JP2005271587A - Optical recording material and optical recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical recording material which is capable of recording and reconstruction by a blue laser with a short wavelength and has a high level. <P>SOLUTION: The optical recording material comprises an organic coloring matter compound A with the maximum absorption wavelength (λmax) of 340-440 nm and a metal complex compound B with the maximum absorption wavelength (λmax) of 500-900 nm, has the content of the organic coloring matter compound A being larger than the content of the metal complex compound B, and has a light resistance x measured by a specified test method of 30% or more. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an optical recording material and the like, and more particularly to an optical recording material and the like for blue laser.

Currently, various optical recording media such as CD-R / RW, DVD-R / RW, and MO can store a large amount of information and are easily accessible at random. Therefore, external storage in an information processing apparatus such as a computer is possible. Widely recognized and popular as a device. Among these, organic dye-based optical recording media represented by CD-R and DVD-R are considered to have an advantage in that they are low in cost and easy to manufacture.
Further, it is desired to increase the recording density of the medium by increasing the amount of information handled. In recent years, an optical recording medium capable of high-density recording / reproduction using a laser beam having a short oscillation wavelength (hereinafter referred to as a short wavelength) such as a blue laser which has been remarkably developed has been proposed.

  However, in general, in the case of an optical recording medium that is commercially available as a CD-R or DVD-R, for example, the CD-R is suitable for recording / reproduction with a laser beam having a wavelength of about 780 nm, and the DVD-R has a wavelength. It is designed to be suitable for recording / reproduction with a laser beam of about 600 nm to 700 nm. In such an optical recording medium suitable for optical recording / reproduction using a laser beam having a relatively long wavelength, recording / reproduction with a shorter wavelength laser has a low reflectance and cannot be recorded / reproduced. Have a problem.

  Therefore, the organic dye compound used in the recording layer of the optical recording medium suitable for recording / reproducing with such a short wavelength laser beam also has an absorption characteristic at a wavelength shorter than the wavelength of the conventionally used laser beam. Dyes have been studied, and an optical recording medium using such a dye as a recording layer has been reported (see Patent Document 1). There are also reports on optical recording media in which a carbostyril compound having a specific molecular structure is contained in a recording layer (see Patent Document 2 and Patent Document 3).

JP 2001-096918 A JP 2001-287466 A JP 2003-127542 A

  By the way, in addition to the reflectance described above, the performance required for the recording dye used in the optical recording medium using a blue laser is not only the recording characteristics when made into a disk, but also the recording sensitivity and the coating during coating on the substrate. Various performances such as film properties, storage stability, and light resistance are required. However, recording dyes for blue lasers that satisfy these characteristics simultaneously have not been realized yet.

  In order to improve the recording characteristics of such a recording layer, a method of mixing an additive having a property of supplementing characteristics with a dye at an arbitrary ratio in CD-R, DVD-R, or the like has been studied.

  However, the optimum additives and addition amounts for improving the recording characteristics without losing the recording sensitivity of the organic dye compound used in the recording layer of the optical recording medium suitable for recording / reproducing with a short wavelength laser beam have not yet been found. An organic dye-based optical recording medium satisfying a high level of coating properties, storage stability, light resistance and the like at the time of application on a substrate has not been realized.

  The present invention has been made to solve the problems in developing an optical recording material used for such an optical recording medium using a blue laser. In particular, the present invention alone is intended to achieve a light resistance of 30% or more, even for many blue laser recording dyes having a light resistance of less than 30%.

That is, an object of the present invention is to provide a high-level optical recording material that can be recorded and reproduced by a short wavelength blue laser.
Another object of the present invention is to provide an optical recording medium capable of recording / reproducing with a short wavelength blue laser.

As a result of intensive studies, the present inventors have a high level of light resistance and the like by combining a compound having a high sensitivity to a blue laser and having an absorption maximum at a wavelength of 340 nm to 440 nm with a specific metal complex. The present inventors have found that an optical recording material satisfying the requirements can be obtained, and have completed the present invention based on this finding.
That is, according to the present invention, the organic dye compound A having a maximum absorption wavelength (λmax) of 340 nm to 440 nm and the metal complex compound B having a maximum absorption wavelength (λmax) of 500 nm to 900 nm are contained, There is provided an optical recording material characterized in that the content of the organic dye compound A is larger than the content of the metal complex compound B, and the light resistance x calculated by the following formula is 30% or more.
Light resistance x = {(I ₁ / I ₀ ) × 100}
(In the above formula, I ₀ is the absorbance at the absorption maximum existing in the wavelength range of 340 nm to 440 nm in the absorption spectrum of the film measured by the spectrophotometer of the organic dye compound A and the metal complex compound B mixture). I ₁ is the absorbance of the absorption maximum present in the wavelength range of 340 nm to 440 nm in the absorption spectrum of the film measured by a spectrophotometer after the film of the organic dye compound A and the metal complex compound B mixture is irradiated with light. .)

In the optical recording material to which the present invention is applied, the above-mentioned organic dye compound A includes an absorption maximum absorbance (I _A0 ) existing in the wavelength range of 340 nm to 440 nm of the absorption spectrum of the film measured by a spectrophotometer, and organic Light absorption x = {calculated using the absorption maximum absorbance (I _A1 ) existing in the wavelength range of 340 nm to 440 nm of the absorption spectrum of the film measured after the film of the dye compound A was subjected to light irradiation treatment The effect of the present invention is further exhibited when (I _A1 / I _A0 ) × 100} is less than 30%.

Here, the light resistance x is preferably calculated by the following operation steps.
(Operation steps)
(Step 1) A solution containing the organic dye compound A and the metal complex compound B is spin-coated on a transparent substrate and then dried to prepare a dye-coated disk.
(Step 2) Using a spectrophotometer, the absorption spectrum of the dye-coated disk prepared in (Step 1) is measured at a wavelength of 300 nm to 900 nm, and the absorbance of the absorption maximum existing in the wavelength range of 340 nm to 440 nm is expressed as I ₀ . To do.
(Step 3) The dye-coated disk prepared in (Step 1) was subjected to a light irradiation treatment in which a xenon lamp was irradiated at 250 W / m ² for 8 hours, and then the absorption spectrum was measured under the same conditions as in (Step 2). the absorbance of the absorption maximum present in the wavelength range 340nm~440nm and _{I 1.}
(Step 4) Based on (I ₀ ) in (Step 2) and (I ₁ ) in (Step 3), {(I ₁ / I ₀ ) × 100} is calculated.
In addition, the “solution” in Step 1 means a liquid containing a solid content of the organic dye compound A and the metal complex compound B having an absorption maximum absorbance of 0.1 to 1.0.

  In the optical recording material to which the present invention is applied, the organic dye compound A having a maximum absorption wavelength (λmax) of 340 nm or more and 440 nm or less contains the metal complex compound B, whereby the light resistance of the organic dye compound A is weak. It is possible to compensate for this. The reason for this is that the light resistance may be improved by coordination of the metal as compared with the case where the metal is not coordinated, and the light resistance of the metal complex compound B is strong in the first place.

  In particular, in the short wavelength region of the present invention, the metal complex compound B has a weak absorption band in the vicinity of the maximum absorption maximum wavelength (λmax) of the organic dye compound A. It is considered to shield or mask the photodegradation of the absorption band of the organic dye compound A. Such a “weak absorption band” is considered to be an absorption having a small interaction with a ligand derived from a metal ion or a weak absorption band of a ligand. More preferably, the absorption band is optically or thermally stable.

  In addition, since the metal complex compound B has a bulky steric structure as compared with the organic dye compound A, for example, an amorphous structure in which the organic dye compound A alone is easily crystallized is appropriately dispersed by the metal complex compound B. It is considered that the coating properties can be improved.

The metal complex compound B is preferably an azo metal complex compound or an indoaniline metal complex compound from the viewpoint of light resistance or coating properties.
In the optical recording material to which the present invention is applied, the azo metal complex compound is a metal complex compound of an azo compound represented by the following general formula (I) and a metal ion. It is possible to improve recording properties such as coating properties at the time of coating, storage stability, light resistance, and recording sensitivity.

(In Formula (I), Ring A is a nitrogen-containing heteroaromatic ring formed together with a carbon atom and a nitrogen atom, and XL is capable of coordinating a metal with X becoming an anion when L is eliminated. R ₁ and R ₂ each independently represents a hydrogen atom, a linear or branched alkyl group, a cyclic alkyl group, an aralkyl group or an alkenyl group, which are each condensed with adjacent substituents or with each other. R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, carbon A linear or branched alkenyl group having 2 to 12 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 12 carbon atoms, a linear or branched alkylthio group having 1 to 12 carbon atoms, A monocyclic saturated heterocyclic group, Androgenic atom, a nitro group, a cyano group, a mercapto group, hydroxy group, formyl group, acyl group represented by -COR _34, amino group represented by _-NR 35 _{R 36,} an acylamino group represented by -NHCOR _37, A carbamate group represented by —NHCOOR _38; a carboxylic acid ester group represented by —COOR _39; an acyloxy group represented by —OCOR _40; a carbamoyl group represented by —CONR ₄₁ R ₄₂ ; and —SO ₂ R ₄₃ . the sulfonyl group represented, sulfinyl group represented by -SOR _44, a sulfamoyl group represented by -SO _{2 NR} 45 _{R 46,} sulfonic acid ester group represented by -SO _{3 R 47,} at -NHSO ₂ R ₄₈ Represents a sulfonamide group represented (provided that R ₃₄ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₃ , R _{4). 4} , R ₄₇ and R ₄₈ each independently represent a hydrocarbon group or a heterocyclic group, and R ₃₅ , R ₃₆ , R ₄₁ , R ₄₂ , R ₄₅ and R ₄₆ each independently represent a hydrogen atom, It represents either a hydrocarbon group or a heterocyclic group.))

In the azo compound represented by the general formula (I), ring A represents a 5- or 6-membered monocyclic or bicondensed nitrogen-containing heteroaromatic ring, XL represents a hydroxy group, a sulfonic acid group, an acylamino group, Represents a sulfonamide group, a mercapto group, or a carboxyl group, and R ₁ and R ₂ each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or 7 carbon atoms. -12 represents an aralkyl group, or each forms a saturated condensed ring with adjacent substituents or each other, R ₃ , R ₄ , and R ₅ are each independently a hydrogen atom or a linear or branched group having 1 to 8 carbon atoms Alkyl group, C 7-12 aralkyl group, C 1-8 linear or branched alkoxy group, C 1-8 linear or branched alkylthio group, monocyclic 5-6 membered saturated Heterocyclic group, halogen atom, di B group, a cyano group, a mercapto group, hydroxy group, acyl group represented by -COR _34, amino group represented by _-NR 35 _{R 36,} an acylamino group represented by -NHCOR _37, represented by -NHCOOR ₃₈ A carbamate group, a carboxylate group represented by -COOR ₃₉ , an acyloxy group represented by -OCOR ₄₀ , a carbamoyl group represented by -CONR ₄₁ R ₄₂ , a sulfonyl group represented by -SO ₂ R ₄₃ , It preferably represents a sulfamoyl group represented by —SO ₂ NR ₄₅ R ₄₆ and a sulfonamide group represented by —NHSO ₂ R ₄₈ .

  In the optical recording material to which the present invention is applied, the indoaniline-based metal complex compound is preferably a metal complex compound comprising a compound represented by the following general formula (II), a metal ion, and an arbitrary anion. .

(In the formula (II), R ₆ and R ₇ each independently represents a hydrogen atom, a linear or branched alkyl group, a cyclic alkyl group, an aralkyl group, or an alkenyl group, each of these being adjacent substituents or R _{8 to} R ₁₆ may each independently form a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or a carbon number. 2-12 linear or branched alkenyl group, C7-18 aralkyl group, C1-12 linear or branched alkoxy group, C1-12 linear or branched alkylthio group, saturation Or an unsaturated heterocyclic group, an aryl group having 6 to 18 carbon atoms, a halogen atom, a nitro group, a cyano group, a mercapto group, a hydroxy group, a formyl group, an acyl group represented by —COR ₃₄ , —NR ₃₅ R ₃ An amino group represented by _6; an acylamino group represented by —NHCOR _37; a carbamate group represented by —NHCOOR _38; a carboxylic acid ester group represented by —COOR _39; an acyloxy group represented by —OCOR ₄₀ ; A carbamoyl group represented by —CONR ₄₁ R _42; a sulfonyl group represented by —SO ₂ R _43; a sulfinyl group represented by —SOR _44; a sulfamoyl group represented by —SO ₂ NR ₄₅ R ₄₆ ; ₃ represents a sulfonic acid ester group represented by R ₄₇ and a sulfonamide group represented by —NHSO ₂ R ₄₈ (provided that R ₃₄ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₃ , R ₄₄ , R ₄₇ and R ₄₈ each independently represent a hydrocarbon group or a heterocyclic group, and R ₃₅ , R ₃₆ , R ₄₁ , R ₄₂ , R ₄₅ , R ₄₆ each independently represents a hydrogen atom, a hydrocarbon group, or a heterocyclic group.))

  The arbitrary anion used in the optical recording material to which the present invention is applied is preferably a monovalent monodentate ligand.

  The metal complex compound B is preferably a metal complex compound having a divalent or trivalent transition metal ion. Furthermore, it is preferable that such a transition metal is selected from the group consisting of nickel, cobalt, copper, iron, zinc, platinum, palladium and manganese.

Next, in the optical recording material to which the present invention is applied, the organic dye compound A includes a γ-pyrone organic dye, a γ-thiopyrone organic dye, a γ-1,1-dioxothiopyrone organic dye, γ- It may be a compound selected from pyridone organic dyes, coumarin organic dyes, carbostyryl organic dyes, and 1-thiocoumarin organic dyes.
In the optical recording material to which the present invention is applied, examples of the γ-pyrone organic dye include compounds represented by the following general formulas (III) and (IV) (generally, the following general formulas (III) and (IV) in), pyrone those Z = O, thiopyrone those Z = S, a di-oxo-thio-pyrones as the Z = SO _2, includes one selected ones Z = N from called a pyridone.).

(In the formula (III) or (IV), R _{17 to} R ₂₀ and R ₁₇ ′ to R ₂₀ ′ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a carbon number. C3-C12 cyclic alkyl group, C2-C12 linear or branched alkenyl group, C7-C18 aralkyl group, C1-C12 linear or branched alkoxy group, C1-C12 A linear or branched alkylthio group, a saturated or unsaturated heterocyclic group, an aryl group having 6 to 18 carbon atoms, a halogen atom, a nitro group, a cyano group, a mercapto group, a hydroxy group, a formyl group, and —COR ₃₄ An acyl group represented by —NR ₃₅ R ₃₆ , an acylamino group represented by —NHCOR ₃₇ , a carbamate group represented by —NHCOOR ₃₈ , and a carboxylic acid group represented by —COOR ₃₉ Steryl group, acyloxy group represented by —OCOR ₄₀ , carbamoyl group represented by —CONR ₄₁ R ₄₂ , sulfonyl group represented by —SO ₂ R ₄₃ , sulfinyl group represented by —SOR ₄₄ , —SO ₂ A sulfamoyl group represented by NR ₄₅ R ₄₆ , a sulfonic acid ester group represented by —SO ₃ R ₄₇ , and a sulfonamide group represented by —NHSO ₂ R ₄₈ (provided that R ₃₄ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₃ , R ₄₄ , R ₄₇ , R ₄₈ each independently represents a hydrocarbon group or a heterocyclic group, and R ₃₅ , R ₃₆ , R ₄₁ , R ₄₂ , R ₄₅ , R Each ₄₆ independently represents any of a hydrogen atom, a hydrocarbon group, and a heterocyclic group.

However, R ₁₇ and R ₁₈ , R ₁₉ and R ₂₀ , R ₁₇ ′ and R ₁₈ ′, and R ₁₉ ′ and R ₂₀ ′ may be condensed to form a hydrocarbon ring or a heterocyclic structure. The hydrocarbon ring and the heterocycle may have a substituent. ). X ₁ is an electron-withdrawing group, X ₂ is a hydrogen atom or -QY (Q is a direct bond, an alkylene group having 1 or 2 carbon atoms, an arylene group or a heteroarylene group, and Y is It is an electron-withdrawing group, and the alkylene group, the arylene group, and the heteroarylene group may have any substituent other than Y. Ring C is a carbocyclic ketone ring or heterocyclic ketone ring which may have a substituent together with C═O. Z and Z ′ are each —O—, —S—, —SO ₂ —, —NR ₂₁ — (wherein R ₂₁ is a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted complex; A cyclic group, a cyano group, a hydroxy group), an amino group represented by —NR ₂₂ R ₂₃ (R ₂₂ and R ₂₃ are each independently a hydrogen atom, a hydrocarbon group or a heterocyclic group), or —COR ₂₄ ( R ₂₄ represents a hydrocarbon group or a heterocyclic group), or represents an acyl group represented by —COR ₂₅ (R ₂₅ represents a hydrocarbon group or a heterocyclic group). )

Further, in the optical recording material to which the present invention is applied, a coumarin organic dye (in the following structural formula, X = O), a carbostyryl organic dye (in the following structural formula, X = NR ₃₃ ), a 1-thiocoumarin organic. Examples of the dye (in the following structural formula, X = S) include compounds represented by the following general formula (V).

(In formula (V), X represents —O—, —S—, —NR ₃₃ —. R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , and R ₃₀ each independently represents a hydrogen atom or a carbon number of 1; -12 linear or branched alkyl group, C3-C12 cyclic alkyl group, C2-C12 linear or branched alkenyl group, C7-C18 aralkyl group, C1-C12 Linear or branched alkoxy group, linear or branched alkylthio group having 1 to 12 carbon atoms, aryl group having 6 to 18 carbon atoms, saturated or unsaturated heterocyclic group, halogen atom, nitro group, cyano group, mercapto Group, hydroxy group, formyl group, acyl group represented by -COR ₃₄ , amino group represented by -NR ₃₅ R ₃₆ , acylamino group represented by -NHCOR ₃₇ , carbamate group represented by -NHCOOR ₃₈ , -CO Carboxylic acid ester group represented by R _39, an acyloxy group represented by -OCOR _40, a carbamoyl group represented by _-CONR 41 _{R 42,} a sulfonyl group represented by -SO _{2 R 43,} tables in -SOR ₄₄ A sulfinyl group represented by —SO ₂ NR ₄₅ R ₄₆ , a sulfonamido group represented by —NHSO ₂ R ₄₇ .

R ₃₁ , R ₃₂ and R ₃₃ each independently represent a hydrogen atom, a linear or branched alkyl group, a cyclic alkyl group, an aralkyl group, a linear or branched alkenyl group or an acyl group. Two adjacent R _{26 to} R ₃₃ may be bonded to form a saturated hydrocarbon ring or a saturated heterocyclic ring. )
(However, R ₃₄ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₃ , R ₄₄ , R ₄₇ , R ₄₈ each independently represents a hydrocarbon group or a heterocyclic group, and R ₃₅ , R ₃₆ , R ₄₁ , R ₄₂ , R ₄₅ , and R ₄₆ each independently represents a hydrogen atom, a hydrocarbon group, or a heterocyclic group.)

In the general formula (V), X is —O— or —NR ₃₃ —, and R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , and R ₃₀ are each independently a hydrogen atom or a carbon number of 1 to 8 straight or branched alkyl groups, 3 to 8 carbon cyclic alkyl groups, 7 to 12 carbon aralkyl groups, 1 to 8 straight or branched alkoxy groups, 1 to 8 carbon atoms Chain or branched alkylthio group, aryl group having 6 to 12 carbon atoms, saturated or unsaturated monocyclic or bicyclic heterocyclic group, halogen atom, nitro group, cyano group, mercapto group, hydroxy group, formyl group, acyl group represented by -COR _34, amino group represented by _-NR 35 _{R 36,} an acylamino group represented by -NHCOR _37, carbamate group represented by -NHCOOR _38, carbo represented by -COOR ₃₉ Ester group, an acyloxy group represented by -OCOR _40, a carbamoyl group represented by _-CONR 41 _{R 42,} it is preferably a sulfonamide group represented by -NHSO ₂ R _48.

In the general formula (V), R ₃₁ , R ₃₂ and R ₃₃ are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, It is preferably an aralkyl group having 7 to ₁₈ and a structure in which one or both of R ₂₉ and R ₃₁ , R ₃₀ and R ₃₂ may form a saturated hydrocarbon ring or a saturated heterocyclic ring.

In the optical recording material to which the present invention is applied, the metal complex compound B preferably inhibits the crystallization of the organic dye compound A.
Furthermore, it is preferable that the decomposition start temperature of the metal complex compound B is not higher than the decomposition start temperature of the organic dye compound A.

Next, according to the present invention, it has a substrate and a recording layer provided on the substrate and capable of recording or reproducing information by light, and the recording layer contains the optical recording material described above. An optical recording medium is provided.
The light used for recording or reproducing information on the optical recording medium is preferably laser light having a wavelength of 350 nm to 530 nm.
Moreover, it is preferable to measure the film thickness of the recording layer and manage the film thickness by measuring the absorption intensity of the metal complex compound B of the optical recording material contained in the recording layer.

  The “maximum absorption wavelength (λmax)” in the optical recording material to which the present invention is applied refers to the wavelength of the absorption maximum measured in a chloroform solution or a methanol solution, and the maximum absorption wavelength in either solution. (Λmax) may be in the range of 340 nm to 440 nm, or 500 nm to 900 nm. The maximum absorption when the optical recording material is formed into a film is considered to vary by about −10 nm to 10 nm from the value measured in a chloroform solution or a methanol solution.

  The “absorption maximum” described in the test method of the present invention means the absorption maximum when the optical recording material is formed in a film shape as described above. In the present invention, “absorption spectrum” means “absorption spectrum measured when a test piece is formed into a film”. Examples of the method of “forming a film” of the test piece include a method of preparing a “dye-coated disk” in the operation step for calculating the light resistance x described above.

  Thus, according to the present invention, recording / reproduction is possible with a short-wavelength blue laser, and a high-level optical recording material is provided.

Hereinafter, the best mode for carrying out the present invention (hereinafter referred to as an embodiment of the present invention) will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention. Also, the drawings used are used to describe the present embodiment and do not represent the actual size.
The optical recording material to which the present embodiment is applied includes an organic dye compound A having a maximum absorption wavelength (λmax) of 340 nm to 440 nm, a metal complex compound B having a maximum absorption wavelength (λmax) of 500 nm to 900 nm, and The organic dye compound A and the metal complex compound B so that the content of the organic dye compound A is greater than the content of the metal complex compound B and the light resistance x calculated by the following formula is 30% or more. Containing.

Light resistance x = {(I ₁ / I ₀ ) × 100}
(In the above formula, I ₀ is the absorbance at the absorption maximum existing in the wavelength range of 340 nm to 440 nm in the absorption spectrum of the film measured by the spectrophotometer of the organic dye compound A and the metal complex compound B mixture). I ₁ is the absorbance of the absorption maximum present in the wavelength range of 340 nm to 440 nm in the absorption spectrum of the film measured by a spectrophotometer after the film of the organic dye compound A and the metal complex compound B mixture is irradiated with light. .)

Here, the light resistance x is calculated by the following operation steps.
(Operation steps)
(Step 1) A solution containing the organic dye compound A and the metal complex compound B is spin-coated on a transparent substrate and then dried to prepare a dye-coated disk.
(Step 2) Using a spectrophotometer, the absorption spectrum of the dye-coated disk prepared in (Step 1) is measured at a wavelength of 300 nm to 900 nm, and the absorbance of the absorption maximum existing in the wavelength range of 340 nm to 440 nm is expressed as I ₀ . To do.
(Step 3) The dye-coated disk prepared in (Step 1) was subjected to a light irradiation treatment in which a xenon lamp was irradiated at 250 W / m ² for 8 hours, and then the absorption spectrum was measured under the same conditions as in (Step 2). the absorbance of the absorption maximum present in the wavelength range 340nm~440nm and _{I 1.}
(Step 4) Based on (I ₀ ) in (Step 2) and (I ₁ ) in (Step 3), {(I ₁ / I ₀ ) × 100} is calculated.

By doing as described above, (a) recording characteristics such as recording sensitivity can be improved, (b) light resistance can be improved, and (c) optical recording medium is coated on a substrate. The coating property at the time can be improved.
If the maximum absorption wavelength (λmax) of the organic dye compound A is 340 nm or more and 440 nm or less, the organic dye compound A has appropriate absorption in the wavelength region of the blue laser. Therefore, by using the organic dye compound A, an optical recording medium having a recording sensitivity that can be used for a blue laser can be obtained. When the maximum absorption wavelength (λmax) of the organic dye compound A exceeds this range, there is a problem that the absorption is too small to perform sufficient recording, or the absorption is too large to obtain a sufficient reflectance. It can happen.

  As for (a), the metal complex compound B used in the present embodiment does not affect the absorption spectrum of the organic dye compound A directly involved in recording / reproduction, so that the maximum absorption wavelength (λmax) is usually 500 nm or more. , Preferably 550 nm or more, preferably 620 nm or more, more preferably 680 nm or more, usually 900 nm or less, preferably 850 nm or less, more preferably 800 nm or less, and the maximum absorption wavelength (λmax ). The weight ratio needs to be organic dye compound A> metal complex compound B. Otherwise, the components having different wavelengths are related to the recording characteristics, and the recording characteristics may be impaired. When the total amount of the organic dye compound A and the metal complex compound B is 100% by weight, the content of the metal complex compound B is 40% by weight or less, more preferably 35% by weight or less, and further preferably 30% by weight or less. is there.

Further, since the metal complex compound B has such absorption in the visible light region, the light in this region is absorbed by the metal complex compound B, and optical damage to the organic dye compound A is reduced, (b) It is thought that the purpose of is achieved.
As described above, the metal complex compound B is first contained in order to reduce the optical damage of the organic dye compound A. Specifically, the metal complex compound B is contained, and the light resistance x measured by the above test method is set to 30% or more. Therefore, the respective contents of the organic dye compound A and the metal complex compound B can be determined in consideration of the light resistance of the organic dye compound A alone and the light resistance of the metal complex compound B alone.

That is, the organic dye compound A is a material having a light resistance x of less than 30% when used alone. Therefore, when the light resistance x of the organic dye compound A alone is a relatively high value in the range of less than 30%, the content of the metal complex compound B can be relatively reduced. On the other hand, when the light resistance x of the organic dye compound A alone is a relatively low value in the range of less than 30%, the content of the metal complex compound B needs to be relatively large. Thus, the content of the metal complex compound B is determined by the degree of the light resistance x of the organic dye compound A alone.
Further, the content of the metal complex compound B is determined by the degree of light resistance x when the metal complex compound B is used alone. That is, the higher the light resistance x alone of the metal complex compound B, the light resistance x of the optical recording material can be secured to 30% or more with a small content.

  The present inventors presume that the following relationship exists between the light resistance x of the optical recording material and the metal complex compound B. That is, in order to improve the light resistance x of the optical recording material, it is considered preferable to use a “weak absorber” of the metal complex compound B in the vicinity of a wavelength of 300 nm to 400 nm. This “weak absorption band” is considered to be an absorption band having a small interaction with a ligand derived from a metal ion or a weak absorption band derived from a ligand. The “weak absorption band” is considered to have an effect of shielding or masking the photodegradation of the organic dye compound A at the maximum absorption wavelength (λmax). This “weak absorption band” is often linked to the maximum absorption wavelength (λmax) of the metal complex compound B.

  Specifically, if the maximum absorption wavelength (λmax) of the metal complex compound B is on the short wavelength side, this “weak absorption band” is also found on the short wavelength side. The metal complex compound B having this “weak absorption band” in the vicinity of 350 nm to 500 nm, particularly in the vicinity of 400 nm, which is considered to be most involved in the deterioration of the dye in the light resistance test, is the maximum absorption wavelength (λmax). Was found to be longer than 620 nm, more specifically 680 nm or more (see FIG. 7). In the metal complex compound B having the maximum absorption wavelength (λmax) at 500 nm to 620 nm, the “weak absorption band” is shorter than 350 nm, and the absorbance near 400 nm is often very small (see FIG. 8).

  Therefore, when the metal complex compound B having a “weak absorption band” in the vicinity of 400 nm and having the maximum absorption wavelength (λmax) at 680 nm or more is used, it is considered that the content of the metal complex compound B can be reduced. On the other hand, since the metal complex compound B having the maximum absorption wavelength (λmax) in the range of 500 nm to 620 nm is small in the effect of improving the light resistance of the organic dye compound A, the amount of the metal complex compound B for ensuring the desired light resistance Will be needed more.

  In the present embodiment, as described above, the metal complex for ensuring practical light resistance by the maximum absorption wavelength (λmax) of the metal complex compound B and the light resistance of the organic dye compound A itself. The weight ratio of Compound B is different, and the weight ratio cannot be expressed numerically uniquely. Therefore, in the present embodiment, the organic dye compound A and the metal complex compound B may be contained so that the predetermined light resistance is 30% or more.

  For the above reasons, when the maximum absorption wavelength (λmax) of the metal complex compound B is 500 nm to 620 nm, the total amount of the organic dye compound A and the metal complex compound B is 100% by weight. The content is preferably 20% by weight or more and 40% by weight or less. The content of the metal complex compound B in the other wavelength range is preferably 5% by weight or more, more preferably 10% by weight or more. The upper limit is 40% by weight or less.

  When the maximum absorption wavelength (λmax) of the metal complex compound B is 680 nm or more and 900 nm or less, a “weak absorption band” is located in the vicinity of 400 nm, so that it is possible to secure desired light resistance with a smaller amount. Is possible.

  For the above reason, the difference between the maximum absorption wavelength (λmax) of the metal complex compound B and the maximum absorption wavelength (λmax) of the organic dye compound A is preferably 100 nm or more, more preferably 150 nm, still more preferably 200 nm or more, More preferably, it is 300 nm or more (see FIG. 10), and the upper limit is 500 nm, more preferably 450 nm, and still more preferably 400 nm.

  In addition, (c) the coating property (film forming property) at the time of coating is improved because the metal complex compound B has a very bulky three-dimensional structure as compared with the organic dye compound A. For example, the organic dye compound A Even if it has a structure that is easily crystallized by itself, it is considered that the metal complex compound B is appropriately dispersed and becomes amorphous, thereby preventing crystallization.

  Further, when the content of the metal complex compound B of the metal complex compound B in the optical recording material is excessively small, no improvement in recording properties such as coating properties at the time of coating, storage stability, and light resistance is observed. On the other hand, if the content is excessively large, the content of the organic dye compound A is reduced, and sufficient recording cannot be performed.

If the light resistance x is not 0%, it can be actually used. However, the light resistance x is preferably 30% from the viewpoint of forming a laminate, a cover layer, a protective coat layer using an ultraviolet curable resin, or preventing deterioration when the recording portion is repeatedly reproduced. Thus, more preferably 50% or more, still more preferably 80% or more, and even more preferably 90% or more.
As a light source used for evaluation of light resistance x, that is, light irradiation treatment, methods such as sunlight exposure and xenon lamp light irradiation are known (see ISO-105-B02). For example, the sample is irradiated with light having a distribution similar to the wavelength distribution of sunlight (natural daylight) (a xenon lamp is generally used) by an amount corresponding to WoolScale 5 (or European Reference # 5). (I ₁ / I ₀ ) may be measured. Such light irradiation treatment is usually performed with the dye film facing the light source.

More specifically, the light resistance x in the present embodiment is obtained by performing the following operations (1) to (4).
(1) An organic dye compound A and a metal complex compound B are contained in an organic solvent, spin-coated on a transparent substrate, and then dried to obtain a dye-coated disk.
(2) The absorption spectrum of the dye-coated disk (1) having a wavelength of 300 nm to 900 nm is measured with an ultraviolet / visible spectrophotometer, and the absorbance at the absorption maximum in the wavelength range of 340 nm to 440 nm is defined as I ₀ .
(3) After irradiating the coated disk of (1) in a light resistance tester for 8 hours with a xenon lamp at 250 W / m ² , an absorption spectrum is measured under the same conditions as in (2), and the wavelength range of 340 nm to 440 nm is obtained. The absorbance at a certain absorption maximum is I ₁ .
(4) Calculate (I ₁ / I ₀ ) × 100 and set it as light fastness x.

Hereinafter, the operations (1) to (4) will be described in more detail.
Operation of (1) When the organic solvent contains the organic dye compound A and the metal complex compound B, its absorption is dissolved to such an extent that the spectrophotometer can detect it, and dissolves the substrate material. Otherwise, there is no particular limitation. Examples of the solvent that dissolves include alcohol solvents. More specifically, for example, tetrafluoropropanol, octafluoropentanol and the like can be mentioned. In the examples of the present embodiment, tetrafluoropropanol was used. When the above compound is contained in an organic solvent, it is preferable to dissolve the solid content (the organic dye compound A and the metal complex compound B) in the organic solvent as much as possible through an ultrasonic disperser (hereinafter referred to as a solution). . The solid content is removed by filtration as much as possible. This is because if a solid is present in the film, the film may crystallize using it as a nucleus.

  Next, a solution containing the organic dye compound A and the metal complex compound B (in the example of the present embodiment, the total amount of the organic dye compound A and the metal complex compound B was 0.6% by weight of the solution weight) .) Is applied onto the substrate. This solution concentration is determined in consideration of the solubility of the organic dye compound A and the metal complex compound B.

  Any substrate can be used as long as transparency to visible light is ensured. Examples of the substrate include a glass substrate and a resin substrate, but it is preferable to use a resin substrate in that a good film can be formed in consideration of the surface tension of the solution. More preferably, a polycarbonate substrate that is practically used in CDs and DVDs is used. When a polycarbonate substrate is used, for example, a substrate having a thickness of 0.6 mm or 1.2 mm may be used.

Application to the substrate is not particularly limited, but spin coating is used as a method generally used for applying the recording layer of the optical recording medium. As a specific method when spin coating is used, a solution containing the organic dye compound A and the metal complex compound B is rotated while rotating a disk-shaped polycarbonate substrate having a thickness of 0.6 mm / diameter of 120 mm at 800 rpm. The method of dripping and apply | coating to the center part vicinity is mentioned. The solution concentration and the rotational speed of spin coating at this time are not particularly limited as long as absorption can be detected, but the absorbance at the absorption maximum is 0.1 or more, more preferably 0.2 or more, and still more preferably 0.3 or more. . The upper limit is approximately 1.0. If possible, it is preferable to set conditions for the density and the number of rotations so that the film thickness is suitable for recording and reproduction.
After coating, the coating is dried to remove the organic solvent from the coating. The drying temperature is a temperature range in which the organic solvent evaporates and is not particularly limited, but is preferably 60 ° C to 100 ° C.

(2) Operation The absorption spectrum from 300 nm to 900 nm of the dye-coated disk obtained in (1) is measured with an ultraviolet / visible spectrophotometer. A known apparatus can be used as the ultraviolet / visible spectrophotometer. An example of such an apparatus is U-3300 manufactured by Hitachi, Ltd. Then, in the absorption spectrum from 300 nm to 900 nm, the absorbance I ₀ of the wavelength (absorption maximum wavelength) showing the maximum absorbance in the wavelength range of 340 nm to 440 nm is obtained.

Operation (3) The xenon lamp is irradiated at 250 W / m ² for 8 hours to the dye-coated disk of (1). Irradiation with a xenon lamp may be performed using, for example, a light resistance tester. Thereafter, in the same manner as in the above (2), the absorption spectrum from 300 nm to 900 nm of the dye-coated disk was measured with an ultraviolet / visible spectrophotometer, and the absorbance I ₁ having a wavelength indicating the maximum absorbance in the wavelength range of 340 nm to 440 nm. Ask for.

(4) Operation (I ₀ / I ₁ ) × 100 is calculated using I ₀ and I ₁ obtained in (2) and (3) above, and this is defined as light resistance x.
In addition, when calculating | requiring the light fastness x of the organic dye compound A or the metal complex compound B alone, instead of the combined use of the organic dye compound A and the metal complex compound B, the organic dye compound A for which the light fastness x is desired. Alternatively, the metal complex compound B may be used alone.

  Examples of the metal complex compound B used in the present embodiment include an azo metal complex compound or an indoaniline metal complex compound. These azo metal complex compounds or indoaniline metal complex compounds are preferably poorly water-soluble in consideration of the use of optical recording materials. Hereinafter, specific examples of these azo metal complex compounds or indoaniline metal complex compounds will be described.

  As the metal complex compound B used in the present embodiment, an azo metal complex compound composed of an azo dye represented by the general formula (I) and a metal ion, a compound represented by the general formula (II) and a metal ion, any Mention may be made of metal complex compounds composed of anions. In addition, a metal complex compound is not restricted to the same kind, You may use multiple types of metal complex compounds.

  A metal complex compound is formed by a chelate bond between the compound represented by the general formula (I) and a metal. The molecular weight of the azo compound represented by the general formula (I) is usually 2000 or less, preferably 1500 or less.

  The metal constituting the metal complex compound B used in the present embodiment is not particularly limited as long as it has the ability to form coordination with the general formula (I), and may be a transition element or a typical element, and the oxidation number is not limited. Moreover, the ratio of the metal and the azo compound in the complex is not particularly limited, but a structure coordinated at a ratio of the azo compound 2 to the transition metal 1 is preferable. In order to obtain a stable complex structure, a transition metal having a divalent or trivalent ion is preferable. Among these, it is particularly preferable to be selected from the group consisting of nickel, cobalt, copper, iron, zinc, platinum, palladium, and manganese.

  In the compound represented by the general formula (I), the ring A represents a nitrogen-containing heteroaromatic ring formed together with the carbon atom and the nitrogen atom to which the ring A is bonded. The structure of the aromatic ring may be a single ring or a condensed ring as long as it has a nitrogen atom at a coordinateable position, and examples thereof include aromatic rings as exemplified below.

Here, D ₁ to D ₉ is a hydrogen atom or an optionally substituted alkyl group, and an acyl group. The aromatic ring may have an arbitrary substituent other than a hydrogen atom, and the number and position of the substituent are not particularly limited. Among these, preferable structures as the ring A include a 5-membered monocyclic ring and a 2-condensed ring. Among them, a benzothiazole ring, a benzoxazole ring, a benzimidazole ring, from the viewpoint of ease of synthesis and solubility, An imidazole ring, thiazole ring, thiadiazole ring, triazole ring, oxazole ring, pyridine ring, pyrazole ring and isoxazole ring are preferred. The bond in which the azo compound represented by the general formula (I) and the metal are chelate-bonded includes, for example, the following forms such as a and a ′, b and b ′.
M represents a central metal.

Hereinafter, R _{1 to} R ₅ in the general formula (I) will be described.
In the general formula (I), R ₁ and R ₂ are each independently a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- A linear or branched alkyl group such as a butyl group; a cyclic alkyl group such as a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group; an aralkyl group such as a benzyl group or a phenethyl group; an alkenyl group such as a vinyl group, a propenyl group, or a hexenyl group; Represent.

These structures represented by R ₁ and R ₂ generally shift λmax to a longer wavelength by increasing the number of carbon atoms in the alkyl chain portion or by taking a condensed ring structure as described later, but the number of carbon atoms is not so much. If the amount is too large, the wavelength is not so effective, and conversely the absorption intensity per gram may be lowered, and the product may not be solidified.

Therefore, as R ₁ and R ₂ , a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms (these aromatic ring portions are optional) Particularly preferably a linear or branched alkyl group having 1 to 8 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. It is.

One or both of R ₁ and R ₂ may be bonded to R ₃ or R ₅ of the adjacent benzene ring to form a saturated carbocycle (fused ring), and R ₃ and R ₅ are each independently It may have a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and may be condensed with R ₁ or R ₂ to form a saturated heterocyclic ring (condensed ring). Further, R ₁ and R ₂ may be bonded to each other to form a saturated carbocyclic structure (condensed ring). At this time, a saturated heterocyclic ring (condensed ring) containing one or more other hetero atoms in addition to the carbon atom may be formed. The ring (fused ring) thus formed is preferably a 5- to 7-membered ring, more preferably a 5- to 6-membered ring. Furthermore, a substituent may be bonded to a ring (condensed ring) formed by combining R ₁ and R ₂ or a ring formed by combining R ₁ and R ₂ with a benzene ring. .

Here, as an example when (-NR < ₁ > R < ₂ >) is a ring structure, what is shown below is mentioned.

Here, D < ₁₀ > -D < ₁₂ > represents either a hydrogen atom or the alkyl group and acyl group which may be substituted. The aromatic ring may have an arbitrary substituent, and the number and position of the substituent are not particularly limited as long as they are within the scope of the gist of the present invention.

R ₃ , R ₄ and R ₅ are each a hydrogen atom or a carbon number such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an n-heptyl group. A linear or branched alkyl group having 1 to 12 carbon atoms; a cyclic alkyl group having 3 to 12 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and adamantyl group; and 2 carbon atoms such as vinyl group, propenyl group, and hexenyl group. 12 straight-chain or branched alkenyl groups, benzyl groups, phenethyl groups and other aralkyl groups having 7 to 18 carbon atoms; methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, n-butoxy groups, sec-butoxy groups A linear or branched alkoxy group having 1 to 12 carbon atoms such as tert-butoxy group; methylthio group, ethylthio group, n-propylthio group, n-buty A linear or branched alkylthio group having 1 to 12 carbon atoms such as a thio group, a sec-butylthio group, a tert-butylthio group; a monocyclic saturated heterocyclic group such as a 4-piperidyl group and a morpholino group; a fluorine atom, a chlorine atom, represented by -NHCOR _37; amino group represented by _-NR 35 _{R 36;} nitro group; cyano group; a mercapto group; hydroxy group; acyl group represented by -COR _34; formyl group halogen atom such as a bromine atom A carbamate group represented by —NHCOOR ₃₈ ; a carboxylic acid ester group represented by —COOR ₃₉ ; an acyloxy group represented by —OCOR ₄₀ ; a carbamoyl group represented by —CONR ₄₁ R ₄₂ ; sulfinyl group represented by -SOR _44;; sulfonyl group represented by ₂ R ₄₃ represented by -SO _{2 NR} 45 _{R 46} That a sulfamoyl _group; represents a sulfonamide group represented by -NHSO ₂ R _48; sulfonate group represented by -SO _{3 R 47.}

Here, R ₃₄ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₃ , R ₄₄ , R ₄₇ , R ₄₈ represent a hydrocarbon group or a heterocyclic group, and R ₃₅ , R ₃₆ , R ₄₁ , R ₄₂ , R ₄₅ and R ₄₆ represent any of a hydrogen atom, a hydrocarbon group and a heterocyclic group.

The hydrocarbon group represented by R _{34 to} R ₄₈ is a carbon such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an n-heptyl group. A linear or branched alkyl group having 1 to 18 carbon atoms; a cyclic alkyl group having 3 to 18 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group and adamantyl group; 2 carbon atoms such as vinyl group, propenyl group and hexenyl group A linear or branched alkenyl group of -18; a cyclic alkenyl group of 3-18 carbon atoms such as a cyclopentenyl group or a cyclohexenyl group; an aralkyl group of 7-20 carbon atoms such as a benzyl group or a phenethyl group; a phenyl group, tolyl Represents an aryl group having 6 to 18 carbon atoms such as a group, a xylyl group and a mesityl group. The alkyl chain part and aryl group part of these groups may be further substituted with a substituent which the alkyl chain part described later may have.

The heterocyclic group represented by R _{34 to} R ₄₈ may be a saturated heterocyclic ring such as 4-piperidyl group, morpholino group, 2-morpholinyl group, piperazyl group, 2-furyl group, 2-pyridyl group, 2- An aromatic heterocyclic ring such as a thiazolyl group and a 2-quinolyl group may be used. These may contain a plurality of heteroatoms, may further have a substituent, and may have any bonding position. Preferred structures for the heterocyclic ring are a 5- or 6-membered saturated heterocyclic ring, a 5- or 6-membered monocyclic ring and an aromatic heterocyclic ring thereof.

An acyl group represented by —COR ₃₄ ; an amino group represented by —NR ₃₅ R ₃₆ ; an acylamino group represented by —NHCOR ₃₇ ; a carbamate group represented by —NHCOOR ₃₈ ; a carvone represented by —COOR ₃₉ Acid ester group; acyloxy group represented by -OCOR ₄₀ ; carbamoyl group represented by -CONR ₄₁ R ₄₂ ; sulfonyl group represented by -SO ₂ R ₄₃ ; sulfinyl group represented by -SOR ₄₄ ; -SO sulfonic acid ester group represented by -SO _{3 R 47;;} sulfamoyl group represented by ₂ NR ₄₅ R ₄₆ examples of the sulfonamide group represented by -NHSO ₂ R _48, include those shown below It is done.

Examples of the acyl group (—COR ₃₄ ) include substituents having the following structure.

Examples of the amino group (—NR ₃₅ R ₃₆ ) include substituents having the following structure.

Examples of the acylamino group (—NHCOR ₃₇ ) include substituents having the following structure.

Examples of the carbamate group (—NHCOOR ₃₈ ) include substituents having the following structure.

Examples of the carboxylic acid ester group (—COOR ₃₉ ) include substituents having the following structure.

Examples of the acyloxy group (—OCOR ₄₀ ) include substituents having the following structure.

Examples of the carbamoyl group (—CONR ₄₁ R ₄₂ ) include substituents having the following structure.

Examples of the sulfonyl group (—SO ₂ R ₄₃ ) include substituents having the following structure.

Examples of the sulfinyl group (—SOR ₄₄ ) include substituents having the following structure.

Examples of the sulfamoyl group (—SO ₂ NR ₄₅ R ₄₆ ) include substituents having the following structure.

Examples of the sulfonic acid ester group (—SO ₃ R ₄₇ ) include substituents having the following structure.

Examples of the sulfonamide group (—NHSO ₂ R ₄₈ ) include substituents having the following structure.

Preferred as R ₃ , R ₄ , and R ₅ are a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a linear or branched group having 1 to 8 carbon atoms. In an alkoxy group, a linear or branched alkylthio group having 1 to 8 carbon atoms, a monocyclic 5- to 6-membered saturated heterocyclic group, a halogen atom, a nitro group, a cyano group, a mercapto group, a hydroxy group, and —COR ₃₄ An acyl group represented by: an amino group represented by —NR ₃₅ R _36; an acylamino group represented by —NHCOR _37; a carbamate group represented by —NHCOOR _38; a carboxylic acid ester group represented by —COOR ₃₉ ; acyloxy group represented by -OCOR _40, a carbamoyl group represented by _-CONR 41 _{R 42,} a sulfonyl group represented by -SO _{2 R 43,} in -SO _{2 NR} 45 _{R 46} It is the sulfamoyl group, a sulfonamide group represented by -NHSO ₂ R _48.

In general formula (I), XL represents a substituent capable of coordinating with a metal when the leaving group L is eliminated. Specific examples of the substituent represented by XL include a hydroxy group (—O ⁻ ; X, H ⁺ ; L), a sulfonic acid group (—SO ₃ H ⁻ ; X, H ⁺ ; L), an amino group (— N—H; X, H ⁺ ; L), acylamino group (—N—COR ₃₇ , H ⁺ ; L), sulfonamide group (—N—SO ₂ R ₄₈ , H ⁺ ; L), mercapto group (—S) ^- ; X, H ^<+> ; L), a carboxyl group (-COO ^{< - >} ; X, H ^<+> ; L), etc. are mentioned.

  Preferred structures of the azo compound represented by the general formula (I) are shown in the following (1) to (48-2).

  As the metal complex compound B of the optical recording material to which the present embodiment is applied, an indoaniline-based metal complex compound formed by combining a compound represented by the general formula (II) with a metal ion and an anion is used. Can be used. The molecular weight of the compound represented by the general formula (II) is usually 4500 or less, preferably 3000 or less, although it depends on the coordination structure between the ligand and the metal.

In the compound represented by the general formula (II), R ₆ and R _{7 each} represents a hydrogen atom, a linear or branched alkyl group, a cyclic alkyl group, an aralkyl group, or a linear or branched alkenyl group.
The structure represented by these R ₆ and R ₇ is also preferably a linear or branched alkyl group having 1 to 12 carbon atoms or a cyclic alkyl group having 3 to 12 carbon atoms for the same reason as R ₁ and R ₂ described above. , An aralkyl group having 7 to 20 carbon atoms (these aromatic ring portions may have an arbitrary substituent), particularly preferably a linear or branched alkyl group having 1 to 8 carbon atoms, They are a C3-C8 cyclic alkyl group and a C7-C12 aralkyl group.

One or both of R ₆ and R ₇ may be condensed with R ₈ or R ₁₀ of the adjacent benzene ring to form a saturated carbocycle (condensed ring), and R ₈ and R ₁₀ are each independently It may have a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and may be condensed with R ₆ or R ₇ to form a saturated heterocyclic ring (condensed ring). Further, R ₆ and R ₇ may be condensed with each other to form a saturated carbocyclic (condensed ring) structure. At this time, a saturated heterocyclic ring containing one or more other hetero atoms in addition to the carbon atom may be formed. The ring thus formed is preferably a 5- to 7-membered ring, more preferably a 5- to 6-membered ring. Furthermore, a substituent may be bonded to the ring formed by combining these R ₆ and R ₇ or the ring formed by combining R ₆ and R ₇ with a benzene ring.

As such a structure, a structure similar to that shown as an example in the case where the aforementioned (—NR ₁ R ₂ ) is a ring structure can be used.

In the general formula (II), R _{8 to} R ₁₆ are each a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a straight chain having 2 to 12 carbon atoms, or A branched alkenyl group, an aralkyl group having 7 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 12 carbon atoms, a linear or branched alkylthio group having 1 to 12 carbon atoms, a monocyclic saturated heterocyclic group, Aryl group having 6 to 18 carbon atoms, halogen atom, nitro group, cyano group, mercapto group, hydroxy group, formyl group, acyl group represented by —COR ₃₄ ; amino group represented by —NR ₃₅ R ₃₆ ; acyloxy group represented by -OCOR _40;; carboxylic acid ester group represented by -COOR _39; carbamate group represented by -NHCOOR _38; acylamino group represented by NHCOR ₃₇ -C Sulfamoyl group represented by _{-SO 2 NR 45 R 46;;} NR 41 carbamoyl group represented by R _42; sulfinyl group represented by -SOR _44; -SO ₂ sulfonyl group represented by _{R 43} -SO ₃ A sulfonic acid ester group represented by R ₄₇ ; a sulfonamide group represented by —NHSO ₂ R ₄₈ (where R ₃₄ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₃ , R ₄₄ , R ₄₇ and R ₄₈ each independently represent a hydrocarbon group or a heterocyclic group, and R ₃₅ , R ₃₆ , R ₄₁ , R ₄₂ , R ₄₅ and R ₄₆ each independently represent a hydrogen atom or a hydrocarbon Represents either a group or a heterocyclic group.)

R _{8 to} R ₁₆ are preferably a linear or branched alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 12 carbon atoms, or 1 to 1 carbon atoms. 12 straight chain or branched alkylthio groups, aryl groups having 6 to 18 carbon atoms, saturated or unsaturated monocyclic or bicyclic heterocyclic groups, halogen atoms, nitro groups, cyano groups, mercapto groups, hydroxy groups, An acyl group represented by —COR ₃₄ , an amino group represented by —NR ₃₅ R ₃₆ , an acylamino group represented by —NHCOR ₃₇ , a carbamate group represented by —NHCOOR ₃₈ , and a carvone group represented by —COOR ₃₉ ester group, an acyloxy group represented by -OCOR _40, a carbamoyl group represented by _-CONR 41 _{R 42,} a sulfonyl group represented by -SO _{2 R 43,} The sulfamoyl group represented by SO ₂ NR ₄₅ R _46, a sulfonamide group represented by -NHSO ₂ R _48.

  The metal constituting the metal complex compound B used in the present embodiment is not particularly limited as long as it has a coordination formation ability with the compound represented by the general formula (II), and may be a transition element or a typical element, and its oxidation number is also It is not limited. Moreover, the ratio of the metal and the azo compound in the complex is not particularly limited, but a structure coordinated at a ratio of the azo compound 2 to the transition metal 1 is preferable. In order to obtain a stable complex structure, a transition metal having a divalent or trivalent ion is preferable. Among these, it is particularly preferable to be selected from the group consisting of nickel, cobalt, copper, iron, zinc, platinum, palladium, and manganese.

  The anion that forms a complex with the indoaniline compound and the metal ion may be any anion as long as the whole complex is neutral in terms of charge. Examples thereof include those having a monovalent charge such as halogen atoms, nitrate ions, chlorate ions, and perchlorate ions. Further, examples of such anions include those having a divalent charge such as oxalate ions, sulfate ions, and carbonate ions. Moreover, as such an anion, what has the electric charge beyond it may be sufficient. In addition, the number of conformations may be a monodentate ligand or a multidentate ligand having a plurality of coordination atoms such as a bidentate ligand or a tridentate ligand. Preferably, the anion is a monovalent monodentate ligand. It is preferable that the anion is a monovalent monodentate ligand because a single component compound can be easily synthesized. A monovalent valence is preferable because it is relatively easy to synthesize. Further, the anion may be directly coordinated to a metal atom as a ligand, or may be separated from each other like a salt.

  Examples of these ligands include the following.

  The ratio of the compound represented by the general formula (II) to the metal ion and the anion is not particularly specified, and may vary depending on the charge of the metal ion and the coordination structure of the metal complex compound. This is a structure in which two or three compounds represented by the general formula (II) are coordinated with the ion 1. A compound having such a structure tends to form the following complex. In the following structural formula, M represents a metal ion and X represents an anion.

  When these are coordinated, a compound or anion represented by a plurality of types of general formula (II) is coordinated in addition to a metal complex compound composed of the same type of compound represented by general formula (II) and a metal ion and an anion. It may be shaped. Below, the preferable structure of the compound shown by general formula (II) is shown.

  Next, the organic dye compound A in the optical recording material to which this embodiment is applied will be described. As the organic dye compound A used in the optical recording material to which the present embodiment is applied, any known one can be used as long as it can record with a so-called blue laser having an absorption maximum in the range of 340 nm to 440 nm. Can be used. In general, organic dye compounds A capable of recording with a blue laser generally have a light resistance x measured by the above test method of less than 30% when used alone. Such an organic dye compound A is not particularly limited, and includes γ-pyrone organic dyes, coumarin organic dyes, carbostyryl organic dyes, and 1-thiocoumarin organic dyes.

  The molecular weights of γ-pyrone organic dyes, coumarin organic dyes, carbostyryl organic dyes, and 1-thiocoumarin organic dyes are not particularly limited, but in the case of pyrone organic dyes, the molecular weight is usually 900 or less, preferably 600 or less. In the case of a coumarin organic dye or a carbostyril organic dye, the molecular weight is usually 700 or less, preferably 500 or less. If the molecular weight is excessively large, the OD value decreases particularly in a portion that does not contribute to absorption, and it is not preferable because it is impossible to ensure the absorption necessary for recording.

  More specifically, it is preferable to use a compound selected from the compounds represented by the aforementioned general formulas (III), (IV) and (V).

Hereinafter, first, general formula (III) or general formula (IV) will be described. In addition, about R < ₁₇ '>-R < ₂₀ >' in general formula (III) or (IV), the same thing as R < ₁₇ > -R < ₂₀ > is mentioned.

In General Formula (III) or General Formula (IV), R _{17 to} R ₂₀ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms. , A linear or branched alkenyl group having 2 to 12 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 12 carbon atoms, a linear or branched alkylthio group having 1 to 12 carbon atoms Group, saturated or unsaturated heterocyclic group, aryl group having 6 to 18 carbon atoms, halogen atom, nitro group, cyano group, mercapto group, hydroxy group, formyl group, acyl group represented by —COR ₃₄ ; An amino group represented by ₃₅ R ₃₆ ; an acylamino group represented by —NHCOR ₃₇ ; a carbamate group represented by —NHCOOR ₃₈ ; a carboxylic acid ester group represented by —COOR ₃₉ ; An acyloxy group represented by —OCOR ₄₀ ; a carbamoyl group represented by —CONR ₄₁ R ₄₂ ; a sulfonyl group represented by —SO ₂ R ₄₃ ; a sulfinyl group represented by —SOR ₄₄ ; and —SO ₂ NR ₄₅ R. A sulfamoyl group represented by ₄₆ ; a sulfonic acid ester group represented by —SO ₃ R ₄₇ ; a sulfonamide group represented by —NHSO ₂ R ₄₈ .

However, R ₁₇ and R ₁₈ , R ₁₉ and R ₂₀ , R ₁₇ ′ and R ₁₈ ′, and R ₁₉ ′ and R ₂₀ ′ may be condensed to form a hydrocarbon ring or a heterocyclic structure. The hydrocarbon ring and the heterocycle may have a substituent. X ₁ is an electron-withdrawing group, X ₂ is a hydrogen atom or -QY (Q is a direct bond, an alkylene group having 1 or 2 carbon atoms, an arylene group or a heteroarylene group, and Y is It is an electron-withdrawing group, and the alkylene group, the arylene group, and the heteroarylene group may have any substituent other than Y. Ring C is a carbocyclic ketone ring or heterocyclic ketone ring which may have a substituent together with C═O. Z and Z ′ are each —O—, —S—, —SO ₂ —, —NR ₂₁ — (wherein R ₂₁ is a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted complex; A cyclic group, a cyano group, a hydroxy group, an amino group represented by —NR ₂₂ R ₂₃ (R ₂₂ and R ₂₃ are each independently a hydrogen atom, a hydrocarbon group or a heterocyclic group, or —COR ₂₄ (R ₂₄ Is a hydrocarbon group or a heterocyclic group), or -COR ₂₅ (R ₂₅ represents an acyl group represented by a hydrocarbon group or a heterocyclic group).

Among the above substituents, preferred as R _{17 to} R ₂₀ are linear or branched alkyl groups having 1 to 8 carbon atoms, cyclic alkyl groups having 3 to 8 carbon atoms, linear or branched chains having 2 to 8 carbon atoms. An alkenyl group having 7 to 12 carbon atoms, a linear or branched alkoxy group having 1 to 8 carbon atoms, a linear or branched alkylthio group having 1 to 8 carbon atoms, a saturated or unsaturated monocyclic ring, or 2 Condensed heterocyclic group, aryl group having 6 to 12 carbon atoms, halogen atom, nitro group, cyano group, mercapto group, hydroxy group, acyl group represented by —COR ₃₄ ; represented by —NR ₃₅ R ₃₆ acyloxy group represented by -OCOR _40; carboxylic acid ester group represented by -COOR _39; carbamate group represented by -NHCOOR _38; acylamino group represented by -NHCOR _37; amino group; In a sulfonamide group represented by -NHSO ₂ R _48; sulfamoyl group represented by -SO _{2 NR} 45 _{R 46;} sulfonyl group represented by -SO _{2 R 43;} carbamoyl groups represented by CONR ₄₁ R ₄₂ is there.

R ₁₇ and R ₁₈ , R ₁₉ and R ₂₀ , R ₁₇ ′ and R ₁₈ ′, R ₁₉ ′ and R ₂₀ ′ are preferably condensed to form a hydrocarbon ring or heterocyclic structure, The following condensed ring structures are mentioned.

(In the condensed ring structure, D _{13 to} D _{15 each} represents a hydrogen atom, an alkyl group which may be substituted, or an acyl group. The aromatic ring may have an arbitrary substituent, and The number and position of the substituents are not particularly limited as long as they are within the scope of the present invention.) These condensed rings may be substituted with a substituted or unsubstituted alkyl group as described above. As a substituent which this alkyl group may have, the same kind as the substituent which the alkyl chain part of R < ₁₇ > -R < ₂₀ > mentioned later may have is mentioned, for example.

In the general formula (III) or general formula (IV) of the organic dye compound A, as the electron withdrawing group of Y in X ₁ and X ₂ , generally, the sigma constant σ (σm and σp, particularly σp) is positive in Hammett's rule. Those with the value of. Examples of these include halogen-substituted alkyl groups such as cyano group, nitro group, nitroso group, halogen atom, carboxyl group, formyl group, acyl group, carboxylic acid ester group, carbamoyl group, trialkylamino group, trifluoromethyl group, etc. Sulfonic acid group, sulfonic acid ester group, sulfonyl group, sulfamoyl group, sulfinyl group and the like. As for the halogen-substituted alkyl group such as acyl group, carboxylic acid ester group, carbamoyl group, trialkylamino group, trifluoromethyl group, sulfonic acid group, sulfonic acid ester group, sulfonyl group, sulfamoyl group, sulfinyl group as described above The thing is mentioned.

Formula of the organic dye compound A (III) or general formula (IV), linking group Q is a direct bond _{(X 2} becomes -Y.), An alkylene group, an arylene group having 1 to 2 carbon atoms, a hetero Represents an arylene group. Here, Y is an electron-withdrawing group, and the alkylene group, the arylene group, and the heteroarylene group may have any substituent other than Y. When Q is an alkylene group, the carbon atom has an alkyl chain branched therefrom, even if it has a substituent other than a hydrogen atom that may be possessed when R _{1 to} R ₄₈ described later are an alkyl chain. It may be. When Q represents a 6-membered arylene group or heteroarylene group, the electron-withdrawing group Y is preferably in the ortho or para position with respect to the bond, and when it is a 5-membered heteroarylene group, It is preferable that the bonding portion and the electron-withdrawing group are in the 2-position and 4-position. A plurality of Ys may be bonded to these linking groups. Moreover, you may have a substituent in places other than Y couple | bonded. Preferred bonds between these linking groups and electron-withdrawing groups are exemplified below.

(In the above _{illustration,} G 1 ~G ₆ represents an optional substituent or an optionally substituted alkyl chain be of from 1 to 4 carbon _{atoms, X} 1, Y is as .X ₁ having an electron-withdrawing group More preferably, a cyano group, a nitro group, an acyl group, a carboxylic acid ester group, a carbamoyl group, a halogen-substituted alkyl group, a sulfonyl group, a sulfamoyl group, and a sulfinyl group can be mentioned. A nitro group, an acyl group, a carboxylic acid ester group, a carbamoyl group, a halogen-substituted alkyl group, a sulfonyl group, a sulfamoyl group, a sulfinyl group, and more preferably an arylene group or heteroarylene as a continuous group of Q. Group).

In general formula (III) or general formula (IV) of organic dye compound A, ring C represents a carbocyclic ketone structure or a heterocyclic ketone structure together with> C═O. The carbocyclic ketone and heterocyclic ketone are those in which —CH ₂ — or ═CH— in an unsaturated or aromatic ring system is replaced by> C═O. Also, the ring structure portion of the ring C indicated by the dotted line may have a plurality of> C = O,> C = S,> C = NH, and the like. The carbocyclic ketone structure or heterocyclic ketone structure formed by the ring C may be saturated or unsaturated, and the number of ring members is not particularly limited. In the heterocycle, the number of heteroatoms is not particularly limited. Moreover, the hydrocarbon group part in a ring and the hydrogen atom of -NH- which comprises a ring may be substituted by arbitrary substituents. As the substituent, an alkyl group or an aryl group is particularly preferable.

  These carbocyclic ketone structures and heterocyclic ketone structures may form a condensed ring structure by condensing a further ring with a part of the ring. The ring structure condensed to the cyclic ketone structure may be a hydrocarbon ring or a heterocyclic ring, but is preferably a benzene ring or a 5- to 6-membered heteroaromatic ring. Below, the structure which a cyclic ketone shows is illustrated.

  Preferable examples of the carbocyclic ketone structure and the heterocyclic ketone structure formed by the ring C include a 5- or 6-membered saturated hydrocarbon ring or a 5- or 6-membered saturated or unsaturated heterocyclic ring. .

In the general formula (III) or general formula (IV) of the organic dye compound A, the hydrocarbon group in R ₂₁ of —NR ₂₁ — of Z is methyl, ethyl, propyl, isopropyl, n-butyl. Group having 3 to 18 carbon atoms such as a straight-chain or branched alkyl group having 1 to 18 carbon atoms such as a group, sec-butyl group, tert-butyl group and n-heptyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and adamantyl group -18-cyclic alkyl group, vinyl group, propenyl group, hexenyl group, etc., straight-chain or branched alkenyl group having 2-18 carbon atoms, cyclopentenyl group, cyclic alkenyl group having 3-18 carbon atoms, such as cyclohexenyl group, 6 to 18 carbon atoms such as aralkyl group having 7 to 20 carbon atoms such as benzyl group and phenethyl group, phenyl group, tolyl group, xylyl group and mesityl group It represents an aryl group. The alkyl chain part and aryl group part of these groups may be further substituted with a substituent which R _{1 to} R ₄₈ described later may have when it becomes an alkyl chain.

The heterocyclic group represented by R ₂₁ may be a saturated heterocyclic ring such as 4-piperidyl group, morpholino group, 2-morpholinyl group, piperazyl group, 2-furyl group, 2-pyridyl group, 2-thiazolyl group, 2 -An aromatic heterocyclic ring such as a quinolyl group may be used. These may contain a plurality of heteroatoms, may further have a substituent, and may have any bonding position. Preferred structures for the heterocyclic ring are a 5- or 6-membered saturated heterocyclic ring, a 5- or 6-membered monocyclic ring and an aromatic heterocyclic ring thereof. These groups may be further substituted with a substituent that may be possessed when R _{1 to} R ₄₈ described later are alkyl chains.

When R ₂₁ has an alkyl chain as an optionally substituted hydrocarbon group, it is bonded to R ₁₈ or R ₂₀ , R ₁₈ ′ or R ₂₀ ′ to form a saturated or unsaturated hydrocarbon ring, saturated or unsaturated A heterocyclic structure of The number of members in the cyclic structure is not particularly limited, but a hydrocarbon ring and a heterocyclic ring are preferably 5 to 6 membered rings. These preferred fused ring structures are shown below.

Examples of R ₂₂ and R _{23 in} —NR ₂₂ R ₂₃ include the same groups as the hydrocarbon groups and heterocyclic groups exemplified as R ₂₁ . Examples of R ₂₄ of —COR ₂₄ include the same hydrocarbon groups and heterocyclic groups as those of R ₂₁ . R _{25 in} —COR ₂₅ represents either a hydrocarbon group or a heterocyclic group, and the same group as the hydrocarbon group and the heterocyclic group may be mentioned in the same manner as R ₂₁ . Examples of preferred —NR ₂₁ — are given below.

  Preferred examples of the compound represented by the general formula (III) or the general formula (IV) of the organic dye compound A include the following (A (1) to A (103)). Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

Next, as the organic dye compound A in the optical recording material to which the present embodiment is applied, it is preferable to use the compound represented by the general formula (V) described above.
In the general formula (V), X represents an oxygen atom, a sulfur atom or —N—R ₃₃ . R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or 2 to 2 carbon atoms. 12 straight or branched alkenyl groups, 7 to 18 aralkyl groups, 1 to 12 straight or branched alkoxy groups, 1 to 12 straight or branched alkylthio groups, 6 carbon atoms -18 aryl group, saturated or unsaturated heterocyclic group, halogen atom, nitro group, cyano group, mercapto group, hydroxy group, formyl group, acyl group represented by -COR ₃₄ , represented by -NR ₃₅ R ₃₆ amino group, an acylamino group represented by -NHCOR _37, carbamate group represented by -NHCOOR _38, a carboxylate group represented by -COOR _39, in -OCOR ₄₀ Is the acyloxy group, a carbamoyl group represented by _-CONR 41 _{R 42,} a sulfonyl group represented by -SO _{2 R 43,} a sulfinyl group represented by -SOR _44, represented by -SO _{2 NR} 45 _{R 46} sulfamoyl group, a sulfonamide group represented by -NHSO ₂ R _47.

R ₃₁ , R ₃₂ and R ₃₃ each independently represent a hydrogen atom, a linear or branched alkyl group, a cyclic alkyl group, an aralkyl group, a linear or branched alkenyl group or an acyl group. Further, two adjacent R _{26 to} R ₃₃ may be bonded to form a saturated hydrocarbon ring or a saturated heterocyclic ring (provided that R ₃₄ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R _43). , R ₄₄ , R ₄₇ , R ₄₈ each independently represents a hydrocarbon group or a heterocyclic group, and R ₃₅ , R ₃₆ , R ₄₁ , R ₄₂ , R ₄₅ , R ₄₆ are each independently hydrogen Represents any of atoms, hydrocarbon groups, and heterocyclic groups.)

Among the above groups, R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, Aralkyl group having 7 to 12 carbon atoms, linear or branched alkoxy group having 1 to 8 carbon atoms, linear or branched alkylthio group having 1 to 8 carbon atoms, aryl group having 6 to 12 carbon atoms, saturated or unsaturated A monocyclic or bicyclic heterocyclic group, a halogen atom, a nitro group, a cyano group, a mercapto group, a hydroxy group, a formyl group, an acyl group represented by —COR ₃₄ , an amino group represented by —NR ₃₅ R ₃₆ group, an acylamino group represented by -NHCOR _37, carbamate group represented by -NHCOOR _38, a carboxylate group represented by -COOR _39, Ashiruo represented by -OCOR ₄₀ Shi group, a carbamoyl group represented by _-CONR 41 _{R 42,} a sulfonamide group represented by -NHSO ₂ R _48.

These substituents can increase the solubility in coating solvents (especially those having an alkyl group moiety), and can shift the maximum absorption wavelength (λmax) to longer wavelengths (especially aryl groups, unsaturated complexes). It is useful in terms of a ring, an electron-withdrawing group such as a halogenated alkyl group and a cyano group, and those having these in R ₂₆ and R ₂₇ are particularly preferable.

R ₃₁ , R ₃₂ and R ₃₃ are each independently a hydrogen atom, a linear or branched alkyl group which may be substituted, a cyclic alkyl group which may be substituted, an aralkyl group which may be substituted, or a substituted group. Or a straight-chain or branched alkenyl group or acyl group.
R ₃₁ , R ₃₂ , and R ₃₃ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms.

In particular, in R ₃₁ and R ₃₂ , the maximum absorption wavelength (λmax) is shifted to the longer wavelength side by increasing the electron donating property of the amino group, so that the absorption to the blue laser can be further increased. Therefore, R ₃₁ and R ₃₂ are particularly preferably an unsubstituted linear or branched alkyl group or a cyclic alkyl group. However, even if there are too many carbon atoms, there is a problem that the effect is not so much seen in the wavelength and the absorption intensity is lowered, and the product is not solidified. Therefore, the carbon number of R ₃₁ and R ₃₂ is 1 To about 8 are preferable.

Further, two adjacent R _{26 to} R ₃₃ may be bonded to form a saturated hydrocarbon ring, and each of R _{26 to} R ₃₀ is independently heterogeneous such as an oxygen atom, a sulfur atom, or a nitrogen atom. A saturated heterocyclic ring which represents an atom and is condensed at the end may be formed.
The condensed ring structure is preferably a 5- to 7-membered ring structure in which R ₂₉ and R ₃₁ or R ₃₀ and R ₃₂ are condensed. R ₃₁ and R ₃₂ having an amino group structure are preferable since they can shift λmax to a longer wavelength by taking a condensed structure with an adjacent substituent and can be expected to improve solubility. Furthermore, the ring formed by combining these may further have a substituent. Specific examples of the ring structure include the structures shown below.

Here, D represents the same substituent as R ₃₁ and R ₃₂ .

  Preferred specific examples of the compound represented by formula (V) are shown below.

In addition, the linear or branched alkyl group, cyclic alkyl group, linear or branched alkenyl group, cyclic alkenyl group, aralkyl group, linear or branched alkoxy group, linear or linear represented by R _{1 to} R ₄₈ described above When it becomes a branched alkylthio group, the alkyl chain part of these substituents may have a substituent as needed. However, the substituent in that case or “substituent” in the description “may be substituted” or “may have a substituent” is a water-soluble group such as a sulfonic acid group, a carboxylic acid group, or a hydroxyl group. Not included.

  Examples of the substituent include the following. Alkoxy groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group; methoxymethoxy group, ethoxymethoxy group, propoxymethoxy Groups, ethoxyethoxy groups, propoxyethoxy groups, methoxybutoxy groups, etc., alkoxyalkoxy groups having 2 to 12 carbon atoms; methoxymethoxymethoxy groups, methoxymethoxyethoxy groups, methoxyethoxymethoxy groups, methoxymethoxyethoxy groups, ethoxyethoxymethoxy groups, etc. An alkoxyalkoxyalkoxy group having 3 to 15 carbon atoms; an aryloxy group having 6 to 12 carbon atoms such as a phenoxy group, a tolyloxy group, a xylyloxy group and a naphthyloxy group; an alkenyl having 2 to 12 carbon atoms such as an allyloxy group and a vinyloxy group Aryloxy group and the like.

  Further, as other substituents, heterocyclic groups such as 2-thienyl group, 2-pyridyl group, 4-piperidyl group, morpholino group; cyano group; nitro group; hydroxy group; mercapto group; methyl mercapto group, ethyl mercapto group An alkylthio group such as N, N-dimethylamino group, N, N-diethylamino group, etc .; a methylsulfonylamino group, an ethylsulfonylamino group, an n-propylsulfonylamino group; An alkylsulfonylamino group having 1 to 6 carbon atoms such as: a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; an alkylcarbonyl group such as a methylcarbocarbonyl group, an ethylcarbonyl group or an isopropylcarbonyl group; a methoxycarbonyl group, an ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl C2-C7 alkoxycarbonyl groups such as n-butoxycarbonyl group; carbon numbers such as methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group An alkoxycarbonyloxy group having 2 to 7 carbon atoms such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an isopropoxycarbonyloxy group, and an n-butoxycarbonyloxy group; Etc. The position of these substituents is not particularly limited, and the number of substituents can be in the range of 1 to 4. In the case of having a plurality of substituents, the species may be different.

(Optical recording medium)
Next, the optical recording medium will be described.
The optical recording medium to which the present embodiment is applied is at least a substrate, an organic dye compound A having an absorption maximum in a chloroform or methanol solution of 340 nm or more and 440 nm or less, and an absorption maximum in a chloroform or methanol solution of 500 nm or more, And a recording layer containing a metal complex compound B of 900 nm or less. If necessary, an undercoat layer, a reflective layer, a protective layer and the like may be further provided.

FIG. 1 is a diagram for explaining an optical recording medium to which the present embodiment is applied. FIG. 1 (a) is a first embodiment, and FIG. 1 (b) is a second embodiment. An optical recording medium 10 shown in FIG. 1A includes a substrate 1 made of a light-transmitting material, a recording layer 2 provided on the substrate 1, a reflective layer 3 and a protective layer laminated on the recording layer 2. 4 are stacked in order. In the optical recording medium 10, information is recorded / reproduced by laser light emitted from the substrate 1 side.
For convenience of explanation, in the optical recording medium 10, the side where the protective layer 4 exists is the upper side, the side where the substrate 1 exists is the lower side, and the surfaces of each layer corresponding to these directions are the upper and lower surfaces of each layer, respectively. And

  As the substrate 1, various materials can be used as long as they are basically transparent at the wavelengths of recording light and reproducing light. Specific examples include resins such as acrylic resins, methacrylic resins, polycarbonate resins, polyolefin resins (particularly amorphous polyolefins), polyester resins, polystyrene resins, and epoxy resins; and glass. Moreover, the structure which provided the resin layer which consists of radiation curable resins, such as photocurable resin, on glass is mentioned. Among these, from the viewpoints of high productivity, cost, moisture absorption resistance, etc., the polycarbonate resin used in the injection molding method, and from the viewpoints of chemical resistance and moisture absorption resistance, amorphous polyolefin is preferable. Furthermore, glass is preferable from the viewpoint of high-speed response and the like.

  When a resin substrate 1 is used, or when a substrate 1 having a resin layer provided on the side in contact with the recording layer (upper side) is used, guide grooves and pits for recording / reproducing light are formed on the upper surface. Also good. Examples of the shape of the guide groove include a concentric shape and a spiral shape based on the center of the optical recording medium 10. When forming spiral guide grooves, the groove pitch is preferably about 0.2 μm to 1.2 μm.

  The recording layer 2 is formed directly on the upper side of the substrate 1 or on the upper side of an undercoat layer or the like provided on the substrate 1 as necessary, and the maximum absorption wavelength (λmax) of the organic dye compound A in a chloroform or methanol solution. ) Contains a compound having a wavelength of 340 nm or more and 440 nm or less, and a metal complex compound B having a maximum absorption wavelength (λmax) in a chloroform solution or a methanol solution of 500 nm or more and 900 nm or less. The organic dye compound A and the metal so that the content of the organic dye compound A in the recording layer 2 is greater than the content of the metal complex compound B and the light resistance x when measured by the following test method is 30% or more. Complex compound B is contained.

The decomposition start temperature of the metal complex compound B is preferably not higher than the decomposition start temperature of the organic dye compound A. When the decomposition temperature of the metal complex compound B is lower than the decomposition temperature of the organic dye compound A, the decomposition temperature of the entire recording layer 2 can be lowered, and the recording sensitivity of the recording layer 2 can be improved.
The difference between the decomposition temperature of the metal complex compound B and the decomposition temperature of the organic dye compound A is preferably 5 ° C or higher, more preferably 10 ° C or higher, preferably 50 ° C or lower, more preferably 40 ° C or lower.

  The decomposition start temperature of the present embodiment is 30 by a differential thermal balance method in which a pigment amount of 3 mg to 4 mg is placed in an aluminum pan at a heating rate of 10 ° C./min (min) in the air or in a nitrogen flow. It is determined by measuring TG-DTA from ℃ to 600 ℃. In the weight loss process where the weight loss is 10% or more, the intersection of the tangent lines of the weight loss before and after the weight loss is set as the weight loss start temperature of the weight loss process.

  Examples of the method for forming the recording layer 2 include various commonly used thin film forming methods such as a vacuum deposition method, a sputtering method, a doctor blade method, a casting method, a spin coating method, and an immersion method. From the viewpoint of mass productivity and cost, the spin coating method is preferable, and from the viewpoint of obtaining the recording layer 2 having a uniform thickness, the vacuum evaporation method or the like is more preferable than the coating method. In the case of film formation by a spin coating method, the rotation speed is preferably 500 rpm to 15000 rpm. In some cases, after spin coating, a treatment such as heating or solvent vapor may be applied.

  When the recording layer 2 is formed by a coating method such as a doctor blade method, a cast method, a spin coating method, or a dipping method, the organic dye compound A and the metal complex compound B are dissolved and applied to the substrate 1. The coating solvent is not particularly limited as long as it is a solvent that does not erode the substrate 1 and is capable of producing a solution having a concentration that can be detected with a spectrophotometer, and is soluble in the organic dye compound A and the metal complex compound B. Not. Specifically, for example, ketone alcohol solvents such as diacetone alcohol and 3-hydroxy-3-methyl-2-butanone; cellosolv solvents such as methyl cellosolve and ethyl cellosolve; chain forms such as n-hexane and n-octane Hydrocarbon solvents: Cyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, n-butylcyclohexane, tert-butylcyclohexane, cyclooctane; tetrafluoropropanol, octafluoropentanol, hexafluorobutanol, etc. Examples include perfluoroalkyl alcohol solvents; hydroxycarboxylic acid ester solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate.

When using the vacuum deposition method, for example, if necessary, recording layer components such as other dyes and various additives are placed in a crucible installed in the vacuum vessel, and the inside of this vacuum vessel is filled with an appropriate vacuum pump. Then, after evacuating to about 10 ⁻² Pa to 10 ⁻⁵ Pa, the crucible is heated to evaporate the components of the recording layer, and vapor deposited on the substrate placed facing the crucible to form the recording layer 2. .

  Further, in order to improve stability and light resistance, the recording layer 2 further includes a transition metal chelate compound (for example, acetylacetonate chelate, bisphenyldithiol, salicylaldehyde oxime, bisdithio-α-) as a singlet oxygen quencher. Diketone and the like) or a recording sensitivity improver such as a metal compound may be added to improve the recording sensitivity. Here, the metal compound refers to a compound in which a metal such as a transition metal is included in the compound in the form of atoms, ions, clusters, etc., for example, ethylenediamine complex, azomethine complex, phenylhydroxyamine complex, phenanthroline complex. Organic metal compounds such as dihydroxyazobenzene complex, dioxime complex, nitrosoaminophenol complex, pyridyltriazine complex, acetylacetonate complex, metallocene complex, and porphyrin complex. Although it does not specifically limit as a metal atom, It is preferable that it is a transition metal. The transition metal chelate compounds and metal compounds listed here do not have an absorption maximum in a chloroform or methanol solution of 500 nm or more and 900 nm or less.

  The recording layer 2 may be used in combination with a plurality of organic dye compounds A as required. In that case, all the plural types (total) are regarded as the organic dye compound A. Furthermore, in the recording layer 2, an optical recording medium 10 corresponding to recording / reproduction using a plurality of types of laser beams belonging to different wavelength bands can be manufactured by using the metal complex compound used in combination with the organic dye compound A. it can.

  In addition to the metal complex compound of the present embodiment, other types of dyes other than the organic dye compound A include benzophenone dyes, phthalocyanine dyes, naphthalocyanine dyes, cyanine dyes, azo compounds, squarylium as necessary. And dyes such as azo dyes, triarylmethane dyes, merocyanine dyes, azurenium dyes, naphthoquinone dyes, anthraquinone dyes, indophenol dyes, xanthene dyes, oxazine dyes, and pyrylium dyes. Furthermore, a binder, a leveling agent, an antifoaming agent, etc. can also be used together as needed. Preferable binders include polyvinyl alcohol, polyvinyl pyrrolidone, nitrocellulose, cellulose acetate, ketone resin, acrylic resin, polystyrene resin, urethane resin, polyvinyl butyral, polycarbonate, polyolefin and the like.

The film thickness of the recording layer 2 is not particularly limited because a suitable film thickness varies depending on the recording method and the like. It is 1 nm or more, preferably 5 nm or more. However, if it is too thick, there is a possibility that recording cannot be performed satisfactorily, and it is usually 300 nm or less, preferably 200 nm or less, more preferably 100 nm or less.
The recording layer 2 has an extinction coefficient (imaginary part of complex refractive index) k at a recording and reproducing light wavelength of 0 to 0.50, preferably 0.05 to 0.35. Further, the refractive index (real part of the complex refractive index) n is in the range of 1 to 3, preferably 1.5 to 2.5.

As a method of measuring the film thickness of the recording layer 2 and managing the film thickness so as to have a predetermined value, the recording layer 2 is irradiated with laser light, and the absorption intensity of the recording dye layer constituting the recording layer 2 is determined. That is, there is a method of measuring and managing the film thickness of the recording layer 2 by measuring the transmission spectrum.
However, in this method, it may be difficult to measure the film thickness of the recording layer 2 having a maximum absorption of 400 nm or less. The reason why it is difficult to measure the film thickness of the recording layer 2 is that the maximum absorption of the material used for the substrate 1 of the optical recording medium 10 is often 400 nm or less, which overlaps with the maximum absorption of the recording layer 2. In addition, if the wavelength of the laser beam to be irradiated becomes small (especially 500 nm or less), the influence of the diffraction of the laser beam by the guide groove formed on the substrate 1 becomes large, and it is considered that accurate data cannot be measured.

  In the present embodiment, the transmission spectrum of the metal complex compound B having a maximum absorption of 500 nm or more and 900 nm or less, not the organic dye compound A (maximum absorption of 340 nm or more and 440 nm or less) contained in the recording layer 2 is shown. By measuring, the above-described problems can be solved, the accurate film thickness of the recording layer 2 can be measured, and the optical recording medium 10 having an optimum film thickness can be provided.

  The reflective layer 3 is formed on the recording layer 2. The thickness of the reflective layer 3 is preferably 50 nm to 300 nm. As the material of the reflective layer 3, a material having a sufficiently high reflectance at the wavelength of the reproduction light, for example, a metal such as Au, Al, Ag, Cu, Ti, Cr, Ni, Pt, Ta, Pd, alone or an alloy Can be used. Among these, Au, Al, and Ag have high reflectivity and are suitable as the material for the reflective layer 3.

  In addition to these metals as main components, other materials may be added. Here, the main component means one having a content of 50% or more. Examples of materials other than the main component include Mg, Se, Hf, V, Nb, Ru, W, Mn, Re, Fe, Co, Rh, Ir, Cu, Zn, Cd, Ga, In, Si, Mention may be made of metals and semi-metals such as Ge, Te, Pb, Po, Sn, Bi, Ta, Ti, Pt, Pd, Nd.

  Among them, those containing Ag as a main component are particularly preferable because they are low in cost, easily produce high reflectivity, and obtain a beautiful white background when a print receiving layer described later is provided. For example, an alloy containing about 0.1 atomic% to 5 atomic% of one or more selected from Au, Pd, Pt, Cu, and Nd in Ag has high reflectivity, high durability, high sensitivity, and low cost. It is preferable. Specifically, for example, an AgPdCu alloy, an AgCuAu alloy, an AgCuAuNd alloy, an AgCuNd alloy, or the like. As a material other than metal, a multilayer film can be formed by alternately stacking low refractive index thin films and high refractive index thin films, and this can be used as the reflective layer 3.

  Examples of the method for forming the reflective layer 3 include sputtering, ion plating, chemical vapor deposition, and vacuum vapor deposition. In addition, a known inorganic or organic intermediate layer or adhesive layer may be provided on the substrate 1 or under the reflective layer 3 in order to improve reflectivity, improve recording characteristics, and improve adhesion. it can.

The protective layer 4 is formed on the reflective layer 3. The material of the protective layer 4 is not particularly limited as long as it protects the reflective layer 3 from external force. Examples of the organic material include thermoplastic resins, thermosetting resins, electron beam curable resins, and UV curable resins.
Examples of the inorganic substance include silicon oxide, silicon nitride, MgF ₂ and SnO ₂ .

  When a thermoplastic resin, a thermosetting resin, or the like is used, the protective layer 4 can be formed by applying a coating solution prepared by dissolving in a suitable solvent on the reflective layer 3 and drying it. When a UV curable resin is used, it is directly applied on the reflective layer 3, or a coating solution prepared by dissolving in a suitable solvent is applied on the reflective layer 3 and cured by irradiation with UV light. Thus, the protective layer 4 can be formed. Examples of the UV curable resin include acrylate resins such as urethane acrylate, epoxy acrylate, and polyester acrylate. These materials may be used alone or as a mixture of plural kinds. The protective layer 4 may be formed as a single layer or a multilayer.

  As a method for forming the protective layer 4, as with the recording layer 2, a coating method such as a spin coating method and a casting method, a sputtering method, a chemical vapor deposition method, and the like are used. Among these, a spin coating method is preferable. The film thickness of the protective layer 4 is generally 0.1 μm or more, preferably 3 μm or more because a certain degree of thickness is required to fulfill its protective function. However, if it is too thick, not only does the effect not change, but it may take a long time to form the protective layer 4 and the cost may increase, so it is usually 100 μm or less, preferably 30 μm or less.

As described above, the layer structure of the optical recording medium 10 has been described by taking as an example the structure in which the substrate, the recording layer, the reflective layer, and the protective layer are laminated in this order. However, other layer structures may be employed. I do not care.
For example, another substrate 1 may be bonded to the upper surface of the protective layer 4 in the above layer structure, or to the upper surface of the reflective layer 3 by omitting the protective layer 4 from the above layer structure. The substrate 1 at this time may be the substrate itself without any layer, or may have an arbitrary layer such as the reflective layer 3 on the bonded surface or the opposite surface. Similarly, the optical recording medium 10 having the layer structure of the above example, or the optical recording medium 10 in which the protective layer 4 is omitted from the layer structure of the above example, the upper surfaces of the protective layer 4 and / or the reflective layer 3 are mutually connected. Two sheets may be bonded to face each other.

Next, a second embodiment of the optical recording medium will be described.
FIG. 1B is a diagram for explaining a second embodiment of the optical recording medium. Portions common to the optical recording medium 10 of the first embodiment are denoted by the same reference numerals, and description thereof is omitted. An optical recording medium 20 shown in FIG. 1B includes a substrate 1 made of a light transmissive material, a reflective layer 3 provided on the substrate 1, a recording layer 2 laminated on the reflective layer 3, and a protective film. 5 are stacked in order. Information is recorded / reproduced on the optical recording medium 20 by a laser beam irradiated from the protective coating 5 side.

  The protective coating 5 may be a film or a sheet-like material bonded together by an adhesive, and by using the same material as the protective layer 4 described above, applying a coating liquid for film formation, and curing or drying. It may be formed. The thickness of the protective coating 5 is generally 0.1 μm or more, preferably 3 μm or more because a certain amount of thickness is required to fulfill its protective function. However, if it is too thick, not only the effect does not change, but also the formation of the protective coating 5 may take time and the cost may increase, and therefore it is usually 300 μm or less, preferably 200 μm or less. Incidentally, the recording layer 2, the reflective layer 3 and the like can usually be the same as those in the optical recording medium 10 described above. However, in this layer structure, the substrate 1 does not have to be transparent, and therefore, in addition to the above-described materials, opaque resin, ceramic, metal (including alloy), and the like are used. Even in such a layer structure, an arbitrary layer may be provided between the above-described layers as necessary as long as the characteristics of the present invention are not impaired.

  Incidentally, as one means for increasing the recording density of the optical recording media 10 and 20, there is a case where the numerical aperture of the objective lens is increased. Thereby, the light spot condensed on the information recording surface can be miniaturized. However, if the numerical aperture of the objective lens is increased, the aberration of the light spot due to the warp of the optical recording media 10 and 20 tends to increase when the laser beam is irradiated for recording / reproduction. There are cases where a recording / reproducing signal cannot be obtained stably.

  Such aberration tends to increase as the film thickness of the transparent substrate 1 and the protective coating 5 through which the laser beam passes increases. Therefore, in order to reduce the aberration, it is preferable to make the substrate 1 and the protective coating 5 as thin as possible. . However, since the substrate 1 usually requires a certain thickness in order to ensure the strength of the optical recording media 10 and 20, in this case, the structure of the optical recording medium 20 (the substrate 1, the reflective layer 3, the recording layer 2, the protective film). It is preferable to employ an optical recording medium 20) having a basic layer structure of 5. Since the protective film 5 of the optical recording medium 20 can be easily made thinner than making the substrate 1 of the optical recording medium 10 thinner, the optical recording medium 20 is preferably used.

However, even in the structure of the optical recording medium 10 (the optical recording medium 10 having a basic layer structure including the substrate 1, the recording layer 2, the reflective layer 3, and the protective layer 4), the recording / reproducing laser beam is transparent. By reducing the thickness of the substrate 1 to about 50 μm to 300 μm, it becomes possible to use it with a reduced aberration.
In addition, after the other layers are formed, an ultraviolet curable resin layer, an inorganic thin film, etc. are used for the purpose of protecting the surface and preventing dust from adhering to the recording / reproducing laser beam incident surface (usually the lower surface of the substrate 1). May be formed on the surface that is not the recording / reproducing laser light incident surface (usually the upper surface of the reflective layer 3 or the protective layer 4) using various printers such as inkjet and thermal transfer, or various writing instruments. A print-receiving layer that can be filled in and printed may be provided.

  In the optical recording media 10 and 20 to which the present embodiment is applied, the laser light used for recording / reproducing information is preferably as short as possible from the viewpoint of realizing high-density recording, but in particular, the wavelength is from 350 nm to 530 nm. The laser beam is preferable. Typical examples of such laser light include laser light having center wavelengths of about 405 nm, about 410 nm, and about 515 nm (about allows a wavelength shift of about ± 5 nm).

  Laser light with a wavelength of 350 to 530 nm can be obtained by using a blue or green 515 nm high-power semiconductor laser light with a wavelength of 405 nm, 410 nm. In addition, for example, (a) a semiconductor laser beam capable of continuous oscillation having a fundamental oscillation wavelength of 740 nm to 960 nm, and (b) a solid capable of continuous oscillation having a fundamental oscillation wavelength of 740 nm to 960 nm excited by the semiconductor laser beam. It can also be obtained by converting the wavelength of any laser light of the laser light by a second harmonic generation element (SHG).

SHG may be any piezoelectric element that lacks inversion symmetry, but KDP, ADP, BNN, KN, LBO, compound semiconductors, and the like are preferable. As a specific example of the second harmonic, in the case of semiconductor laser light having a fundamental oscillation wavelength of 860 nm, 430 nm which is a harmonic of the fundamental oscillation wavelength, and in the case of solid laser light excited by semiconductor laser light, Cr-doped And 430 nm of a double wave from the LiSrAlF ₆ crystal (basic oscillation wavelength 860 nm).

  As a wavelength used for recording / reproducing, it is most preferable to use a wavelength of 405 nm, which is a short wavelength advantageous for increasing the density and for which a practical laser diode is supplied. When this wavelength is used, the maximum absorption wavelength (λmax) of the organic dye compound A is preferably 340 nm to 400 nm, more preferably 350 nm to 400 nm, and still more preferably 370 nm to 400 nm. It is.

When recording information on the optical recording media 10 and 20 to which the present embodiment is applied, the recording layer 2 (usually, the substrate 1 is transmitted from the substrate 1 side) is usually 0. A laser beam focused to about 4 to 0.6 μm is irradiated. The portion of the recording layer 2 irradiated with the laser beam is subjected to thermal deformation such as decomposition, heat generation and dissolution and a change in the complex refractive index by absorbing the energy of the laser beam, so that the optical characteristics change.
When the information recorded on the recording layer 2 is reproduced, the recording layer 2 is irradiated with a laser beam having a lower energy (usually from the same direction as when recording). In the recording layer 2, the difference between the reflectance of the portion where the change in optical characteristics (optical constant, phase difference, etc.) has occurred (that is, the portion where information is recorded) and the reflectance of the portion where no change has occurred. By reading, information is reproduced.

  Hereinafter, the present embodiment will be described more specifically based on examples. The present embodiment is not limited to the examples. Moreover, in the following table | surface, the organic pigment compound A is described as (A) component, the metal complex compound B as (B) component, and the compound as a comparison with the metal complex compound B is described as (C) component.

(Example of compound synthesis)
The method for synthesizing the compound used in the present embodiment is not particularly limited, but the method for synthesizing the azo compound represented by the formula (I) is described in, for example, JP-A-6-329616. The synthesis method is mentioned. Examples of the method for synthesizing the compound represented by the formula (II) include JP-A-63-057846. Examples of the method for synthesizing the compounds represented by formula (III) and formula (IV) include Japanese Patent Application No. 2001-372199 (USP6815033), and methods for synthesizing the compound represented by formula (V) include, for example, Can be synthesized by the method described in U.S. Pat.

(1) Synthesis of metal complex compound B To each methanol solution of the exemplified compounds (45), (46), and (47), a methanol solution of nickel acetate (0.6 equivalents) was added dropwise, followed by filtration. 1 was synthesized as a metal complex compound B (B component: B1 to B3). Also, filtered off was added dropwise aqueous nickel chloride solution and NH ₄ PF ₆ aqueous ethanol solution of Exemplified Compound (63), a metal complex compound (B component: B4) was synthesized. Table 1 shows the maximum absorption wavelength λmax and the molar extinction coefficient ε in the chloroform solution.

(2) Light resistance test An injection molding of a 0.6 wt% tetrafluoropropanol solution of an optical recording material prepared by mixing an organic dye compound A and a metal complex compound B at a predetermined composition ratio with a thickness of 0.6 mm and a diameter of 12 cm. A spin-coated polycarbonate resin substrate was spin-coated at 800 rpm, dried, then cut to a suitable size, prepared into a disk slice, a light resistance tester (manufactured by Toyo Seiki Seisakusho: Suntest XLS +) The Xe lamp was irradiated for 8 hours at 45 ° C. and 250 W / m ² .

For the absorption band capable of monitoring the organic dye compound A (that is, the absorption maximum in the wavelength range of 340 nm to 440 nm) in the optical recording material, the absorbance I ₀ of the absorption maximum before irradiation of the Xe lamp and the irradiation of the Xe lamp The absorbance I _{1 at} the absorption maximum was measured, and light resistance x = I ₁ / I ₀ was calculated. Usually, the wavelengths of I ₁ and I ₀ are the same. The higher the value, the better the light resistance.
Incidentally, the absorption of 440 nm or less of the mixed B component itself is very small compared to the A component, and considering the content at the time of mixing, the magnitude of the absorption of λmax can be regarded as almost the absorption of the A component.

(Examples 1-13, Comparative Examples 1-7)
The optical recording material having the composition shown in Table 2 was tested to evaluate the light resistance x. The results are shown in Table 2. In addition, the organic pigment compound A used the following compounds (A1, A2).

From the results of Table 2, the weight of the organic dye compound A / the weight of the metal complex compound B (hereinafter sometimes referred to as “(A) component / (B) component”) (A) component / (B) component = It can be confirmed that the optical recording materials (Examples 1 to 13) of 85/15 to 70/30 have a light resistance x of 50% or more carried out by the above-mentioned (2) light resistance test method and are excellent in light resistance. It was.
On the other hand, (A) component / (B) component = 100/0 and, for example, optical recording materials (Comparative Examples 1 to 7) of 90/10 excluding Example 10 have a light resistance x of less than 30%. It turns out that it is inferior to light resistance.

  The optical recording material used in Example 13 was dissolved in octafluoropentanol and adjusted to 0.6 wt%. A solution obtained by filtering this was dropped onto an injection-molded polycarbonate resin substrate having a diameter of 120 mm and a thickness of 0.6 mm, applied by a spinner method, and dried at 100 ° C. for 30 minutes after application. The maximum absorption wavelength (λmax) of this coating film was 388.5 nm, and the next largest absorption wavelength was 803.5 nm. FIG. 2 shows an absorption spectrum.

(Comparative Examples 8-11)
The compound A1 used in Example 1 and the following compounds C (C components: C1 to C4) were prepared with the compositions shown in Table 3 and subjected to a light resistance test. The results are shown in Table 3. C1 is an anthraquinone dye having λmax in the range of 500 nm to 900 nm, C2 is a cyanine dye, C3 is an azo compound that is not coordinated to the metal ion of B1, and C4 is λmax It is an azo metal complex compound outside the range of 500 nm to 900 nm. The maximum absorption wavelength (λmax) and ε of compound C are measured values in a chloroform solution for C1, C2, C4, and C5, and C3 in a methanol solution.

  From the results of Table 3, it can be seen that none of these (Comparative Examples 8 to 11) shows improvement in light resistance.

(Examples 14-17, Comparative Examples 12-15)
(1) Production Example of Optical Recording Medium An octafluoropentanol solution (0.6 wt%) of an optical recording material having the composition shown in Table 4 was formed with a groove having a track pitch of 425 nm, a groove width of 163 nm, and a groove depth of 90 nm and a diameter of 120 mm. Then, it was dropped onto an injection molded polycarbonate resin substrate having a thickness of 0.6 mm and applied by a spinner method. The coating was performed by increasing the rotation speed from 600 rpm to 4900 rpm over 25 seconds and holding at 4900 rpm for 5 seconds. Further, the recording layer was dried at 100 ° C. for 30 minutes. Next, a silver alloy film was formed to a thickness of 100 nm by a sputtering method to form a reflective layer. Thereafter, a protective coating agent made of a UV curable resin was applied by a spinner method, and UV light was irradiated to form a protective layer having a thickness of 5 μm. Furthermore, an optical recording medium for evaluation was prepared by adhering a 0.6 mm thick polycarbonate substrate to the surface having the protective layer using a delayed curable adhesive.

(2) Recording Example While rotating the optical recording medium described above at a linear velocity of 5.7 m / sec, with a laser beam having a wavelength of 405 nm (numerical aperture NA = 0.65 of the objective lens), (8T mark / 8T space) and A single frequency signal of (3T mark / 3T pace) was recorded on the groove, and each recording characteristic was measured. The results are shown in Table 4. T is a reference clock period corresponding to a frequency of 66 MHz. As a recording pulse strategy, the number of divided pulses is nT (n-1), the head recording pulse width is 2T, the subsequent recording pulse width is 0.6T, the bias power is 0.2mW, the reproduction power is 0.2mW, and the recording power is variable. It was.

  From the results of Table 4, the recording characteristics and the recording sensitivity of the optical recording media (Examples 14 to 17) using the optical recording material of (A) component / (B) component = 80/20, 70/30 are improved. I understand.

(Examples 18 to 21, Comparative Examples 16 to 19)
The optical recording media used in Examples 14 to 17 and Comparative Examples 12 to 15 were each read 10 ⁵ times with a reproducing light power of 0.2 mW, and the C / N reduction dB of 8T was measured to compare the deterioration of the reproducing light. did. The smaller the value, the better the degradation of the reproduction light. The results are shown in Table 5.

  From the results of Table 5, it is understood that the reproduction light deterioration of the optical recording media (Examples 18 to 21) using the optical recording material of (A) component / (B) component = 80/20, 70/30 is good. I understand.

(Example 22, Comparative Example 20)
Using the optical recording material having the composition shown in Table 6, an optical recording medium was prepared in the same manner as in Example 14, and the recording sensitivity and the like were measured. The organic dye compound A used the following compound (A3). The results are shown in Table 6.

  From the results in Table 6, it can be seen that the recording sensitivity is improved.

(Examples 23 to 26, Comparative Examples 21 to 26)
The optical recording materials having the compositions shown in Tables 7 and 8 were subjected to TG-DTA (DTG) measurement, and the thermal decomposition behavior was observed. In the TG-DTA (DTG) measurement, the powder of the optical recording material was ground in a mortar to make it uniform, and each sample (about 3.5 mg) was TG-DTA (DTG) (manufactured by Seiko Instruments Inc .: TG / DTA). 6200), the temperature was increased from 30 ° C. to 600 ° C. at a rate of 10 ° C./min, under the respective conditions of nitrogen and air as the flow gas. The results are shown in Tables 7 and 8, and the measurement charts are shown in FIGS.

  From the results of Tables 7 and 8, in the optical recording material (A) component / (B) component = 80/20, 70/30, the decomposition start temperature of TG shifts to a low temperature side beyond a simple weight ratio, It turns out that the DTG (differential peak of TG) peak temperature falls. Such thermal decomposition behavior is considered to improve the recording sensitivity of the optical recording medium.

(Examples 27 and 28, Comparative Examples 27 to 30)

  Similarly to Examples 23 to 26, TG-DTA (DTG) measurement was performed on the powder in which A5, B1, B3, and C5 were mixed at the ratio shown in Table 9, and the thermal decomposition behavior was observed. The conditions for TG-DTA (DTG) measurement are the same as in the previous section. The results are shown in Tables 9 and 10. A measurement chart of Comparative Example 27 is shown in FIG.

From the results of Tables 9 and 10, the (A) component / (B) component = 70/30 mixed powder also has a TG decomposition start temperature shifted to a low temperature side above a simple weight ratio. (TG differential peak) It can be seen that the peak temperature also decreases.
On the other hand, the powder mixed with C5, which is a non-gold-containing monoazo compound used as a comparative example, was decomposed by the mixing ratio first at the decomposition temperature of C5 alone, as is apparent from FIG. It is clear that it does not contribute to the decrease in the decomposition start temperature of the organic dye compound A for recording.

(Examples 29-44, Comparative Examples 31-39)
In the same manner as in Examples 1 to 13, the organic dye compounds A2, A4 and A5 were mixed with the metal complex compounds B5, B6, B3 and B4 in the ratios shown in Table 11 to prepare a dye-coated disk, and light resistance Table 11 shows the results of the light resistance test and the light resistance x calculated. In addition, Table 12 shows components of B5 and B6.

  From this result, it is clear that the light resistance is significantly improved by containing the metal complex compounds B3, B4, and B5 as compared with the results of 100% for A2, A4, and A5.

  Moreover, in FIG. 9, the result of Examples 1-13, Comparative Examples 1-7, Examples 29-44, and Comparative Examples 31-39 was shown in figure collectively. From FIG. 9, the A / B at which the desired light resistance x can be obtained differs depending on the combination of the light resistance of the organic dye compound A and the metal complex compound B when the metal complex compound B is 0% by weight. I understand.

  Further, as can be seen by comparing the effects on light resistance of B4, B5, and B6 whose maximum absorption wavelength (λmax) for A2 is 793.5 nm, 577 nm, and 579.5 nm, respectively, the maximum absorption wavelength (λmax) is 620 nm or less. The required amounts of B5 and B6 are larger than B4 having the maximum absorption wavelength (λmax) on the longer wavelength side, and in this example, the metal complex compound B is estimated to be 15% by weight or more. In order to make the light resistance x 50% or more, about 20% by weight is necessary.

FIG. 10 shows the relationship between the difference in maximum absorption wavelength (λmax) between the organic dye compound A2 and the metal complex compound B (Δλ = λmax (B) −λmax (A)) and the light resistance x.
That is, Comparative Example 1 (A2 = 100% Δλ = 0), Example 13 (A2 / B4 = 70/30, Δλ = 404.5 nm), Example 30 (A2 / B5 = 70/30, Δλ = 188 nm) ), Light resistance x of Example 32 (A2 / B6 = 70/30, Δλ = 190.5 nm) is shown. FIG. 10 shows that the longer the maximum absorption wavelength (λmax) of the metal complex compound B with respect to the organic dye compound A, the greater the effect on the light resistance x. In this example, it is understood that the wavelength is preferably longer by 100 nm or more in order to obtain the light resistance x50% or more. In order to obtain light resistance of 80% or more, the wavelength is preferably longer by 200 nm or more. In order to obtain more preferable light resistance x 90% or more, the wavelength is preferably longer by 300 nm or more.

(Comparative Example 40)
C4, which is not a metal complex compound and has a maximum absorption wavelength (λmax) of 354.5 nm and shorter than A4 (maximum absorption wavelength (λmax) = 377 nm), is converted into A4 / C4 = When a dye-coated disk was prepared as 70/30 and the light resistance x was examined, no improvement in light resistance was seen at 13.3%. The results are shown in Table 13.

  In addition, this application is based on the Japanese application (Japanese Patent Application No. 2004-052421) for which it applied on February 26, 2004, The whole is used by reference.

It is a figure explaining the optical recording medium with which this Embodiment is applied. FIG. 1 (a) is a first embodiment, and FIG. 1 (b) is a second embodiment. 14 is an absorption spectrum of the optical recording material used in Example 13. 16 is a TG-DTA chart measured in the air of the optical recording material used in Comparative Example 24. 27 is a TG-DTA chart measured in the air of the optical recording material used in Example 26. FIG. 27 is a chart of TG-DTA measured in the air of the optical recording material used in Comparative Example 26. FIG. 27 is a TG-DTA chart in the air of the optical recording material used in Comparative Example 27. FIG. It is an absorption spectrum of a film made of a metal complex compound B having a “weak absorption band” in the vicinity of 400 nm. It is an absorption spectrum of a film made of the metal complex compound B having no “weak absorption band” in the vicinity of 400 nm. It is a figure which shows the light resistance x of the optical recording material shown in Table 2 and Table 11. It is a figure which shows the relationship between the difference (((DELTA) (lambda) = (lambda) max (B)-(lambda) max (A))) of the maximum absorption wavelength ((lambda) max) of the organic pigment | dye compound A2 and the metal complex compound B, and light resistance x.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Recording layer, 3 ... Reflective layer, 4 ... Protective layer, 5 ... Protective film, 10, 20 ... Optical recording medium

Claims (22)

An organic dye compound A having a maximum absorption wavelength (λmax) of 340 nm to 440 nm;
A metal complex compound B having a maximum absorption wavelength (λmax) of 500 nm or more and 900 nm or less,
The content of the organic dye compound A is greater than the content of the metal complex compound B,
An optical recording material having a light resistance x calculated by the following formula of 30% or more.
Light resistance x = {(I ₁ / I ₀ ) × 100}
(However, in the above formula, I ₀ is the absorbance of the absorption maximum existing in the wavelength range of 340 nm to 440 nm in the absorption spectrum of the film measured by a spectrophotometer of the organic dye compound A and the metal complex compound B mixture). I ₁ is present in a wavelength range of 340 nm to 440 nm in the absorption spectrum of the film measured by a spectrophotometer after the film of the organic dye compound A and the metal complex compound B mixture is subjected to light irradiation treatment. It is the absorbance at the absorption maximum.) The organic dye compound A is subjected to a light irradiation treatment on the absorption maximum (I _A0 ) existing in the wavelength range of 340 nm to 440 nm of the absorption spectrum of the film measured by a spectrophotometer, and the organic dye compound A film. And the light absorption x = {(I _A1 / I _A0 ) × 100} calculated using the absorbance (I _A1 ) of the absorption maximum existing in the wavelength range 340 nm to 440 nm of the absorption spectrum of the film measured after 2. The optical recording material according to claim 1, wherein the content is less than 30%. 3. The optical recording material according to claim 1, wherein the light resistance x is calculated by the following operation steps.
(Operation steps)
(Step 1) A solution containing the organic dye compound A and the metal complex compound B is spin-coated on a transparent substrate and then dried to prepare a dye-coated disk.
(Step 2) Using a spectrophotometer, the absorption spectrum of the dye-coated disk prepared in (Step 1) above is measured at a wavelength of 300 nm to 900 nm, and the absorbance of the absorption maximum existing in the wavelength range of 340 nm to 440 nm is expressed as I. ₀ .
(Step 3) The dye-coated disk prepared in (Step 1) was subjected to a light irradiation treatment in which a xenon lamp was irradiated at 250 W / m ² for 8 hours, and then an absorption spectrum was obtained under the same conditions as in (Step 2). Measure and set the absorbance at the absorption maximum existing in the wavelength range of 340 nm to 440 nm as I ₁ .
(Step 4) Based on (I ₀ ) in (Step 2) and (I ₁ ) in (Step 3), {(I ₁ / I ₀ ) × 100} is calculated.   When the maximum absorption wavelength (λmax) of the metal complex compound B is 500 nm to 620 nm, the content of the metal complex compound B when the total amount of the organic dye compound A and the metal complex compound B is 100% by weight 4. The optical recording material according to claim 1, wherein the amount% is 20% by weight or more and 40% by weight or less.   The difference between the maximum absorption wavelength (λmax) of the organic dye compound A and the maximum absorption wavelength (λmax) of the metal complex compound B is 100 nm or more. Optical recording material.   6. The optical recording material according to claim 1, wherein the metal complex compound B has a maximum absorption wavelength (λmax) of 680 nm to 900 nm.   The optical recording material according to claim 1, wherein the light resistance x is 50% or more.   The organic dye compound A is a γ-pyrone organic dye, γ-thiopyrone organic dye, γ-1,1-dioxothiopyrone organic dye, γ-pyridone organic dye, coumarin organic dye, carbostyril 8. The optical recording material according to claim 1, wherein the optical recording material is at least one selected from organic dyes and 1-thiocoumarin organic dyes.   9. The optical recording material according to claim 1, wherein the metal complex compound B is an azo metal complex compound or an indoaniline metal complex compound. The optical recording material according to claim 9, wherein the metal complex compound B is an azo metal complex compound comprising a metal ion and an azo compound represented by the following general formula (I).

(In Formula (I), Ring A is a nitrogen-containing heteroaromatic ring formed together with a carbon atom and a nitrogen atom, and XL is capable of coordinating a metal with X becoming an anion when L is eliminated. R ₁ and R ₂ each independently represents a hydrogen atom, a linear or branched alkyl group, a cyclic alkyl group, an aralkyl group or an alkenyl group, which are each condensed with adjacent substituents or with each other. R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, carbon A linear or branched alkenyl group having 2 to 12 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 12 carbon atoms, a linear or branched alkylthio group having 1 to 12 carbon atoms, A monocyclic saturated heterocyclic group, Androgenic atom, a nitro group, a cyano group, a mercapto group, hydroxy group, formyl group, acyl group represented by -COR _34, amino group represented by _-NR 35 _{R 36,} an acylamino group represented by -NHCOR _37, A carbamate group represented by —NHCOOR _38; a carboxylic acid ester group represented by —COOR _39; an acyloxy group represented by —OCOR _40; a carbamoyl group represented by —CONR ₄₁ R ₄₂ ; and —SO ₂ R ₄₃ . the sulfonyl group represented, sulfinyl group represented by -SOR _44, a sulfamoyl group represented by -SO _{2 NR} 45 _{R 46,} sulfonic acid ester group represented by -SO _{3 R 47,} at -NHSO ₂ R ₄₈ Represents a sulfonamide group represented by the formula (However, R ₃₄ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₃ , R) ₄₄ , R ₄₇ , R ₄₈ each independently represents a hydrocarbon group or a heterocyclic group, and R ₃₅ , R ₃₆ , R ₄₁ , R ₄₂ , R ₄₅ , R ₄₆ each independently represent a hydrogen atom, It represents either a hydrocarbon group or a heterocyclic group.)) In the azo compound represented by the general formula (I), ring A represents a 5- or 6-membered monocyclic or bicondensed nitrogen-containing heteroaromatic ring, XL represents a hydroxy group, a sulfonic acid group, an acylamino group, Represents a sulfonamide group, a mercapto group, or a carboxyl group, and R ₁ and R ₂ each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or 7 carbon atoms. -12 represents an aralkyl group, or each forms a saturated condensed ring with adjacent substituents or each other, R ₃ , R ₄ , and R ₅ are each independently a hydrogen atom or a linear or branched group having 1 to 8 carbon atoms Alkyl group, C 7-12 aralkyl group, C 1-8 linear or branched alkoxy group, C 1-8 linear or branched alkylthio group, monocyclic 5-6 membered saturated Heterocyclic group, halogen atom, di B group, a cyano group, a mercapto group, hydroxy group, acyl group represented by -COR _34, amino group represented by _-NR 35 _{R 36,} an acylamino group represented by -NHCOR _37, represented by -NHCOOR ₃₈ A carbamate group, a carboxylate group represented by -COOR ₃₉ , an acyloxy group represented by -OCOR ₄₀ , a carbamoyl group represented by -CONR ₄₁ R ₄₂ , a sulfonyl group represented by -SO ₂ R ₄₃ , The optical recording material according to claim 10, wherein the optical recording material represents a sulfamoyl group represented by —SO ₂ NR ₄₅ R ₄₆ and a sulfonamide group represented by —NHSO ₂ R ₄₈ . 10. The optical recording material according to claim 9, wherein the metal complex compound B is a metal complex compound composed of a metal ion and an arbitrary anion and a compound represented by the following general formula (II).

(In the formula (II), R ₆ and R ₇ each independently represents a hydrogen atom, a linear or branched alkyl group, a cyclic alkyl group, an aralkyl group, or an alkenyl group, each of these being adjacent substituents or R _{8 to} R ₁₆ may each independently form a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or a carbon number. 2-12 linear or branched alkenyl group, C7-18 aralkyl group, C1-12 linear or branched alkoxy group, C1-12 linear or branched alkylthio group, saturation Or an unsaturated heterocyclic group, an aryl group having 6 to 18 carbon atoms, a halogen atom, a nitro group, a cyano group, a mercapto group, a hydroxy group, a formyl group, an acyl group represented by —COR ₃₄ , —NR ₃₅ R ₃ An amino group represented by _6; an acylamino group represented by —NHCOR _37; a carbamate group represented by —NHCOOR _38; a carboxylic acid ester group represented by —COOR _39; an acyloxy group represented by —OCOR ₄₀ ; A carbamoyl group represented by —CONR ₄₁ R _42; a sulfonyl group represented by —SO ₂ R _43; a sulfinyl group represented by —SOR _44; a sulfamoyl group represented by —SO ₂ NR ₄₅ R ₄₆ ; ₃ represents a sulfonic acid ester group represented by R ₄₇ and a sulfonamide group represented by —NHSO ₂ R _48. (However, R ₃₄ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₃ , R ₄₄₎ , R ₄₇ and R ₄₈ each independently represents a hydrocarbon group or a heterocyclic group, and R ₃₅ , R ₃₆ , R ₄₁ , R ₄₂ , R _45. And R ₄₆ each independently represents a hydrogen atom, a hydrocarbon group, or a heterocyclic group.))   The optical recording material according to claim 12, wherein the arbitrary anion is a monovalent monodentate ligand.   14. The optical recording material according to claim 1, wherein the metal complex compound B is a metal complex compound having a divalent or trivalent transition metal ion.   The optical recording material according to claim 14, wherein the transition metal is at least one selected from the group consisting of nickel, cobalt, copper, iron, zinc, platinum, palladium, and manganese. 16. The optical recording material according to claim 1, wherein the organic dye compound A is selected from compounds represented by the following general formulas (III) and (IV).

(In the formula (III) or (IV), R _{17 to} R ₂₀ and R ₁₇ ′ to R ₂₀ ′ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a carbon number. C3-C12 cyclic alkyl group, C2-C12 linear or branched alkenyl group, C7-C18 aralkyl group, C1-C12 linear or branched alkoxy group, C1-C12 A linear or branched alkylthio group, a saturated or unsaturated heterocyclic group, an aryl group having 6 to 18 carbon atoms, a halogen atom, a nitro group, a cyano group, a mercapto group, a hydroxy group, a formyl group, and —COR ₃₄ An acyl group represented by —NR ₃₅ R ₃₆ , an acylamino group represented by —NHCOR ₃₇ , a carbamate group represented by —NHCOOR ₃₈ , and a carboxylic acid group represented by —COOR ₃₉ Steryl group, acyloxy group represented by —OCOR ₄₀ , carbamoyl group represented by —CONR ₄₁ R ₄₂ , sulfonyl group represented by —SO ₂ R ₄₃ , sulfinyl group represented by —SOR ₄₄ , —SO ₂ A sulfamoyl group represented by NR ₄₅ R ₄₆ , a sulfonic acid ester group represented by —SO ₃ R ₄₇ , and a sulfonamide group represented by —NHSO ₂ R ₄₈ (provided that R ₃₄ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₃ , R ₄₄ , R ₄₇ , R ₄₈ each independently represents a hydrocarbon group or a heterocyclic group, and R ₃₅ , R ₃₆ , R ₄₁ , R ₄₂ , R ₄₅ , R ₄₆ are each independently a hydrogen atom, a hydrocarbon group, and a heterocyclic group. _{However, R 17} and _{R 18, R 19} and _{R 20, R 17} 'and _{R 18',} and _{R 19} ' _{20 'are} each fused hydrocarbon ring or heterocyclic structure may be formed. The hydrocarbon ring and the heterocyclic ring may have a substituent.). X ₁ is an electron withdrawing X ₂ is a hydrogen atom or -QY (Q is a direct bond, an alkylene group having 1 or 2 carbon atoms, an arylene group or a heteroarylene group, and Y is an electron-withdrawing group. The alkylene group, the arylene group, and the heteroarylene group may have any substituent other than Y. The ring C may have a substituent together with C═O. Good carbocyclic ketone ring or heterocyclic ketone ring, wherein Z and Z ′ are —O—, —S—, —SO ₂ —, —NR ₂₁ — (wherein R ₂₁ represents a hydrogen atom, Optionally substituted hydrocarbon group, optionally substituted heterocyclic group, cyano group Hydroxy group), _{- NR} 22 _{R 23} amino groups _{(R 22, R 23} represented by each independently, a hydrogen atom, a hydrocarbon group or a heterocyclic group), or _-COR 24 _{(R 24} is a hydrocarbon Or an acyl group represented by —COR ₂₅ (wherein R ₂₅ is a hydrocarbon group or a heterocyclic group). 16. The optical recording material according to claim 1, wherein the organic dye compound A is a compound represented by the following general formula (V).

(In formula (V), X represents —O—, —S—, —NR ₃₃ —. R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , and R ₃₀ each independently represents a hydrogen atom or a carbon number of 1; -12 linear or branched alkyl group, C3-C12 cyclic alkyl group, C2-C12 linear or branched alkenyl group, C7-C18 aralkyl group, C1-C12 Linear or branched alkoxy group, linear or branched alkylthio group having 1 to 12 carbon atoms, aryl group having 6 to 18 carbon atoms, saturated or unsaturated heterocyclic group, halogen atom, nitro group, cyano group, mercapto Group, hydroxy group, formyl group, acyl group represented by -COR ₃₄ , amino group represented by -NR ₃₅ R ₃₆ , acylamino group represented by -NHCOR ₃₇ , carbamate group represented by -NHCOOR ₃₈ , -CO Carboxylic acid ester group represented by R _39, an acyloxy group represented by -OCOR _40, a carbamoyl group represented by _-CONR 41 _{R 42,} a sulfonyl group represented by -SO _{2 R 43,} tables in -SOR _{44 .R 31} representing the the sulfinyl _group, a sulfamoyl group represented by -SO _{2 NR} 45 _{R 46,} sulfonic acid ester group represented by -SO _{3 R 47,} sulfonamide group represented by -NHSO ₂ R ₄₈ , R ₃₂ and R ₃₃ each independently represents a hydrogen atom, a linear or branched alkyl group, a cyclic alkyl group, an aralkyl group, a linear or branched alkenyl group, or an acyl group, and R _{26 to} R _33. Adjacent two of them may combine to form a saturated hydrocarbon ring or a saturated heterocyclic ring, provided that R ₃₄ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₃ , R ₄₄ , R ₄₇ , R ₄₈ each independently represents a hydrocarbon group or a heterocyclic group, and R ₃₅ , R ₃₆ , R ₄₁ , R ₄₂ , R ₄₅ , R ₄₆ are Each independently represents a hydrogen atom, a hydrocarbon group, or a heterocyclic group.) In the general formula (V), X is —O— or —NR ₃₃ —, and R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , and R ₃₀ are each independently a hydrogen atom or a carbon number of 1 to 8 straight or branched alkyl groups, 3 to 8 carbon cyclic alkyl groups, 7 to 12 carbon aralkyl groups, 1 to 8 straight or branched alkoxy groups, 1 to 8 carbon atoms Chain or branched alkylthio group, aryl group having 6 to 12 carbon atoms, saturated or unsaturated monocyclic or bicyclic heterocyclic group, halogen atom, nitro group, cyano group, mercapto group, hydroxy group, formyl group, acyl group represented by -COR _34, amino group represented by _-NR 35 _{R 36,} an acylamino group represented by -NHCOR _37, carbamate group represented by -NHCOOR _38, carbo represented by -COOR ₃₉ Ester group, an acyloxy group represented by -OCOR _40, a carbamoyl group represented by _-CONR 41 _{R 42,} a sulfonamide group represented by _{-NHSO 2 R 48, R 31,} R 32, R 33 is Are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and R ₂₉ and R ₃₁ , R ₃₀ and 16. The optical recording material according to claim 15, wherein one or both of R ₃₂ has a structure which may form a saturated hydrocarbon ring or a saturated heterocyclic ring.   The optical recording material according to claim 1, wherein the metal complex compound B inhibits crystallization of the organic dye compound A.   The optical recording material according to any one of claims 1 to 19, wherein a decomposition start temperature of the metal complex compound B is not higher than a decomposition start temperature of the organic dye compound A. An optical recording medium capable of recording or reproducing information,
A substrate,
A recording layer provided on the substrate and capable of recording or reproducing the information by light irradiation;
21. An optical recording medium, wherein the recording layer contains the optical recording material according to any one of claims 1 to 20.   The optical recording medium according to claim 21, wherein the light is laser light having a wavelength of 350 nm to 530 nm.

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