycarbonyl group are preferable. Preferable examples of the anion of Q ⁻ include ClO ₄ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , and SbF ₆ ⁻ .

  Examples of compounds represented by formula (A) (compound numbers AA-1 to AA-8) are shown in Table 18 below.

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

Barrier layer The barrier layer can be provided for improving the storage stability of the recording layer, improving the adhesion between the recording layer and the cover layer, adjusting the reflectance, adjusting the thermal conductivity, and the like.
The material used for the barrier layer is not particularly limited as long as it is a material that transmits light used for recording and reproduction and can express the above functions. For example, in general, It is preferable to use a material that does not cause corrosion due to contact with a reflective layer material such as a gas or moisture, a material that does not cause corrosion in a wet heat environment, and a dielectric material. preferable.
Specifically, a material made of nitride, oxide, carbide, sulfide such as Zn, Si, Ti, Te, Sn, Mo, Ge, Nb, Ta is preferable. MoO ₂ , GeO ₂ , TeO, SiO ₂ , TiO ₂ , ZnO, SnO ₂ , ZnO—Ga ₂ O ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ are preferable, SnO ₂ , ZnO—Ga ₂ O ₃ , SiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ Is more preferable.

The barrier layer can be formed by a vacuum film forming method such as vacuum deposition, DC sputtering, RF sputtering, or ion plating. Among these, it is more preferable to use sputtering.
The thickness of the barrier layer is preferably in the range of 1 to 200 nm, more preferably in the range of 2 to 100 nm, and still more preferably in the range of 3 to 50 nm.

Cover layer The cover layer is bonded onto the barrier layer via the aforementioned intermediate layer.
The cover layer is not particularly limited as long as it is a transparent film, but is not limited to acrylic resins such as polycarbonate and polymethyl methacrylate; vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers; epoxy resins; amorphous polyolefins Polyester; cellulose triacetate or the like is preferably used, and among them, polycarbonate or cellulose triacetate is more preferably used.
Note that “transparent” means that the transmittance is 80% or more with respect to light used for recording and reproduction. The optical information recording medium of the present invention can be formed by subjecting an ultraviolet curable composition applied on a barrier layer to a curing treatment by irradiating with ultraviolet rays through a cover layer. Therefore, it is preferable that the cover layer has ultraviolet transparency. Specifically, it is preferable to have a transmittance of 80% or more with respect to the ultraviolet rays irradiated for curing the ultraviolet curable composition.

Further, the cover layer may contain various additives as long as the effects of the present invention are not hindered. For example, a UV absorber for cutting light having a wavelength of 400 nm or less and / or a dye for cutting light having a wavelength of 500 nm or more may be contained.
Further, as the surface physical properties of the cover layer, it is preferable that the surface roughness is 5 nm or less for both the two-dimensional roughness parameter and the three-dimensional roughness parameter.
Further, from the viewpoint of the concentration of light used for recording and reproduction, the birefringence of the cover layer is preferably 10 nm or less.

The thickness of the cover layer, the wavelength and the NA of the the laser beam irradiation for recording and reproducing, the wavelength or the like of the ultraviolet rays irradiated for curing the ultraviolet-curable composition, as appropriate, may be defined However, in the present invention, it is preferably in the range of 0.01 to 0.5 mm, and more preferably in the range of 0.05 to 0.12 mm.
Further, the total thickness of the cover layer and the adhesive layer is preferably 0.09 to 0.11 mm, and more preferably 0.095 to 0.105 mm.
The light incident surface of the cover layer is provided with a protective layer (a hard coat layer 44 in the embodiment shown in FIG. 1 described later) for preventing the light incident surface from being damaged during the production of the optical information recording medium. May be.

  The cover layer may be formed by spin coating using a UV curable resin.

Other Layers The optical information recording medium of the present invention may have other arbitrary layers in addition to the essential layers as long as the effects of the present invention are not impaired. As other optional layers, for example, a label layer having a desired image formed on the back surface of the substrate (the non-formation surface side opposite to the side where the write-once recording layer is formed), a reflective layer and recording Examples thereof include an interface layer provided between the layers. Here, the label layer can be formed using an ultraviolet curable resin, a thermosetting resin, a heat drying resin, or the like.
The essential and optional layers described above may be a single layer or a multilayer structure.

  The optical information recording medium having the write-once recording layer having the preferred configuration can be easily manufactured because it can be formed by a method similar to the method for forming a recording layer in a conventional CD-R, DVD-R, or the like. According to the present invention, in the optical information recording medium having the above-described configuration, excellent short wavelength recording characteristics and mechanical strength (adhesive force between the cover layer and the barrier layer) can be obtained, and further productivity can be achieved.

  Information can be recorded on the recording layer by irradiating the optical information recording medium of the present invention with laser light. Information recording on the optical information recording medium is performed by changing the optical characteristics of the portion of the recording layer irradiated with the laser light. The change in optical properties is caused by the fact that the portion of the recording layer irradiated with the laser light absorbs the light and the temperature rises locally, causing a physical or chemical change (for example, generation of pits). Conceivable. Reading (reproduction) of information recorded on the recording layer is not changed from a portion (recording portion) where the optical characteristics of the recording layer are changed by irradiating laser light having the same wavelength as that of the recording laser light, for example. This can be done by detecting a difference in optical characteristics such as reflectance from a part (unrecorded part). As described above, in the present invention, information recording is preferably performed by thermally decomposing a dye compound contained in the recording by laser light irradiation and forming a void in the pit by the generated gas. . More preferably, the dye compound generates heat by absorbing laser light, and the heat generated thereby decomposes a substituent or dye skeleton in the dye compound to generate gas. As a result, voids are formed in the recording layer, and a large difference in refractive index can be generated between the portion where the voids are formed by laser light irradiation and the laser light non-irradiated portion, and the recording characteristics can be improved. Conceivable. The wavelength of the laser beam is preferably 390 to 440 nm. Details of information recording on the optical information recording medium of the present invention will be described later.

[Method of manufacturing optical information recording medium]
Furthermore, the present invention relates to a method for producing an optical information recording medium having a substrate pregroove on the surface, a reflective layer, a dye-containing recording layer, a barrier layer, and a cover layer in this order. In the method for producing an optical information recording medium of the present invention, an ultraviolet curable composition containing a conjugated diene polymer having at least two (meth) acryloyl groups in one molecule is applied on a barrier layer. Forming an intermediate layer having a glass transition temperature of −25 ° C. or lower between the barrier layer and the cover layer. The details are as described above. The optical information recording medium of the present invention can be obtained by the method for manufacturing an optical information recording medium of the present invention.

[Information recording method]
Furthermore, the present invention relates to an information recording method for recording information on a recording layer by irradiating the optical information recording medium of the present invention with laser light having a wavelength of 390 to 440 nm.

  The recording light is a laser light having a wavelength of 390 to 440 nm, and a semiconductor laser light having an oscillation wavelength in the range of 440 nm or less is preferably used. A blue-violet semiconductor laser beam having a wavelength and a blue-violet SHG laser beam having a center oscillation wavelength of 425 nm, which is a half wavelength of an infrared semiconductor laser beam having a center oscillation wavelength of 850 nm using an optical waveguide device, can be given. In particular, it is preferable to use a blue-violet semiconductor laser beam having an oscillation wavelength in the range of 390 to 415 nm in terms of recording density. The information recorded as described above is reproduced by irradiating the semiconductor laser light from the cover layer side while rotating the optical information recording medium at the same constant linear velocity as described above, and detecting the reflected light. Can do.

Specifically, information recording on the optical information recording medium shown in FIG. 1 is performed, for example, as follows.
First, while rotating the optical information recording medium at a constant linear velocity (for example, 0.5 to 10 m / second) or a constant angular velocity, a recording laser beam 46 such as a semiconductor laser beam is applied from the cover layer 16 side. Irradiation is performed through one objective lens 42 (for example, the numerical aperture NA is 0.85). By the irradiation of the laser beam 46, the write-once recording layer 14 absorbs the laser beam 46 and the temperature rises locally, causing a physical or chemical change (for example, generation of pits) to change its optical characteristics. Thus, it is considered that information is recorded.
The other details of the information recording method of the present invention are as described for the optical information recording medium of the present invention.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the embodiments shown in the examples.

<< Preparation of UV-curable composition >>
After UV curing composition used as an adhesive for forming an intermediate layer is added to a monofunctional monomer with a conjugated diene polymer or thickener having at least two (meth) acryloyl groups in one molecule, photopolymerization is performed. It was prepared by adding initiator and stirring in the dark to make it uniform. Hereinafter, the preparation method will be described by taking the ultraviolet curable compositions A and B as examples. Ultraviolet curable compositions C to L were similarly prepared.

Preparation example: UV curable composition A
As a conjugated diene polymer having at least two (meth) acryloyl groups in one molecule, Poly bd (R-45HT: number average molecular weight 2800, OH group value 46.6 mgKOH / g, OH content 0. 82 mol / kg) and acryloyl chloride dehydrochlorination reaction, 100 g of conjugated diene polymer A having at least two (meth) acryloyl groups in one molecule is used, and 2-ethylhexyl acrylate (140 g) is used as a monofunctional monomer. : Wako Pure Chemical Industries, Ltd., glass transition temperature of homopolymer −80 ° C.), and Irgacure 907 (Irgacure 907) manufactured by Ciba Specialty Chemicals as photopolymerization initiator: 2-methyl-4 ′-(methylthio) 2-morpholinopropiophenone (10 g) was stirred in the dark for 3 hours And left overnight to obtain an ultraviolet-curable composition A.

Preparation example: UV curable composition B
Maleinization obtained by ene addition reaction of Poly ip (OH content 0.80 mol / kg) made by Idemitsu Kosan Co., Ltd. and maleic anhydride as a conjugated diene polymer having at least two (meth) acryloyl groups in one molecule. Using 100 g of conjugated diene polymer B having at least two (meth) acryloyl groups in one molecule obtained by esterifying 2-hydroxyethyl acrylate with polyisoprene, 2-ethylhexyl acrylate (140 g) as a monofunctional monomer : Wako Pure Chemical Industries, Ltd., glass transition temperature of homopolymer −80 ° C.), and Irgacure 907 (Irgacure 907) manufactured by Ciba Specialty Chemicals as photopolymerization initiator: 2-methyl-4 ′-(methylthio) -2-morpholinopropiophenone (10 g) 3 hours stirring and left overnight to obtain an ultraviolet-curable composition A at.

Preparation example: UV curable compositions CL
As conjugated diene polymers having at least two (meth) acryloyl groups in one molecule, Kuraray UC-102, Kuraray UC-203, Osaka Organic Chemical Industries BAC-45, Nippon Soda Co., Ltd. TE -2000 was used in the amounts shown in Table 19, respectively, and the UV curable compositions C to C were used in the same manner as UV curable compositions A and B except that the monofunctional monomers and photopolymerization initiators shown in Table 19 were used. L was adjusted.

Viscosity measurement About the obtained ultraviolet curable composition, the viscosity in 25 degreeC was measured using the Toki Sangyo Co., Ltd. R500 type | mold viscosity meter. The results are shown in Table 19.

２ＥＨＡ：２−エチルヘキシルアクリレート（ホモポリマーのガラス転移温度−８０℃）
ＤｏＡ：ドデシルアクリレート（ホモポリマーのガラス転移温度−３℃）
Ｅｂｅｃｒｙｌ１１０：ＥＯ変性フェノールアクリレート（ダイセル・サイテック社製、ホモポリマーのガラス転移温度−２５℃）
イルガキュア１８４：１−ヒドロキシシクロヘキシルフェニルケトン（チバ・スペシャリティ・ケミカルズ社製）
イルガキュア６５１：２,２−ジメトキシー１，２−ジフェニルエタンー１−オン（チバ・スペシャリティ・ケミカルズ社製）
ダロキュア１１７３：２−ヒドロキシー２−メチルー１−フェニルプロパンー１−オン（チバ・スペシャリティ・ケミカルズ社製）

2EHA: 2-ethylhexyl acrylate (glass transition temperature of homopolymer −80 ° C.)
DoA: dodecyl acrylate (glass transition temperature of homopolymer −3 ° C.)
Ebecryl 110: EO-modified phenol acrylate (manufactured by Daicel-Cytec, glass transition temperature of homopolymer −25 ° C.)
Irgacure 184: 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals)
Irgacure 651: 2,2-dimethoxy-1,2-diphenylethane-1-one (Ciba Specialty Chemicals)
Darocur 1173: 2-hydroxy-2-methyl-1-phenylpropan-1-one (Ciba Specialty Chemicals)

Comparative preparation example: UV curable composition M
As a monofunctional monomer, 2-ethylhexyl acrylate (8.4 g, manufactured by Wako Pure Chemical Industries, Ltd.) and as a polyfunctional monomer, Ebecryl-81 (6.0 g, manufactured by Daicel Cytec, 2.5 functional amine-modified polyether acrylate) Irgacure 907: 2-methyl-4 ′-(methylthio) -2-morpholinopropiophenone (0.6 g, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator was stirred for 3 hours in the dark and left overnight. Thus, an ultraviolet curable composition M was obtained. When the viscosity was measured by the same method as described above, it was 5.5 mPa · s.

Comparative preparation example: UV curable composition N
1 drop of isophorone diisocyanate 2 mol dibutyltin laurate was added and stirred at 70 ° C., then 1 mol of polypropylene glycol 400 (mass average molecular weight 683, number average molecular weight 567) was added and stirred and reacted for 3 hours. -2 mol of hydroxyethyl acrylate was added dropwise and stirred for 3 hours to obtain polyfunctional urethane acrylate N. 2-ethylhexyl acrylate (8.4 g: manufactured by Wako Pure Chemical Industries, Ltd.) as a monofunctional monomer, polyfunctional urethane acrylate N 6.0 g as a polyfunctional monomer, and Irgacure 907: 2-methyl-4 ′ as a photopolymerization initiator -(Methylthio) -2-morpholinopropiophenone (0.6 g: manufactured by Ciba Specialty Chemicals) was stirred in the dark for 3 hours and allowed to stand overnight to obtain an ultraviolet curable composition M. It was 45 mPa * s when the viscosity was measured by the method similar to the above.

Comparative preparation example: UV curable composition O
Cross-linking agent obtained by reacting with acrylic acid chloride after adding 40 mol of ethylene oxide to 1 mol of glycerin as a polyfunctional monomer to 2-ethylhexyl acrylate (21 g: Wako Pure Chemical Industries, Ltd.) as a monofunctional monomer (0.5 g, NK Esther ASO 40EO manufactured by Shin-Nakamura Chemical Co., Ltd.), polybutyl acrylate (7 g: Aldrich, Mw = 101000, Mn = 38000) as a thickener, 1-hydroxy as a photopolymerization initiator Cyclohexyl phenyl ketone (0.5 g: Wako Pure Chemical Industries, Ltd.) was stirred in the dark for 3 hours and allowed to stand overnight to obtain an ultraviolet curable composition O. When the viscosity was measured by the same method as described above, it was 56 mPa · s.

[Synthesis of Exemplified Dye Compound (M-50)]

(1) Synthesis of Compound (Q-5) 1 g of Compound (1) is placed in a 100 ml Erlenmeyer flask, 1.3 ml of acetic acid and 2 ml of propionic acid are poured, and 1.9 ml of hydrochloric acid (35 to 37%) is slowly added under ice cooling. It was dripped. After cooling to 0-5 ° C. in an ice bath and slowly dropping 1 ml of an aqueous solution in which 0.46 g of NaNO ₂ was dissolved (cooled to 5 ° C. or lower), the mixture was stirred at 0-5 ° C. for 1 hour. did. This acidic solution was gradually added to 20 ml of a methanol solution containing 0.94 g of compound (2) kept at 0 to 5 ° C. under ice cooling, and stirred for 1 hour. After returning to room temperature and stirring for 2 hours, the precipitate was filtered and washed with a minimum amount of methanol. The obtained solid was dried to obtain 0.8 g of compound (Q-5). The compound was identified by 300 MHz ¹ H-NMR.
¹ H-NMR (DMSO-d6) [ppm]; δ13.70 (1H, br), 13.31 (1H, s), 3.331 (3H, s), 1.413 (9H, s), 1.331 (9H, s)

(2) Synthesis of Illustrative Dye Compound (M-50) Next, 0.7 g of the compound (Q-5) synthesized in (1) above and 10 ml of methanol were placed in a 50 ml eggplant flask, and 1.5 ml of triethylamine was stirred. Was dripped. The mixture was stirred for 10 minutes, 0.43 g of Cu (OAc) ₂ .H ₂ O was further added, and the mixture was heated to reflux for 1 hour. The temperature was returned to room temperature, the precipitate was filtered, washed with methanol, and dried to obtain 0.44 g of compound (M-50).

[Synthesis of Illustrative Dye Compound (I-49)]
Exemplified dye compound (I-49) was synthesized according to Synthesis Example 1 described in JP-A-2004-188727.

<Evaluation of physical properties of pigment>
<Measurement analysis of refractive index n and extinction coefficient k>
A pigment-containing coating solution similar to that of Example 1 described later was prepared, and the prepared pigment-containing coating solution was changed on a glass plate having a thickness of 1.1 mm to 23 ° C. while changing the rotational speed from 500 to 1000 rpm by a spin coating method. And 50% RH. About this pigment | dye film | membrane, the refractive index n and the extinction coefficient k were measured and analyzed using the spectroscopic ellipsometry apparatus (JA Woollam Japan company make, model M-2000). The refractive index n of the exemplified dye compound (M-50) at 405 nm was 1.56, and the extinction coefficient k was 0.23. Similarly, the refractive index n of the exemplified dye compound (I-49) was 1.81, and the extinction coefficient k was 0.052.

<Measurement of thermal decomposition temperature>
TG / DTA measurement was performed for the exemplified dye compound (M-50). Measurements were taken from Seiko Instruments Inc. Using EXSTAR6000 manufactured, the temperature was raised at 10 ° C./min in the range of 30 ° C. to 550 ° C. under N ₂ air flow (flow rate 200 ml / min). The temperature at which the mass reduction rate reached 10% was read and found to be 321 ° C. Similarly, when the temperature at which the mass reduction rate of the exemplified dye compound (I-49) reached 10% was read, it was 353 ° C.

<< Production of optical information recording medium >>
(Production of substrate)
Thickness 1.1 mm, outer diameter 120 mm, inner diameter 15 mm, spiral pre-groove (track pitch: 320 nm, groove width: groove (recess) width 190 nm, groove depth: 47 nm, groove inclination angle: 65 °, wobble amplitude: An injection molded substrate made of polycarbonate resin having a thickness of 20 nm) was produced. Mastering of the stamper used at the time of injection molding was performed using laser cutting (351 nm).

(Formation of light reflection layer)
An ANC light reflecting layer (Ag: 98.1 at%, Nd: 0.7 at%, as a vacuum film-forming layer having a film thickness of 60 nm was formed on the substrate by DC sputtering in an Ar atmosphere using Cube manufactured by Unaxis. Cu: 0.9 at%) was formed. The film thickness of the light reflecting layer was adjusted by the sputtering time.

(Formation of write-once recording layer)
1.2 g of the synthesized exemplary compound (M-50) was added and dissolved in 100 ml of 2,2,3,3-tetrafluoropropanol to prepare a dye-containing coating solution. And the prepared pigment | dye containing coating liquid was apply | coated on the conditions of 23 degreeC and 50% RH, changing the rotation speed to 300-4000 rpm with a spin coat method on the light reflection layer. Then, it was stored at 23 ° C. and 50% RH for 1 hour to form a write-once recording layer. The thickness of the write-once recording layer was 40 nm on the groove and 15 nm on the land.

  After the write-once recording layer was formed, annealing treatment was performed in a clean oven. The annealing treatment was performed by supporting the substrate on a vertical stack pole while leaving a gap with a spacer, and holding at 80 ° C. for 1 hour.

(Formation of barrier layer)
Thereafter, a barrier layer having a thickness of 5 nm made of Nb ₂ O ₅ was formed by DC sputtering in an Ar atmosphere on the write-once recording layer using Cube manufactured by Unaxis.

The medium on which the barrier layer was formed was placed on a spin coater, and the ultraviolet curable composition A was applied in a ring shape around the inner periphery of 30 mm. After a polycarbonate film having an inner diameter of 15 mm and an outer diameter of 120 mm (Teijin Pure Ace, thickness: 90 μm) was placed thereon, 2000 to 8000 r. p. m. It was rotated at the number of rotations. As a result, the adhesive was extended to the outer periphery by centrifugal force, and an adhesive layer having a uniform thickness could be obtained. This sample was moved to a UV light irradiation table, irradiated with UV light, and the UV adhesive was cured. At this time, the UV lamp used for curing was a 4.2 inch-SPIRAL LAMP manufactured by Xenon Corporation, and was cured by irradiating a flash with an irradiation time of 0.5 seconds each time. The distance between the lamp surface and the sample surface was about 35 mm. The amount of ultraviolet irradiation was 2000 mJ / cm ² . The thickness of the formed adhesive layer was 10 μm.
Thereby, the optical information recording medium of Example 1 was produced.

[Examples 2 to 9, Comparative Examples 1 to 3]
Example except that the ultraviolet curable composition shown in Table 21 was used instead of the ultraviolet curable composition A, and the ultraviolet irradiation amount was changed by changing the ultraviolet irradiation time for the curing treatment of the composition. 1 were used to produce optical information recording media (Examples 2 to 8, Comparative Examples 1 to 3). Similarly, an optical information recording medium was produced in the same manner as in Example 1 except that the exemplified dye compound (I-49) was used (Example 9).

Ultraviolet irradiation amount The irradiation amount of ultraviolet rays irradiated for curing the adhesive layer was measured as follows.
An EC-100FL model manufactured by Ushio Electric Co., Ltd. was used as the irradiance measuring instrument, and the measurement was performed in the integrated light quantity measurement mode. A polycarbonate film (Teijin Pure Ace, thickness: 90 μm) is placed on the light-receiving part of this measuring machine and set on the UV light irradiation part. Irradiation was performed 10 times, and the integrated light quantity was measured each time. When the relationship between the irradiation time and the integrated light amount was plotted, the relationship between the irradiation time and the integrated light amount showed a good linear relationship. Therefore, the slope of the approximate straight line passing through the origin is defined as the irradiation amount per unit time, and the product of the irradiation amount per unit time and the irradiation time is defined as the irradiation amount. The results are shown in Table 20 below. Since the light receiving part of the measuring machine is at a radius of 40 mm, the values shown in Table 20 are obtained by using the measurement result at a radius of 40 mm as a representative value. Depending on the lamp, the in-plane strength may vary. .
Although this measuring machine measures relative values and has no units, Table 21 shows the numerical values obtained by substituting mJ / cm ² for energy. This is because the integrated amount of light when irradiated for 3 seconds without placing a polycarbonate film substantially coincides with the manufacturer data (measured as energy having a unit of mJ / cm ² ).

<Measurement of glass transition temperature of adhesive layer>
(1) Preparation of glass transition temperature sample After each UV curable composition was applied on a glass substrate, a metal halide lamp M02-L31 (made by Eye Graphics, with cold mirror, lamp output 120 W / cm) was used. The sample for measurement was prepared by irradiating and curing ultraviolet rays at a dose shown in Table 21 in a nitrogen atmosphere.
(2) Measurement of glass transition temperature (DSC) The glass transition temperature of the obtained cured coating film was measured by SC / DSC. Table 21 shows the measurement results. The measurement method will be described below.
DSC apparatus: Seiko Instruments Inc. The sample was sealed in a closed cell made of SUS using DSC6200R manufactured, and the temperature was raised at a rate of 10 ° C./min in the range of −100 ° C. to 100 ° C. to determine the first glass transition temperature. Further, after the temperature was lowered from 100 ° C. to −100 ° C. at 50 ° C./min, the temperature was raised at 10 ° C./min in the range from −100 ° C. to 100 ° C. to determine the second glass transition temperature. This point was defined as the glass transition temperature (DSC).
In addition, for the glass transition temperature measurement, the cured coating film in the measurement sample was formed thicker than the adhesive layers in the optical information recording media of Examples and Comparative Examples. However, since the glass transition temperature is not affected by the film thickness, the results shown in Table 21 below can be regarded as the evaluation results of the corresponding examples and comparative examples, respectively.

<Measurement of glass transition temperature and storage modulus of adhesive layer>
(1) Preparation of samples for measurement of dynamic viscoelastic behavior After each of the UV curable compositions A to E was applied on a glass substrate, a metal halide lamp M02-L31 (produced by Eye Graphics, with cold mirror, lamp output) 120 W / cm) was irradiated with ultraviolet rays at a dose shown in Table 20 in a nitrogen atmosphere and cured to prepare measurement samples (samples A to E).
The obtained cured coating film was measured for dynamic viscoelastic behavior at a frequency of 1 Hz using a dynamic viscoelasticity measuring device: DVA-200 (ITG Measurement Control Co., Ltd.) (temperature rising speed 5 ° C./min). . The measurement mode was the shear mode, and the storage elastic modulus and loss tangent (tan δ) at 30 ° C. were determined. Table 20 shows the measurement results.

<Measurement of peel strength>
(1) Preparation of peel strength measurement sample On one side, the same substrate as that used for the preparation of the optical recording medium was placed on the spin coater with the grooved side facing upward, and the inner periphery was around 30 mm. The ultraviolet curable composition A was applied in a ring shape. After a polycarbonate film having an inner diameter of 15 mm and an outer diameter of 120 mm (Teijin Pure Ace, thickness: 90 μm) was placed thereon, 2000 to 8000 r. p. m. It was rotated at the number of rotations. As a result, the ultraviolet curable composition was extended to the outer periphery by centrifugal force, and an adhesive layer having a uniform thickness could be obtained. This sample was moved to a UV light irradiation table, irradiated with UV light, and the UV adhesive was cured. At this time, the UV lamp used for curing was M03-041 manufactured by Eye Graphics, and irradiated for 2.1 seconds. The amount of ultraviolet irradiation was 1077 mJ / cm ² . The thickness of the formed adhesive layer was 5 μm.
(2) Measurement of peel strength As shown in FIG. 3, the sample polycarbonate film was cut with a width of 14 mm from the inner periphery to the outer periphery using a cutter knife. The depth of the cut was 100 μm or more so that the sheet was completely separated on the left and right of the cut. The belt was folded back approximately 180 ° at 10 mm from the outer peripheral edge of the band-shaped portion sandwiched between the cuts.
FIG. 4 shows an outline of the measuring apparatus. Using the adhesive sheet, the sample was fixed horizontally on the stage so that the cut and folded part was on the side far from the movable part. As shown in FIG. 5, the cellophane tape was inserted between the sheet folded portion and the sample with the adhesive surface facing upward so as to sufficiently adhere to the folded portion. The other end of the cellophane tape was wound around a hook connected to a load cell (UT-1K manufactured by Minebea Co., Ltd.). In this state, operate the motor and rotate the threaded rotary shaft to move the end of the rotary shaft in contact with the movable part in the direction of the arrow, and move the movable part and the load cell attached to it in the direction opposite to the sample. The plate was moved horizontally at a speed of 14 mm / sec. The movement was carried out until the strip-like portion having a width of 14 mm that had been cut was completely peeled off from the polycarbonate substrate, and the maximum value of the load measured by the load cell during that time was taken as the peel strength of the sample.

<Measurement of transmittance>
A sample was prepared with the same configuration and method as the peel strength measurement sample, and the transmittance (incident light intensity was 1) with a spectrophotometer ETA-RT (manufactured by STEAG ETA-Optik GmbH) at a radius of 40 mm and an incident light wavelength of 405 nm. The specific intensity of the transmitted light was measured.

<Evaluation of recording characteristics>
The produced optical information recording medium was 0.16 μm at a clock frequency of 66 MHz and a linear velocity of 4.92 m / s using a recording / reproduction evaluation machine (manufactured by Pulstec Inc .: DDU1000) loaded with a 403 nm laser and NA 0.85 pickup. The signal (2T) was recorded and reproduced, and the output was measured with a spectrum analyzer (FSP-3 manufactured by Rohde & Schwartz). The peak output seen at around 16 MHz after recording was defined as Carrier output, the output at the same frequency before recording was defined as Noise output, and the output after recording−the output before recording was defined as the C / N value. Recording was done on the groove. The recording power was in the range of 1 to 8 mW, and the reproducing power was 0.3 mW. In Table 21, when the C / N value at a recording power of 6 mW is larger than 35 dB, the level that can be practically used is “◯”, and when the recording power is less than 35 dB, it is “x”.
The above results are shown in Table 21 and Table 22.

As shown in Table 21, Examples 1 to 8 have a glass transition temperature of −25 ° C. or less from an ultraviolet curable composition containing a conjugated diene polymer having at least two (meth) acryloyl groups in one molecule. An intermediate layer could be formed. When peel strength and transmittance were measured for Examples 1 to 4, both were good. Moreover, all the ultraviolet curable compositions used in Examples 1 to 8 had good coating suitability.
On the other hand, in Comparative Examples 2 and 3, the glass transition temperature of the intermediate layer was −25 ° C. or lower, but the peel strength was lower than in Examples 1 to 4. By using an ultraviolet curable composition containing a conjugated diene polymer having at least two (meth) acryloyl groups in one molecule, the glass transition temperature can be greatly reduced without greatly reducing the peel strength. It seems that it became possible. Comparative example 1 will be described later.

As shown in Table 22, the optical information recording media of Examples 1 to 4 and 9 exhibited good recording characteristics.
On the other hand, the optical information recording medium of Comparative Example 1 obtained good recording characteristics as shown in Table 22 although the peel strength and transmittance were the same as those in Examples 1 to 4 as shown in Table 21. I couldn't. This is considered due to the fact that the glass transition temperature of the intermediate layer was more than −25 ° C.

  The optical information recording medium of the present invention is suitable as a Blu-ray optical information recording medium for recording information by irradiating a short wavelength laser beam.

It is a schematic sectional drawing which shows an example of the optical information recording medium of this invention. It is explanatory drawing of the measuring method of the mass reduction | decrease rate in the main weight loss process in a thermal mass spectrometry. It is the schematic of a peeling strength measurement sample. It is the schematic of a peeling strength measuring apparatus. It is the schematic of a peeling strength measurement sample.

Explanation of symbols

10A ... first optical information recording medium 12 ... substrate 14 ... recording layer 16 ... cover layer 18 ... light reflecting layer 20 ... barrier layer 22 ... intermediate layer 42 ... first objective lens 44 ... hard coat layer 46 ... laser light

Claims (19)

An optical information recording medium having a reflective layer, a dye-containing recording layer, a barrier layer, and a cover layer in this order on a surface having a pregroove of a substrate,
-25 formed between the barrier layer and the cover layer by subjecting an ultraviolet curable composition containing a conjugated diene polymer having at least two (meth) acryloyl groups in one molecule to a curing treatment. An optical information recording medium comprising an intermediate layer having a glass transition temperature of 0 ° C. or lower. The optical information recording medium according to claim 1, wherein the ultraviolet curable composition contains 10 to 80 parts by mass of the conjugated diene polymer with respect to 100 parts by mass of the ultraviolet curable composition. The conjugated diene polymer contains polybutadiene having at least two (meth) acryloyl groups in one molecule and / or polyisoprene having at least two (meth) acryloyl groups in one molecule. An optical information recording medium described in 1. The optical information recording medium according to any one of claims 1 to 3, wherein the ultraviolet curable composition contains a monofunctional or polyfunctional (meth) acrylate having a homopolymer glass transition temperature of -90 to 25 ° C. . The optical information recording medium according to claim 1, wherein the dye is a phthalocyanine dye compound. 5. The dye according to claim 1, wherein the dye is at least one azo dye compound selected from the group consisting of an azo compound and an azo compound and an azo metal complex compound containing a metal ion or a metal oxide ion. Optical information recording medium. The optical information recording medium according to claim 6, wherein the azo metal complex compound contains a copper ion. The optical information recording medium according to claim 6 or 7, wherein the dye has an extinction coefficient in a range of 0.15 to 1.0 at a wavelength of 405 nm. The optical information recording medium according to any one of claims 6 to 8, wherein the dye has a refractive index in a range of 1.45 to 1.75 at a wavelength of 405 nm. The optical information recording medium according to any one of claims 5 to 9, wherein a thermal decomposition temperature of the dye is in a range of 150 to 400 ° C. The pre-groove is composed of a plurality of grooves and lands located between adjacent grooves, and the track pitch is in a range of 50 to 500 nm,
The optical information recording medium according to claim 1, wherein the recording layer has a thickness in a range of 1 to 100 nm on a land and a range of 5 to 150 nm on a groove. The pre-groove is composed of a plurality of grooves and lands located between adjacent grooves, and the ratio of the thickness of the recording layer on the land to the thickness of the recording layer on the groove [(thickness of the recording layer on the land) ) / (Thickness of the recording layer on the groove)] is in the range of 0.1 to 1, the optical information recording medium according to any one of claims 1 to 11. The optical information recording medium according to any one of claims 1 to 12, which is used for recording information by irradiating a laser beam having a wavelength of 390 to 440 nm. An information recording method for recording information on a recording layer of an optical information recording medium by irradiating the optical information recording medium according to any one of claims 1 to 13 with laser light having a wavelength of 390 to 440 nm. A method for producing an optical information recording medium having a reflective layer, a dye-containing recording layer, a barrier layer, and a cover layer in this order on a surface having a pregroove of a substrate,
By applying an ultraviolet curable composition containing a conjugated diene polymer having at least two (meth) acryloyl groups in one molecule on the barrier layer, and irradiating the composition with ultraviolet rays, An intermediate layer having a glass transition temperature of −25 ° C. or lower is formed between the layer and the cover layer. The method for producing an optical information recording medium according to claim 15, wherein the ultraviolet curable composition applied on the barrier layer has a viscosity in the range of 20 to 1000 mPa · s. The said ultraviolet curable composition is a manufacturing method of the optical information recording medium of Claim 15 or 16 containing 10-80 mass parts of said conjugated diene polymers with respect to 100 mass parts of ultraviolet curable compositions. The conjugated diene polymer contains polybutadiene having at least two (meth) acryloyl groups in one molecule and / or polyisoprene having at least two (meth) acryloyl groups in one molecule. The method for producing an optical information recording medium according to any one of the above. The optical information recording medium according to any one of claims 15 to 18, wherein the ultraviolet curable composition comprises a monofunctional or polyfunctional (meth) acrylate having a homopolymer glass transition temperature of -90 to 25 ° C. Manufacturing method.

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