JP2003237233A - Optical recording medium and method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic coloring matter optical recording medium where image data can be recorded/regenerated using a shorter wavelength blue laser beam. <P>SOLUTION: The optical recording medium has a recording layer which permits the recording and regeneration of information by a laser beam on a substrate and contains a chemical compound represented by formula (I) or a chemical compound by formula (II). The optical recording method records information in the optical recording medium using a laser beam with a wavelength of 350 to 530 nm. In formula (I) and formula (II), R<SP>1</SP>to R<SP>4</SP>are each H or an optional substituent group and at least two substituent groups to which R<SP>1</SP>to R<SP>4</SP>are adjacent can be combined to form a hydrocarbon ring structure or a heterocyclic structure. X<SP>1</SP>is an electron-inductive group; X<SP>2</SP>is H or -Q-Y (Q is a directly bonded or coupled chain; and Y is an electron-inductive group). X<SP>3</SP>is O, S or =N-R<SP>6</SP>. R<SP>6</SP>is H, a hydrocarbon group or the like.) R<SP>5</SP>is H, a hydrogen group or the like. Ring A is a carbocyclic or heterocyclic ketone ring together with > C=O. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a write-once type optical recording medium and a recording method using an organic dye in a recording layer, and more specifically to a write-once type optical recording medium compatible with a blue laser and the optical recording medium. The recording method of.

[0002]

2. Description of the Related Art Currently, CD-R / RW, DVD-R / R
Since various optical recording media such as W and MO can store a large amount of information and are easily random-accessed, they are widely recognized and popular as external storage devices in information processing devices such as computers. Among these, the organic dye-based optical recording media represented by CD-R and DVD-R are considered to be superior 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, a high-density recordable / reproducible optical recording medium using a laser having a short oscillation wavelength such as a blue laser, which has been remarkably developed, is being proposed.

[0003]

DISCLOSURE OF THE INVENTION Generally, CD-R and D
In the case of an optical recording medium commercially available as VD-R, for example, a CD-R is suitable for recording / reproducing with a laser beam having a wavelength of about 780 nm, and a DVD-R has a wavelength.
It is designed to be suitable for recording / reproducing with laser light of 600 to 700 nm. In such a recording medium suitable for optical recording / reproduction using a laser beam of a relatively long wavelength, when recording / reproducing with a shorter wavelength laser, the reflectance is low and recording / reproducing cannot be performed. have. An object of the present invention is to provide an organic dye-based optical recording medium capable of recording / reproducing with a blue laser having a shorter wavelength.

[0004]

As a result of various investigations by the present inventors on organic dyes having high sensitivity to blue laser, the compounds represented by the above general formulas [I] and [II] correspond to blue laser. The present invention has been achieved by knowing that it can be used for a recording layer of an optical recording medium. That is, the gist of the present invention is an optical recording medium in which a recording layer capable of recording or reproducing information with a laser is provided on a substrate, and the recording layer contains a compound represented by the following general formula [I],
Alternatively, an optical recording medium comprising a compound represented by the following general formula [II], and an optical recording comprising recording information on the optical recording medium using a laser beam having a wavelength of 350 nm to 530 nm In the way.

[0005]

[Chemical 3] {In the formula, R ^{1 to} R ⁴ represent a hydrogen atom or an arbitrary substituent, and at least two adjacent substituents of R ^{1 to} R ⁴ may be bonded to each other to form a hydrocarbon ring or a heterocyclic structure. The hydrocarbon ring and the heterocycle may have a substituent. X ¹ represents an electron-withdrawing group, X ² represents a hydrogen atom or-
Represents Q-Y. (Q represents a direct bond, an alkylene group having 1 or 2 carbon atoms, an arylene group or a heteroarylene group, and Y represents an electron-withdrawing group.) The alkylene group, the arylene group, and the heteroarylene group are other than Y. May have an arbitrary substituent. X ³ represents an oxygen atom, a sulfur atom or = N-R ^6. (R ⁶ is a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted heterocyclic group,
Represents a cyano group and a hydroxy group. R ⁵ is a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted heterocyclic group, a cyano group, a hydroxy group, —NR
⁷ R ⁸ (R ⁷ and R ⁸ each independently represent a hydrogen atom, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group), or —COR ⁹ (R ⁹ is an optionally substituted group. Represents an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group), and R ⁵ is bonded to R ⁴ to form an optionally substituted hydrocarbon ring or an optionally substituted heterocyclic structure. May be. }

[0006]

[Chemical 4] {In the formula, R ^{1 to} R ⁴ represent a hydrogen atom or an arbitrary substituent, and at least two adjacent substituents of R ^{1 to} R ⁴ may be bonded to each other to form a hydrocarbon ring or a heterocyclic structure. The hydrocarbon ring and the heterocycle may have a substituent. Ring A represents a carbocyclic ketone ring or a heterocyclic ketone ring which may have a substituent together with> C═O. X ³ represents an oxygen atom, a sulfur atom or = N-R ^6. (R ⁶ represents a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted heterocyclic group, a cyano group or a hydroxy group.) R ⁵ is a hydrogen atom, an optionally substituted hydrocarbon group, or a substituted Optionally substituted heterocyclic group, cyano group, hydroxy group, -NR ⁷ R
⁸ (R ⁷ and R ⁸ each independently represent a hydrogen atom, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group), or —COR ⁹ (R ⁹ may be substituted. Represents a hydrocarbon group or an optionally substituted heterocyclic group), and R ⁵ may combine with R ⁴ to form an optionally substituted hydrocarbon ring or an optionally substituted heterocyclic structure. good. }

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The compound used in the recording layer of the present invention is 350 to 5
A dye compound having a suitable absorption in the blue light region of 30 nm and suitable for recording with a blue laser is preferable. In the present invention, the dye compounds represented by the above general formulas [I] and [II] are used as the dye. The compounds represented by the general formulas [I] and [II] will be described below.

The above-mentioned general formula showing the dye compound according to the present invention
In [I] and [II], R ^{1 to} R ⁴ each independently represent a hydrogen atom and an optional substituent, and the optional substituent may be further substituted. Examples of the optional substituent include the following. Methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert
-Butyl group, n-heptyl group, etc., which may be substituted, is a linear or branched alkyl group having 1 to 18 carbon atoms; cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, etc., which may be substituted A cyclic alkyl group of 3 to 18; a linear or branched alkenyl group of 2 to 18 carbon atoms which may be substituted, such as vinyl group, propenyl group, hexenyl group; substituted by cyclopentenyl group, cyclohexenyl group, etc. A cyclic alkenyl group having 3 to 18 carbon atoms; 2-
Heterocyclic groups which may be substituted such as thienyl group, 2-pyridyl group, 4-piperidyl group and morpholino group; C 6-18 carbon atoms which may be substituted such as phenyl group, tolyl group, xylyl group and mesityl group An aryl group; an optionally substituted aralkyl group having 7 to 20 carbon atoms such as a benzyl group and a phenethyl group;
A methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, etc., which may be substituted and has a linear or branched alkoxy group having 1 to 18 carbon atoms; Propenyloxy group, butenyloxy group, pentenyloxy group, etc., which may be substituted and has a linear or branched alkenyloxy group having 3 to 18 carbon atoms; methylthio group, ethylthio group, n-propylthio group, n-butylthio group, sec- Examples thereof include a linear or branched alkylthio group having 1 to 18 carbon atoms which may be substituted, such as a butylthio group and a tert-butylthio group.

Other specific examples include halogen atoms such as fluorine atom, chlorine atom and bromine atom; nitro group; nitroso group; cyano group; isocyano group; cyanato group; isocyanato group; thiocyanato group; isothiocyanato group; mercapto group; hydroxy group; a hydroxyamino group; a formyl group; a sulfonic group; a carboxyl group; an acyl group represented by -COR ^20, amino group represented by -NR ²¹ R ^22, -N
Acylamino group represented by HCOR ²³ , -NHCOOR
Carbamate group represented by ²⁴ , carboxylic acid ester group represented by -COOR ²⁵ , acyloxy group represented by -OCOR ²⁶ , carbamoyl group represented by -CONR ²⁷ R ²⁸ , represented by -SO ₂ R ²⁹ Sulfonyl group, -SO ₂ NR
Examples thereof include a sulfamoyl group represented by ³⁰ R ³¹ , a sulfonate group represented by —SO ₃ R ³² , and a sulfonamide group represented by —NHSO ₂ R ³³ .

The positions of these substituents are not particularly limited,
The number of substituents can be in the range of 1 to 4. When it has a plurality of substituents, it may be the same or different. Here, R ²⁰ , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁹ , R ³² , and R ³³ each represent an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and R ²¹ , R ²² , R ²⁷ , R ²⁸ , R ³⁰ , and R ^{31 each} represent a hydrogen atom, an optionally substituted hydrocarbon group, or an optionally substituted heterocyclic group.

The hydrocarbon groups represented by R ^{20 to} R ³³ are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-heptyl group. A linear or branched alkyl group having 1 to 18 carbon atoms such as groups, cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclic alkyl group having 3 to 18 carbon atoms such as adamantyl group, vinyl group, propenyl group, hexenyl group, etc. 3 to 1 carbon atoms such as a linear or branched alkenyl group having 2 to 18 carbon atoms, a cyclopentenyl group, a cyclohexenyl group, etc.
It represents an aralkyl group having 7 to 20 carbon atoms such as a cyclic alkenyl group having 8 carbon atoms, a benzyl group and a phenethyl group, and an aryl group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group and a mesityl group. The alkyl chain portion and the aryl group portion of these groups may be further substituted with a substituent which the alkyl chain portion of R ^{1 to} R ⁴ described later may have.

The heterocyclic group represented by R ^{20 to} R ³³ is 4
It may be a saturated heterocycle such as piperidyl group, morpholino group, 2-morpholinyl group and piperazyl group, or an aromatic heterocycle such as 2-furyl group, 2-pyridyl group, 2-thiazolyl group and 2-quinolyl group. Even if these contain multiple heteroatoms,
Further, it may have a substituent, and the bonding position does not matter. Preferred heterocycles are 5- or 6-membered saturated heterocycles, 5- or 6-membered monocycles, and their two condensed aromatic heterocycles.

[0013] More specifically, an acyl group which may be substituted represented by -COR ^20; amino group which may be substituted represented by -NR ²¹ R ^22; represented by -NHCOR ²³ substituted Optionally substituted acylamino group; -NHCOOR
^An optionally substituted carbamate group represented by ²⁴ ;-
An optionally substituted carboxylic acid ester group represented by COOR ²⁵ ; an optionally substituted acyloxy group represented by -OCOR ²⁶ ; an optionally substituted carbamoyl group represented by -CONR ²⁷ R ²⁸ ; optionally substituted sulfonyl group represented by _{^{-SO 2 R 2 9; -SO 2}} NR
³⁰ R ³¹ represents an optionally substituted sulfamoyl group; —SO ₃ R ³² represents an optionally substituted sulfonic acid ester group; —NHSO ₂ R ³³ represents an optionally substituted group. Preferred specific examples of each of the good sulfonamide groups are shown below.

Acyl group (-COR ²⁰ )

[Chemical 5]

Amino group (-NR ²¹ R ²² )

[Chemical 6]

Acylamino group (-NHCOR ²³ )

[Chemical 7]

Carbamate group (-NHCOOR ²⁴ )

[Chemical 8]

Carboxylic acid ester group (--COOR ²⁵ )

[Chemical 9]

Acyloxy group (--OCOR ²⁶ )

[Chemical 10]

Carbamoyl group (--CONR ²⁷ R ²⁸ ).

[Chemical 11]

Sulfonyl group (-SO ₂ R ²⁹ )

[Chemical 12]

Sulfamoyl group (--SO ₂ NR ³⁰ R ³¹ )

[Chemical 13]

Sulfonate group (-SO ₃ R ³² )

[Chemical 14]

Sulfonamide group (-NHSO ₂ R ³³ )

[Chemical 15]

A linear or branched alkyl group represented by R ^{1 to} R ⁴ , a cyclic alkyl group, a linear or branched alkenyl group,
The cyclic alkenyl group, the linear or branched alkoxy group, the linear or branched alkylthio group, and the alkyl chain portion of the alkyl group represented by R ^{20 to} R ³³ may further have a substituent. , For example: Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group and other alkoxy groups having 1 to 10 carbon atoms; methoxymethoxy group, ethoxymethoxy group, propoxymethoxy Group, ethoxyethoxy group, propoxyethoxy group, methoxybutoxy group, and other alkoxyalkoxy groups having 2 to 12 carbon atoms; methoxymethoxymethoxy group, methoxymethoxyethoxy group, methoxyethoxymethoxy group, methoxyethoxyethoxy group, ethoxyethoxymethoxy group, etc. An alkoxyalkoxyalkoxy group having 3 to 15 carbon atoms;
Aryloxy group having 6 to 12 carbon atoms such as phenoxy group, tolyloxy group, xylyloxy group, naphthyloxy group and the like; Allyloxy group, vinyloxy group and the like having 2 to 1 carbon atoms
2 alkenyloxy groups and the like are exemplified.

Further, as another substituent, a 2-thienyl group,
Heterocyclic groups such as 2-pyridyl group, 4-piperidyl group and morpholino group; cyano group; nitro group; hydroxyl group; amino group; N, N-dimethylamino group, N, N-diethylamino group, etc. 10 alkylamino group; alkylsulfonylamino group having 1 to 6 carbon atoms such as methylsulfonylamino group, ethylsulfonylamino group, n-propylsulfonylamino group; halogen atom such as fluorine atom, chlorine atom, bromine atom; methoxycarbonyl Group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group and the like having 2 to 2 carbon atoms
7-alkoxycarbonyl group; methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group and other alkylcarbonyloxy groups having 2 to 7 carbon atoms; methoxycarbonyloxy group Group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an isopropoxycarbonyloxy group, an n-butoxycarbonyloxy group, and other alkoxycarbonyloxy groups having 2 to 7 carbon atoms.

At least two adjacent substituents of R ^{1 to} R ⁴ can combine with each other to form a hydrocarbon ring or heterocyclic ring structure. The ring formed by two adjacent substituents, R ¹ and R ² , R ² and R ³ , and R ³ and R ^4, which are independently bonded to each other, may be a saturated or unsaturated hydrocarbon ring or a hetero atom. It may be a saturated or unsaturated heterocyclic ring containing one or more of the above, and the cyclic structure may be a monocyclic ring or a condensed ring. The number of ring members is not particularly limited, but a hydrocarbon ring and a heterocyclic ring are preferably 5 to 7 membered rings, and particularly preferably 5 to 6 membered rings. In addition, three adjacent substituents, for example, R ^{1 to} R ³ ,
R ^{2 to} R ⁴ may combine with each other to form a condensed ring. The preferred cyclic structures represented by these are shown below.

[0028]

[Chemical 16] (In the above ring structure, D¹~ D³Represents any substituent
You ) D¹~ D³The optional substituent of R is R¹~ R^FourThe alkyl
The substituent which the chain part may have is mentioned. D¹~ D³As
Preferably, a hydrogen atom, an alkyl group, an aryl group, ara
Examples thereof include a alkyl group, a hydroxy group and an alkoxy group.
Further, the ring of the above-mentioned cyclic structure has the above-mentioned substitution or non-substitution.
It may be substituted with an alternative alkyl group. This alkyl
Examples of the substituent that the group may have include, for example, R described above. ¹~ R^Fourof
The same kind of substituent as the alkyl chain moiety may have
Be done.

R¹~ R^FourPreferred as a substituent represented by
Those having 1 to 12 carbon atoms which may be substituted, or
A branched alkyl group having 3 to 12 carbon atoms which may be substituted.
Cyclic alkyl group, which may be substituted, has 2 to 12 carbon atoms
Chain or branched alkenyl group, 5- or 6-membered saturated heterocycle
Group, a 5- or 6-membered monocyclic or 2-condensed heteroaromatic ring group,
Optionally substituted aryl group having 6 to 18 carbon atoms, substituted
An optionally substituted aralkyl group having 7 to 20 carbon atoms, which is substituted
Good linear or branched alkoxy having 1 to 12 carbon atoms
Group, straight or branched chain having 1 to 12 carbon atoms which may be substituted
Alkylthio group, halogen atom, nitro group, cyano
Group, mercapto group, hydroxy group, -COR ²⁰Represented by
Acyl group, -NR^{twenty one}R^{twenty two}An amino group represented by
COR^{twenty three}An acylamino group represented by -NHCOOR^{twenty four}
A carbamate group represented by^{twenty five}Is represented by
Rubonate ester group, -OCOR²⁶Represented by
Xyl group, -CONR²⁷R²⁸A carbamoyl group represented by
-NHSO₂R³³The sulfonamide group represented by
R¹And R², R²And R³, R³And R^FourForm a ring
Is an optionally substituted 5- or 6-membered hydrocarbon ring,
Or a 5- or 6-membered optionally substituted heterocycle is preferred.
Good

Among them, the particularly preferable substituents represented by R ^{1 to} R ⁴ are the linear or branched alkyl groups having 1 to 12 carbon atoms which may be substituted, and the substituents having 3 to 18 carbon atoms. Good cyclic alkyl group, optionally substituted linear or branched alkoxy group having 1 to 12 carbon atoms, saturated heterocyclic group having 5 to 6 membered ring, heteroaromatic ring group having 5 to 6 membered ring, 6 to 6 carbon atoms
18 aryl groups, C7-20 aralkyl groups, C1-12 optionally substituted linear or branched alkylthio groups, halogen atoms, nitro groups, hydroxy groups,
An acyl group represented by —COR ²⁰ , an acyloxy group represented by —OCOR ²⁶ , an amino group represented by —NR ²¹ R ²² ,
A carboxylic acid ester group represented by -COOR ²⁵ , -CO
A carbamoyl group represented by NR ²⁷ R ²⁸ , -NHSO ₂ R
A sulfonamide group represented by ³³ , R ¹ and R ² , R ²
And R ³ and R ³ and R ⁴ form a ring, any one of these forms a benzene ring structure.

In the above general formulas [I] and [II], R ⁵ is
Hydrogen atom, optionally substituted hydrocarbon group, optionally substituted heterocyclic group, cyano group, hydroxy group, -NR ⁷ R ⁸ ,
Represents any one of —COR ⁹ The optionally substituted hydrocarbon group represented by R ⁵ includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group,
tert-butyl group, n-heptyl group or other straight-chain or branched alkyl group having 1 to 18 carbon atoms, cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclic alkyl group having 3 to 18 carbon atoms such as adamantyl group, A linear or branched alkenyl group having 2 to 18 carbon atoms such as vinyl group, propenyl group, and hexenyl group; cyclic alkenyl group having 3 to 18 carbon atoms such as cyclopentenyl group and cyclohexenyl group; benzyl group, phenethyl group, etc. An aralkyl group having 7 to 20 carbon atoms,
It represents an aryl group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group and a mesityl group. The alkyl chain portion and the aryl group portion of these groups may be further substituted with the above-mentioned substituents that the alkyl chain portion of R ^{1 to} R ⁴ may have.

Examples of the optionally substituted heterocyclic group represented by R ⁵ include a saturated heterocyclic ring such as 4-piperidyl group, morpholino group, 2-morpholinyl group and piperazyl group, 2-furyl group and 2-pyridyl group. It may be an aromatic heterocycle such as a group, a 2-thiazolyl group or a 2-quinolyl group. These may contain a plurality of hetero atoms, may further have a substituent, and the bonding position is not limited. Preferred heterocycles are 5- or 6-membered saturated heterocycles, 5- or 6-membered monocycles, and their two condensed aromatic heterocycles. When R ⁵ has an alkyl chain as an optionally substituted hydrocarbon group, it may combine with R ⁴ to form a saturated or unsaturated hydrocarbon ring or a saturated or unsaturated heterocyclic structure, The cyclic structure may be a single ring or a condensed ring. The number of members of the cyclic structure is not particularly limited, but a hydrocarbon ring and a heterocyclic ring are preferably 5- and 6-membered rings. These preferable cyclic structures are shown below.

[0033]

[Chemical 17]

R ⁷ and R ⁸ of -NR ⁷ R ⁸ represented by R ⁵ are
Each independently represents a hydrogen atom, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group. Examples of R ⁷ and R ⁸ include the same groups as the hydrocarbon group and the heterocyclic group exemplified as R ⁵ , but preferably a hydrogen atom, an optionally substituted straight chain or branched chain having 1 to 18 carbon atoms. Is an alkyl group, an optionally substituted aralkyl group having 7 to 20 carbon atoms, an optionally substituted aryl group having 6 to 18 carbon atoms, or an optionally substituted heterocyclic group. -CO represented by R ⁵
R ⁹ in R ⁹ represents either a hydrocarbon group which may be substituted or a heterocyclic group which may be substituted, preferably a linear or branched alkyl group having 1 to 18 carbon atoms, or substituted A good aralkyl group having 7 to 20 carbon atoms and an optionally substituted aryl group having 6 to 20 carbon atoms. Preferred examples of R ⁵ are shown below.

[0035]

[Chemical 18]

[0036]

[Chemical 19]

In the above general formulas [I] and [II], X ³ is
Oxygen atom or one sulfur atom or = N-R ^6. R ⁶ in = N-R ⁶ represented by X ³ is a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted heterocyclic group, a cyano group, one of the hydroxy groups, preferably A linear or branched alkyl group having 1 to 18 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms,
It is an optionally substituted aryl group having 6 to 20 carbon atoms.
Substituents that these groups may have include R ^{1 to} R ⁴ described above.
The same as those in the substituent that the alkyl chain of may have.

In the above general formula [I], X ¹ represents an electron-withdrawing group, and X ² represents a hydrogen atom or -Q-Y.
Here, Q represents a linking group, and represents an alkylene group having 1 or 2 carbon atoms, an arylene group, or a heteroarylene group, or is directly bonded to Y without a linking group, that is, a direct bond. Y and X ¹ independently represent an electron-withdrawing group.

The electron withdrawing group represented by X ¹ and Y is as follows.
Generally, in the Hammett rule, the sigma constant σ (σm and σp,
Especially, σp) has a positive value. Examples of these are 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 and trifluoromethyl group. , A sulfonic acid group, a sulfonic acid ester group, a sulfonyl group, a sulfamoyl group, a sulfinyl group and the like. Preferred examples of the electron-withdrawing group represented by X ¹ and Y include a cyano group, a nitro group, a halogen-substituted alkyl group, an acyl group represented by —COR ¹⁰ , and —COOR.
A carboxylic acid ester group represented by ¹¹ , -CONR ¹² R ¹³
A carbamoyl group represented by -SOR ¹⁶ , a sulfinyl group represented by -SO ₂ R ¹⁷ , a sulfonyl group represented by -SOR ^16.
It is a sulfamoyl group represented by SO ₂ NR ¹⁸ R ¹⁹ .

[0040] R ¹⁰ of the acyl group represented by -COR ^10, the
It represents either a hydrocarbon group which may be substituted or a heterocyclic group which may be substituted, and among these, preferred as R ¹⁰ is a linear or branched C 1-18 which may be substituted. Alkyl group, optionally substituted C7-20 aralkyl group, optionally substituted C6-18 aryl group, optionally substituted 5-7 membered saturated heterocycle, optionally substituted A good 5- to 6-membered monocyclic ring and its two condensed heteroaromatic rings. Specifically, acetyl group, propionyl group, isovaleryl group, pivaloyl group, benzoyl group,
An acyl group such as a 2-thenoyl group, a 2-furoyl group and a cyclohexanoyl group can be mentioned.

R ^{11 in the} carboxylic acid ester group represented by —COOR ¹¹ represents a hydrocarbon group which may be substituted or a heterocyclic group which may be substituted, and preferably has 1 to 1 carbon atoms which may be substituted. 18 linear or branched alkyl group, optionally substituted C 6-18 aryl group, optionally substituted C 7-20 aralkyl group, 5-7 membered saturated heterocycle, substituted May be a 5- or 6-membered monocycle and its 2
It is a condensed aromatic heterocyclic ring. Specific examples thereof include carboxylic acid ester groups such as methoxycarbonyl group, ethoxycarbonyl group, isobutoxycarbonyl group, phenoxycarbonyl group, cyclohexyloxycarbonyl group and 2-pyridyloxycarbonyl group.

R ¹² and R ¹³ of the carbamoyl group represented by —CONR ¹² R ¹³ are each independently a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted heterocyclic group, or an optionally substituted. Amino group, optionally substituted acylamino group, optionally substituted carbamate group, —COR ¹⁴ , —COO
Represents R ¹⁵ . Here, R ¹⁴ and R ¹⁵ represent arbitrary substituents,
As a preferable substituent, carbon number which may be substituted is 1 to.
And 18 linear or branched alkyl groups, optionally substituted aryl groups having 6 to 18 carbon atoms, and optionally substituted amino groups.

Preferred as R ¹² and R ¹³ are:
Hydrogen atom, optionally substituted C 1-18 linear or branched alkyl group, optionally substituted C 6-18
Aryl group, an optionally substituted aralkyl group having 7 to 20 carbon atoms, a 5- to 7-membered saturated heterocyclic ring, an optionally substituted 5- to 6-membered monocyclic ring and a heteroaromatic ring of its two condensed rings , An optionally substituted amino group, —COR ¹⁴ and —COOR ¹⁵ are exemplified. The structure of the carbamoyl group represented by —CONR ¹² R ¹³ is shown below.

[0044]

[Chemical 20]

R of the sulfinyl group represented by --SOR ^16
16 represents an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and preferable examples thereof include an optionally substituted linear or branched alkyl group having 1 to 18 carbon atoms and an optionally substituted An aryl group having 6 to 18 carbon atoms which may be substituted, an aralkyl group having 7 to 20 carbon atoms which may be substituted, a saturated heterocyclic ring having 5 to 7 membered ring, a monocyclic ring having 5 to 6 membered ring which may be substituted and its It is a heteroaromatic ring having two condensed rings. Specific examples include the sulfinyl group shown below.

[0046]

[Chemical 21]

R of the sulfonyl group represented by --SO ₂ R ^17
17 represents an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and preferable examples thereof include an optionally substituted linear or branched alkyl group having 1 to 18 carbon atoms and an optionally substituted An aryl group having 6 to 18 carbon atoms which may be substituted, an aralkyl group having 7 to 20 carbon atoms which may be substituted, a saturated heterocyclic ring having 5 to 7 membered ring, a monocyclic ring having 5 to 6 membered ring which may be substituted and its It is a heteroaromatic ring having two condensed rings. Specific examples thereof include sulfonyl groups shown below.

[0048]

[Chemical formula 22]

R ¹⁸ and R ¹⁹ of the sulfamoyl group represented by —SO ₂ NR ¹⁸ R ¹⁹ represent a hydrogen atom, a hydrocarbon group which may be substituted, or a heterocyclic group which may be substituted. , Hydrogen atom, optionally substituted carbon atoms 1 to 1
8 straight-chain or branched alkyl group, optionally substituted C 6-18 aryl group, optionally substituted C 7
To 18 aralkyl groups, a 5- to 7-membered saturated heterocycle, an optionally substituted 5- to 6-membered monocyclic ring, and its two condensed heteroaromatic rings. Specific examples include the sulfamoyl group shown below.

[0050]

[Chemical formula 23]

Specific examples of the optionally substituted hydrocarbon group and optionally substituted heterocyclic group represented by R ^{10 to} R ¹⁹ are the same as those described above for R ^{20 to} R ³³ . be able to. The linking group represented by Q represents a direct bond or an alkylene group having 1 to 2 carbon atoms, an arylene group, or a heteroarylene group. In the case of an alkylene group, a carbon atom may be included in the above alkyl chain in addition to a hydrogen atom. It may have a substituent or an alkyl chain branched therefrom. When Q represents a 6-membered ring arylene group or a heteroarylene group, it is preferable that the electron-withdrawing group Y is in the ortho position or the para position with respect to the bonding portion, and when it is a 5-membered ring heteroarylene group, The bond and the electron-withdrawing group are at the 2-position and 4-position.
It is preferable to be in the position. Also, a plurality of Ys bonded to these linking groups may be present. Further, it may have a substituent at a position other than where Y is bonded. Preferred bonds between these linking groups and electron withdrawing groups are illustrated below.

[0052]

[Chemical formula 24]

(G ^{1 to} G ^{6 in the} figure represent arbitrary substituents, and Y
Represents an electron-withdrawing group. ) G ^{1 to} G ⁶ are preferably nitro group, cyano group, amino group, halogen atom, hydroxy group, alkoxy group, alkylthio group, acyl group, aryl group, aralkyl group,
Examples include an acylamino group and an alkoxycarbonyl group.

In the above general formula [II], ring A is> C═O
Represents a carbocyclic ketone structure or a heterocyclic ketone structure. Carbocyclic ketones and heterocyclic ketones mean that —CH ₂ — and ═CH— in the unsaturated or aromatic ring system are> C =
It is replaced by O. Further, a plurality of> C = O,> C = S and> C = NH are also contained in the ring structure portion of the ring A indicated by the dotted line.
Etc. may be included. The carbocyclic ketone structure or heterocyclic ketone structure formed by ring A may be saturated or unsaturated, and the number of ring members is not particularly limited. The number of heteroatoms in the heterocycle is not particularly limited. Further, the hydrocarbon group in the ring and the hydrogen atom of —NH— constituting the ring may be substituted with an arbitrary substituent (particularly preferably an alkyl group or an aryl group). These carbocyclic ketone structures and heterocyclic ketone structures may form a condensed ring structure by condensing a further ring on a part of the ring. The ring structure condensed with the cyclic ketone structure may be a hydrocarbon ring or a heterocycle, but is preferably a benzene ring or a 5- or 6-membered heteroaromatic ring.
The structure of the cyclic ketone is shown below.

[0055]

[Chemical 25]

Preferred examples of the carbocyclic ketone structure and the heterocyclic ketone structure formed by the ring A include a 5- to 6-membered saturated hydrocarbon ring and a 5- to 6-membered saturated or unsaturated heterocyclic ring. It is a thing. The compounds represented by the general formulas [I] and [II] are
A compound having a molecular weight of preferably 1,000 or less, particularly preferably 700 or less. Preferred examples of the compounds represented by the general formulas [I] and [II] include the following.

[0057]

[Chemical formula 26]

[0058]

[Chemical 27]

[0059]

[Chemical 28]

[0060]

[Chemical 29]

The above general formulas [I] and [II] of the present invention are as follows.
The dye consisting of the compound represented by is excellent in thin film forming property when forming a recording layer from a solution containing the dye, and therefore is very useful as a dye used in the recording layer of an optical recording medium. is there. In addition, the dye of the present invention has a recording layer containing the dye, which has absorption suitable for recording / reproducing by laser light in a shorter wavelength region (350 nm to 500 nm), and thus can be used for recording with a short wavelength laser. It is extremely useful as a dye for use in an optical recording medium for reproduction.

The optical recording medium of the present invention basically comprises a substrate and a recording layer containing the above-mentioned dye compound. If necessary, an undercoat layer, a reflective layer and a protective layer may be formed on the substrate. You may provide a layer etc. As an example of a preferable layer structure, a recording layer is provided on a substrate, and gold, silver,
A medium having a high reflectance provided with a metal reflective layer such as aluminum and a protective layer can be mentioned. Hereinafter, the optical recording medium of the present invention will be described by taking a medium having this structure as an example.

The material of the substrate in the optical recording medium of the present invention may basically be transparent to the wavelengths of recording light and reproducing light. Such materials include, for example, acrylic resin, methacrylic resin, polycarbonate resin, polyolefin resin (particularly amorphous polyolefin), polyester resin, polystyrene resin, epoxy resin, or other resin, or glass. It is possible to use, for example, a glass provided with a resin layer made of a radiation curable resin such as a photocurable resin.

From the viewpoints of high productivity, cost, moisture absorption resistance, etc., injection molded polycarbonate is preferable, chemical resistance,
From the viewpoint of moisture absorption resistance, amorphous polyolefin is preferable. A glass substrate is preferable from the viewpoint of high-speed response. A resin substrate or resin layer may be provided in contact with the recording layer, and a guide groove or pit for recording / reproducing light may be provided on the resin substrate or resin layer. If the guide groove is spiral,
The groove pitch is preferably about 0.2 to 1.2 μm.

A recording layer containing the compound of the present invention is formed on the substrate or, if necessary, on the undercoat layer. Examples of the method for forming the recording layer include vacuum deposition method, sputtering method, doctor blade method, casting method, spin coating method, dipping method and other commonly used thin film forming methods. The spin coating method is preferable in terms of mass productivity and cost. Further, from the viewpoint that a recording layer having a uniform thickness can be obtained, the vacuum vapor deposition method or the like is preferable to the coating method. In the case of film formation by the spin coating method, the rotation speed is preferably 500 to 15,000 rpm, and after spin coating, treatment such as heating or applying to solvent vapor may be performed depending on the case.

The coating solvent for forming the recording layer by a coating method such as a doctor blade method, a casting method, a spin coating method or a dipping method may be any solvent that does not attack the substrate and is not particularly limited. For example, a ketone alcohol solvent such as diacetone alcohol and 3-hydroxy-3-methyl-2-butanone; a cellosolve solvent such as methyl cellosolve and ethyl cellosolve; a chain hydrocarbon solvent such as n-hexane and n-octane Cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane,
Cyclic hydrocarbon solvents such as n-butylcyclohexane, tert-butylcyclohexane, cyclooctane; Fluoroalkyl alcohol solvents such as tetrafluoropropanol, octafluoropentanol, hexafluorobutanol; methyl lactate, ethyl lactate, 2-hydroxyiso Hydroxycarboxylic acid ester solvents such as methyl butyrate; amino-substituted alcohol solvents such as 2-dimethylaminoethanol and 2-diethylaminoethanol.

In the case of the vacuum vapor deposition method, for example, the compound of the present invention and, if necessary, other recording layer components such as other dyes and various additives are put in a crucible provided in the vacuum container, and the inside of the vacuum container is filled. After evacuating to about 10 ^-2 to 10 ^-5 Pa with an appropriate vacuum pump, the crucible is heated to evaporate the components of the recording layer,
A recording layer is formed by vapor deposition on a substrate placed facing the crucible.

Further, the recording layer has a transition metal chelate compound (eg, acetylacetonato chelate, bisphenyldithiol, salicylaldehyde oxime, bisdithio-α) as a singlet oxygen quencher in order to improve stability and light resistance of the recording layer. -Diketone, etc.) and a recording sensitivity improver such as a metal compound for improving recording sensitivity. Here, the metal-based compound means that a metal such as a transition metal is contained in the compound in the form of an atom, an ion, a cluster, etc., for example, an ethylenediamine-based complex, an azomethine-based complex, a phenylhydroxyamine-based complex, a phenanthroline-based complex, Dihydroxyazobenzene-based complex,
Dioxime complex, nitrosoaminophenol complex,
Examples thereof include organometallic compounds such as pyridyltriazine-based complexes, acetylacetonate-based complexes, metallocene-based complexes, and porphyrin-based complexes. The metal atom is not particularly limited, but a transition metal is preferable.

Further, dyes of other systems can be used in combination, if necessary. The other type of dye is not particularly limited as long as it has appropriate absorption mainly in the laser wavelength range for recording. Also, like a CD-R 770-8
Corresponding to recording by laser light in multiple wavelength ranges by using a dye suitable for recording with near infrared laser of wavelength selected from 30 nm and red laser selected from 620 to 690 nm such as DVD-R The optical recording medium may also be used. Other types of dyes include metal azo dyes, phthalocyanine dyes, naphthalocyanine dyes, cyanine dyes, azo dyes, squarylium dyes, metal indoaniline dyes, triarylmethane dyes, merocyanine dyes, Examples thereof include azurenium dyes, naphthoquinone dyes, anthraquinone dyes, indophenol dyes, xanthene dyes, oxazine dyes, and pyrylium dyes.

Further, if necessary, a binder, a leveling agent, a defoaming agent and the like can be used in combination. Preferred binders include polyvinyl alcohol, polyvinylpyrrolidone, nitrocellulose, cellulose acetate, ketone resins, acrylic resins, polystyrene resins, urethane resins, polyvinyl butyral, polycarbonate, polyolefins and the like. The thickness of the recording layer is
Since the suitable film thickness differs depending on the recording method, etc., it is not particularly limited, but it is usually 50 to 300 nm.

A reflective layer may be formed on the recording layer, and the thickness thereof is preferably 50 to 300 nm. As the material of the reflective layer, a material having a sufficiently high reflectance at the wavelength of the reproduction light, for example, Au, Al, Ag, Cu, Ti, Cr, Ni, Pt, Ta,
The metals of Cr and Pd can be used alone or as an alloy. Among these, Au, Al and Ag have high reflectance and are suitable as materials for the reflective layer. In addition to using these as main components, the following may be included as other components. Examples of other components include Mg, Se, Hf, V, Nb, Ru, W, Mn, Re,
Fe, Co, Rh, Ir, Cu, Zn, Cd, Ga, In, Si, Ge, Te, P
Examples thereof include metals and semimetals such as b, Po, Sn, Bi, Nd, Ta, Ti, Pt, and Pd. Among them, those containing Ag as a main component are particularly preferable in that the cost is low, high reflectance is likely to occur, and when a print receiving layer described later is provided, a white background color and a beautiful one can be obtained. Here, the main component means one having a content rate of 50% or more.

A low refractive index thin film and a high refractive index thin film made of a material other than metal may be alternately stacked to form a multilayer film, which may be used as a reflective layer. Examples of the method of forming the reflective layer include a sputtering method, an ion plating method, a chemical vapor deposition method, a vacuum vapor deposition method and the like. Further, on the substrate or under the reflective layer, a known inorganic or organic intermediate layer for improving reflectance, improving recording characteristics, improving adhesion, etc.,
An adhesive layer can also be provided. The thickness of the reflective layer is usually 40
Is about 200 nm.

The material of the protective layer formed on the reflective layer is not particularly limited as long as it protects the reflective layer from external force. Examples of the material of the organic substance include a thermoplastic resin, a thermosetting resin, an electron beam curable resin, a UV curable resin and the like. Examples of the inorganic substance include silicon oxide, silicon nitride, MgF ₂ , SnO _{2 and the} like. It can be formed by dissolving a thermoplastic resin, a thermosetting resin, etc. in a suitable solvent to prepare a coating solution, and applying and drying the coating solution. The UV curable resin can be formed as it is or by dissolving it in an appropriate solvent to prepare a coating solution, applying the coating solution, and then irradiating it with UV light to cure it. Examples of the UV curable resin include urethane acrylate, epoxy acrylate,
An acrylate resin such as polyester acrylate can be used. These materials may be used alone or as a mixture, and may be used not only as one layer but also as a multilayer film.

As the method of forming the protective layer, 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 as in the recording layer, and the spin coating method is preferable among them. The thickness of the protective layer is generally 0.1 to 1
Although it is in the range of 00 μm, in the present invention, it is preferably 3 to 30 μm.

The above description is an example of an optical recording medium having a basic layer structure in which a substrate / recording layer / reflection layer / protective layer are laminated in this order, and recording / reproducing is performed by laser light irradiated through the substrate. However, any layer may be provided between these layers as long as the characteristics of the present invention are not impaired.
Further, a substrate may be further bonded on the protective layer or on the reflective layer without providing the protective layer via an adhesive layer or the like. The substrate may be the substrate itself without any layer, or may have any layer on the bonding surface or the opposite surface. An optical recording medium capable of recording / reproducing on both sides may be prepared by preparing two substrates having at least a recording layer and bonding them so that the recording layers face each other.

Further, the optical recording medium of the present invention has a basic layer structure in which a substrate / reflection layer / recording layer / protective film is laminated in this order, and recording / reproduction is performed by laser light irradiated through the protective film. May be performed. This protective film may be formed by adhering a film or sheet in the form of an adhesive, or may be formed by applying a coating liquid for film formation as in the case of the above-mentioned protective layer. Also in the case of such a basic layer structure, any layer may be provided between the above layers as long as the characteristics of the present invention are not impaired.

By the way, as one means for increasing the recording density of the optical recording medium, it has been proposed to increase the numerical aperture of the objective lens to miniaturize the light spot focused on the information recording surface. When the numerical aperture of the objective lens is increased, the aberration of the focused light spot becomes large due to the influence of the warp of the disc, etc., and there is a problem that a good recording / reproducing signal cannot be stably obtained. In order to reduce the above-mentioned aberration caused by the warp of the medium, for example, the recording / reproducing laser beam has a basic layer structure in which the substrate / recording layer / reflection layer / protective layer are laminated in this order. It is preferable to reduce the thickness of the transparent substrate passing through to about 0.1 mm, or to record / reproduce through the protective coating on the optical recording medium in which the substrate / reflection layer / recording layer / protective coating is sequentially laminated. The thickness of the protective coating is usually about 0.1 μm to 0.3 mm, preferably about 0.1 μm to 200 μm. In any of the above laminated media, a print receiver capable of writing (printing) on a surface other than the recording / reproducing light incident surface by various printers such as ink jet, thermal transfer, or various writing instruments as necessary. Layers may be provided.

The laser light used for the optical recording medium of the present invention is preferably shorter in wavelength for high density recording, but is preferably 350 to 530 nm. Typical examples of such laser light, the central wavelength 405nm, 410nm,
Laser light of 515 nm can be mentioned. An example of laser light in the wavelength range of 350 to 530 nm is 405 nm, 410 nm blue or 51
Although it can be obtained by using a blue-green high-power semiconductor laser of 5 nm, other, for example, (a) a semiconductor laser capable of continuous oscillation with a fundamental oscillation wavelength of 740 to 960 nm,
Alternatively, (b) a solid-state laser that is excited by a semiconductor laser and is capable of continuous oscillation with a fundamental oscillation wavelength of 740 to 960 nm can be wavelength-converted by a second harmonic generation element (SHG).

The above SHG may be any piezoelectric element lacking inversion symmetry, but KDP,
ADP, BNN, KN, LBO, compound semiconductor and the like are preferable. As a concrete example of the second harmonic, the fundamental oscillation wavelength is
In the case of a semiconductor laser of 860 nm, its harmonic wave is 430 nm, and in the case of a semiconductor laser pumped solid-state laser, it is 4 times the harmonic wave from a Cr-doped LiSrAlF ₆ crystal (fundamental oscillation wavelength 860 nm).
Examples include 30 nm.

Recording on the optical recording medium of the present invention obtained as described above is performed by irradiating a recording layer provided on both sides or one side of the substrate with a laser beam focused to about 0.4 to 0.6 μm. In the portion irradiated with laser light, thermal deformation of the recording layer such as decomposition, heat generation, and dissolution due to absorption of laser light energy occurs, and optical characteristics change. Reproduction of the recorded information is performed by reading the difference in reflectance between the portion where the change in the optical characteristics has occurred and the portion where the change in the optical characteristics has not occurred, by the laser light.

[0081]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. [Synthesis Example] The method for synthesizing the compounds represented by the above general formulas [I] and [II] is not particularly limited, but as a general production method, Tetrahedron, Vol. 23 (1967), p901 or J . Indian Che
m. Soc., Vol.67 (1990), p490,
It is known to be obtained by reacting an isatin derivative with a compound having active methylene.

Example 1 (a) Production Example 2.94 g (20 mmol) of isatin and 2.49 g (22 mmol) of ethyl cyanoacetate were mixed with 2 parts of ethanol.
The mixture was dissolved in 0 ml with stirring, 2 drops of piperidine were added, and the mixture was refluxed for 4 hours in an oil bath. After the reaction solution was cooled to room temperature, the precipitated solid was filtered and the solid was filtered off to obtain the exemplary compound (1).
There was obtained 3.93 g of the compound represented by (yield 81.1%). Maximum absorption wavelength of this compound in chloroform
(λmax) is 338.5 nm, molar extinction coefficient is 11,100
Met.

(B) Example of Recording Medium The above-exemplified compound (1) was dissolved in octafluoropentanol and adjusted to 1.0 wt%. A solution obtained by filtering this was dropped on an injection molded polycarbonate resin substrate having a diameter of 120 mm and a thickness of 1.2 mm, applied by a spinner method, and then dried at 100 ° C. for 30 minutes. The maximum absorption wavelength (λmax) of this coating film was 339.0 nm.

Example 2 (a) Preparation Example 5-Nitroisatin (1.92 g, 10 mmol) and cyanoacetic acid ethyl ester (1.24 g, 11 mmol) were dissolved in 10 ml of ethanol with stirring, and 1 drop of piperidine was added thereto. Reflux for hours. After the reaction solution was cooled to room temperature, the precipitated solid was filtered and the solid was filtered off to obtain 2.14 g of the compound represented by Exemplified Compound (2) (yield 74.5).
%)was gotten. The maximum absorption wavelength (λmax) of this compound in chloroform is 307.0 nm, and the molar absorption coefficient is 2
It was 1,300.

(B) Example of Recording Medium The above-exemplified compound (2) was dissolved in octafluoropentanol and adjusted to 1.0 wt%. A solution obtained by filtering this was dropped on an injection molded polycarbonate resin substrate having a diameter of 120 mm and a thickness of 1.2 mm, applied by a spinner method, and then dried at 100 ° C. for 30 minutes. The maximum absorption wavelength (λmax) of this coating film was 308 nm.

Example 3 (a) Production Example 2.42 g (10 mmol) of the above exemplified compound (2) was added to 10 ml of acetic anhydride, the solution was refluxed in an oil bath for 4 hours, cooled to room temperature, and then in 100 ml of water. Was added dropwise. The precipitated solid was separated by filtration to obtain 2.45 g (yield 86%) of the compound represented by Exemplified compound (4). The maximum absorption wavelength (λmax) in chloroform of this compound was 341.5 nm, and the molar extinction coefficient was 10,300.

(B) Example of Recording Medium The above-exemplified compound (4) was dissolved in octafluoropentanol and adjusted to 1.0 wt%. A solution obtained by filtering this was dropped on an injection molded polycarbonate resin substrate having a diameter of 120 mm and a thickness of 1.2 mm, applied by a spinner method, and then dried at 100 ° C. for 30 minutes. The maximum absorption wavelength (λmax) of this coating film was 342.0 nm.

Example 4 (a) Preparation Example 2.94 g (20 mmol) of isatin and 1.45 g (22 mmol) of malononitrile were dissolved in 20 ml of ethanol with stirring, 2 drops of piperidine were added, and the mixture was refluxed for 4 hours in an oil bath. After the reaction solution was cooled to room temperature, the precipitated solid was filtered and the solid was filtered off to obtain 3.78 g of the compound represented by Exemplified Compound (3) (yield 96.8%). The maximum absorption wavelength (λmax) of this compound in chloroform is 3
The molar extinction coefficient was 51.0 nm and 13,200.

(B) Example of recording medium The above-exemplified compound (3) was dissolved in methyl lactate to obtain 2.0 wt.
Adjusted to%. The solution obtained by filtering this is 120 m in diameter.
The composition was dropped on an injection-molded polycarbonate resin substrate having a thickness of m and a thickness of 1.2 mm, applied by a spinner method, and after application, dried at 100 ° C. for 30 minutes. The maximum absorption wavelength of this coating (λma
x) was 351.0 nm.

Example 5 (a) Production Example 1.95 g (10 mmol) of the above-exemplified compound (4) was added to 10 ml of acetic anhydride, the solution was refluxed in an oil bath for 4 hours, cooled to room temperature, and then in 100 ml of water. Was added dropwise. The precipitated solid was filtered off to obtain 1.98 g (yield 83.5%) of the compound represented by Exemplified compound (5). The maximum absorption wavelength (λmax) of this compound in chloroform is 358.0n.
The m and molar extinction coefficient were 13,100.

(B) Example of Recording Medium The above-exemplified compound (5) was dissolved in octafluoropentanol and adjusted to 1.0 wt%. A solution obtained by filtering this was dropped on an injection molded polycarbonate resin substrate having a diameter of 120 mm and a thickness of 1.2 mm, applied by a spinner method, and then dried at 100 ° C. for 30 minutes. The maximum absorption wavelength (λmax) of this coating film was 371.0 nm.

On this coating film prepared as described above, a silver film is formed by, for example, a sputtering method or the like to form a reflection layer, and then an ultraviolet curable resin is applied by spin coating or the like.
It can be cured by UV irradiation to form a protective layer and used as an optical recording medium. It is apparent from the value of λmax of the coating film that this optical recording medium can be recorded and reproduced by a laser having a wavelength of 350 nm to 530 nm, for example, a semiconductor laser having a central wavelength of 405 nm.

[0093]

The solution containing the dye compound of the present invention is
Since a coating film having absorption suitable for recording / reproducing with a short wavelength laser beam can be formed and the film forming property is excellent, a recording medium having a recording layer using the compound of the present invention is It is useful as a recording / reproducing optical recording medium compatible with a wavelength laser.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G11B 7/24 516 B41M 5/26 YF term (reference) 2H111 EA03 EA12 EA22 EA25 EA31 EA33 FB42 4H056 CA01 CC04 CC08 CD08 CD09 CD12 CE03 CE06 CE07 DD03 DD06 DD07 DD16 DD23 DD24 DD28 DD29 EA13 FA01 5D029 JA04 5D090 AA01 BB03 CC01 KK06

Claims (11)

[Claims] 1. An optical recording medium in which a recording layer capable of recording or reproducing information by a laser is provided on a substrate,
An optical recording medium, wherein the recording layer contains a compound represented by the following general formula [I]. [Chemical 1] {In the formula, R ^{1 to} R ⁴ represent a hydrogen atom or an arbitrary substituent, and at least two adjacent substituents of R ^{1 to} R ⁴ may be bonded to each other to form a hydrocarbon ring or a heterocyclic structure. The hydrocarbon ring and the heterocycle may have a substituent. X ¹ represents an electron-withdrawing group, X ² represents a hydrogen atom or-
Represents Q-Y. (Q represents a direct bond, an alkylene group having 1 or 2 carbon atoms, an arylene group or a heteroarylene group, and Y represents an electron-withdrawing group. The alkylene group, the arylene group and the heteroarylene group are any other than Y. May have a substituent of)) X ³ represents an oxygen atom, a sulfur atom or = N-R ⁶ . (R ⁶ represents a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted heterocyclic group, a cyano group or a hydroxy group.) R ⁵ is a hydrogen atom, an optionally substituted hydrocarbon group, or a substituted A heterocyclic group which may be
Cyano group, hydroxy group, -NR ⁷ R ⁸ (representative of R ^7, R ⁸ are each independently hydrogen atom, optionally substituted hydrocarbon group or an optionally substituted heterocyclic group.), Or -COR ⁹
(R ⁹ represents an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group), and R ⁵ is an optionally substituted hydrocarbon ring bonded to R ⁴ or an optionally substituted hydrocarbon ring. A good heterocyclic structure may be formed. } 2. An electron-withdrawing group X in the general formula [I].¹Over
And Y are each independently a halogen-substituted alkyl group, a cyano group,
Nitro group, -CO-R^Ten(R^TenMay be substituted carbonization
It represents a hydrogen group or an optionally substituted heterocyclic group. ), -CO
OR¹¹(R¹¹Is a hydrogen atom, an optionally substituted hydrocarbon
Group, which represents an optionally substituted heterocyclic group), -CONR¹²
R¹³[R¹², R¹³Are each independently a hydrogen atom,
Good hydrocarbon groups, optionally substituted heterocyclic groups, substituted
Optionally an amino group, an optionally substituted acylamino group,
Carbamate group which may be substituted, -COR¹⁴, -CO
OR¹⁵(R¹⁴, R ¹⁵Represents an arbitrary substituent). ], -S
OR¹⁶(R¹⁶Is a hydrocarbon group which may be substituted,
Represents a heterocyclic group which may be present. ) -SO₂R¹⁷(R¹⁷Is replaced
Optionally substituted hydrocarbon group, optionally substituted heterocyclic group
Represent ) -SO₂NR¹⁸R¹⁹(R¹⁸, R¹⁹Each is independent
A hydrogen atom, an optionally substituted hydrocarbon group, a substituted
Represents a heterocyclic group which may be present. ), Q is a direct bond, a phenylene group, or a 5- or 6-membered hetero ring
Arylene group (to the phenylene group and the 5- or 6-membered ring)
The teloarylene group may have a substituent other than Y
Yes. ) Is represented, The optical recording of Claim 1 characterized by the above-mentioned.
Recording medium. 3. In the general formula [I], R¹~ R^FourEach is independent
Is a straight chain or branched chain having 1 to 18 carbon atoms which may be substituted.
Alkyl group, optionally substituted cyclic group having 3 to 18 carbon atoms
Alkyl group, optionally substituted straight chain having 2 to 18 carbon atoms
Or a branched alkenyl group, optionally substituted carbon atoms 3 to
18 cyclic alkenyl groups, optionally substituted heterocyclic groups,
Optionally substituted aryl group having 6 to 18 carbon atoms, substituted
An optionally substituted aralkyl group having 7 to 24 carbon atoms, which is substituted
Good linear or branched alkoxy having 1 to 18 carbon atoms
Group, optionally substituted linear or branched chain having 3 to 18 carbon atoms
Alkenyloxy group, optionally substituted carbon number 1 to 1
8 straight-chain or branched alkylthio groups, halogen atoms,
Nitro group, nitroso group, cyano group, isocyano group, sia
Nato group, isocyanato group, thiocyanato group, isothiocyanate
Anato group, mercapto group, hydroxy group, hydroxy group
Mino group, sulfonic acid group, formyl group, carboxyl group,
-COR²⁰An acyl group represented by^{twenty one}R^{twenty two}Represented by
Amino group, -NHCOR ^{twenty three}Acylamino represented by
Group, -NHCOOR^{twenty four}A carbamate group represented by -C
OOR^{twenty five}A carboxylic acid ester group represented by -OCOR
²⁶An acyloxy group represented by²⁷R²⁸Represented by
Carbamoyl group, -SO₂R²⁹Sulfoni represented by
Group, -SO₂NR³⁰R³¹Sulfamoyl represented by
Group, -SO₃R³²A sulfonate group represented by
NHSO₂R³³Represents a sulfonamide group represented by (R
²⁰, R^{twenty three}, R^{twenty four}, R^{twenty five}, R²⁶, R²⁹, R³², R³³Is replaced
Optionally substituted hydrocarbon group, or optionally substituted hetero group
Represents a ring group, R^{twenty one}, R^{twenty two}, R²⁷, R²⁸, R³⁰, R³¹Is water
Elementary atom, optionally substituted hydrocarbon group, optionally substituted
Represents a heterocyclic group. ), R¹And R², R²When
R³, R³And R^FourAre each independently bonded and substituted
May be a 5 to 7 membered hydrocarbon ring, or may be substituted
May form a 5- to 6-membered heterocyclic ring
The optical recording medium according to claim 1 or 2, characterized in that: 4. In the general formula [I], R ^{1 to} R ⁴ are each independently a straight-chain or branched alkyl group having 1 to 12 carbon atoms which may be substituted, and 3 to 3 carbon atoms which may be substituted. 18 cyclic alkyl groups, optionally substituted C 2-12 linear or branched alkenyl groups, 5-6 membered saturated heterocyclic groups,
5- to 6-membered monocyclic or bi-condensed heteroaromatic group, optionally substituted aryl group having 6 to 18 carbon atoms, optionally substituted aralkyl group having 7 to 20 carbon atoms, or optionally substituted Good straight-chain or branched alkoxy group having 1 to 12 carbon atoms, optionally substituted straight-chain or branched alkylthio group having 1 to 12 carbon atoms, halogen atom, nitro group, cyano group, mercapto group, hydroxy group,- An acyl group represented by COR ²⁰ , an amino group represented by -NR ²¹ R ²² , and a -NHCOR ²³
An acylamino group represented by -NHCOOR ²⁴ , a carbamate group represented by -COOR ²⁵ , a carboxylic acid ester group represented by -COOR ²⁵ , an acyloxy group represented by -OCOR ²⁶ ,
A carbamoyl group represented by -CONR ²⁷ R ²⁸ , -NHS
Represents a sulfonamide group represented by O ₂ R ³³ (provided that R 2
²⁰ , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ³³ , R ²¹ , R ²² ,
R ²⁷ and R ²⁸ have the same meaning as in claim 3. ), R ¹
And R ^2, R ² and R ^3, R ³ and bonded R ⁴ each independently is a hydrocarbon ring substituted optionally also be 5-7 membered ring, or 5-6 optionally substituted membered The optical recording medium according to claim 1 or 2, which may form a heterocyclic ring. 5. In the general formula [I], R ⁵ is a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 18 carbon atoms, or an optionally substituted cyclic alkyl group having 3 to 18 carbon atoms. An optionally substituted aryl group having 6 to 24 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, an optionally substituted heterocyclic group, a cyano group, a hydroxy group, -NR
⁷ R ⁸ (R ⁷ and R ⁸ are each independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 18 carbon atoms, an optionally substituted aryl group having 6 to 24 carbon atoms, An optionally substituted aralkyl group having 7 to 20 carbon atoms or an optionally substituted heterocyclic group), -COR ⁹ (R ⁹ is an optionally substituted linear or branched C 1 to 18 carbon atom) An alkyl group,
It represents an optionally substituted aryl group having 6 to 24 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, or an optionally substituted heterocyclic group. ) Is represented, The optical recording medium as described in any one of Claim 1 thru | or 4 characterized by the above-mentioned. 6. An optical recording medium in which a recording layer capable of recording or reproducing information by a laser is provided on a substrate,
An optical recording medium, wherein the recording layer contains a compound represented by the following general formula [II]. [Chemical 2] {In the formula, R ^{1 to} R ⁴ represent a hydrogen atom or an arbitrary substituent, and at least two adjacent substituents of R ^{1 to} R ⁴ may be bonded to each other to form a hydrocarbon ring or a heterocyclic structure. The hydrocarbon ring and the heterocycle may have a substituent. Ring A represents a carbocyclic ketone ring or a heterocyclic ketone ring which may have a substituent together with> C═O. X ³ is an oxygen atom, a sulfur atom or = N-R represents a ⁶ (representing R ⁶ is a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted heterocyclic group, cyano group, hydroxy group.) . R ⁵ is a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted heterocyclic group, a cyano group, a hydroxy group, —NR ⁷ R
⁸ (R ⁷ and R ⁸ each independently represent a hydrogen atom, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group), or —COR ⁹ (R ⁹ may be substituted. Represents a hydrocarbon group or an optionally substituted heterocyclic group), and R ⁵ may combine with R ⁴ to form an optionally substituted hydrocarbon ring or an optionally substituted heterocyclic structure. good. } 7. In the general formula [II], ring A may be a substituted 5- or 6-membered carbocyclic ketone ring or an optionally substituted 5- or 6-membered heterocyclic ketone ring. The optical recording medium according to claim 6, wherein 8. R in the general formula [II]¹~ R^FourEach is independent
Is a straight chain or branched chain having 1 to 18 carbon atoms which may be substituted.
Alkyl group, optionally substituted cyclic group having 3 to 18 carbon atoms
Alkyl group, optionally substituted straight chain having 2 to 18 carbon atoms
Or a branched alkenyl group, optionally substituted carbon atoms 3 to
18 cyclic alkenyl groups, heterocyclic groups, optionally substituted
Aryl group having 6 to 18 carbon atoms, optionally substituted carbon number
7 to 24 aralkyl groups, optionally substituted carbon atoms 1 to
18 straight or branched alkoxy groups, which may be substituted
A straight-chain or branched alkenyloxy having 3 to 18 carbon atoms
Group, linear or branched chain having 1 to 18 carbon atoms which may be substituted
Alkylthio group, halogen atom, nitro group, nitroso
Group, cyano group, isocyanato group, cyanato group, isocyana
Group, thiocyanato group, isothiocyanato group, mercap
Group, hydroxy group, hydroxyamino group, sulfonic acid
Group, formyl group, carboxyl group, -COR²⁰Represented by
Acyl group, -NR^{twenty one}R^{twenty two}An amino group represented by
COR^{twenty three}An acylamino group represented by -NHCOOR^{twenty four}
A carbamate group represented by^{twenty five}Is represented by
Rubonate ester group, -OCOR²⁶Represented by
Xyl group, -CONR ²⁷R²⁸A carbamoyl group represented by
-SO₂R²⁹A sulfonyl group represented by₂NR³⁰R
³¹A sulfamoyl group represented by₃R³²Represented by
Sulfonate group, -NHSO₂R³³Represented by
Represents a sulfonamide group (R²⁰, R^{twenty three}, R^{twenty four}, R^{twenty five}, R
²⁶, R²⁹, R³², R³³Is an optionally substituted hydrocarbon group,
Or a heterocyclic group which may be substituted, R^{twenty one}, R^{twenty two}，
R²⁷, R²⁸, R³⁰, R³¹Is a hydrogen atom, which may be substituted
Represents either a hydrocarbon group or an optionally substituted heterocyclic group.
), R¹And R², R²And R³, R³And R^FourAre joined independently
And optionally substituted 5- to 7-membered hydrocarbon ring,
Or form a 5- to 6-membered optionally substituted heterocycle
8. The method according to claim 6 or 7, characterized in that
Optical recording medium. 9. In the general formula [II], R ^{1 to} R ⁴ are each independently a straight-chain or branched alkyl group having 1 to 12 carbon atoms which may be substituted, and 3 to 3 carbon atoms which may be substituted. 18 cyclic alkyl groups, optionally substituted C 2-12 linear or branched alkenyl groups, 5-6 membered saturated heterocyclic groups,
5- to 6-membered monocyclic or bi-condensed heteroaromatic group, optionally substituted aryl group having 6 to 18 carbon atoms, optionally substituted aralkyl group having 7 to 20 carbon atoms, or optionally substituted A linear or branched alkoxy group having 1 to 12 carbon atoms, an optionally substituted linear or branched alkylthio group having 1 to 12 carbon atoms, a halogen atom, a nitro group, a cyano group, a mercapto group, a hydroxy group, An acyl group represented by COR ²⁰ , an amino group represented by -NR ²¹ R ²² , and a -NHCOR ²³
An acylamino group represented by -NHCOOR ²⁴ , a carbamate group represented by -COOR ²⁵ , a carboxylic acid ester group represented by -COOR ²⁵ , an acyloxy group represented by -OCOR ²⁶ ,
A carbamoyl group represented by -CONR ²⁷ R ²⁸ , -NHS
Represents a sulfonamide group represented by O ₂ R ³³ (provided that R 2
²⁰ , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ³³ , R ²¹ , R ²² ,
R ²⁷ and R ²⁸ have the same meanings as in claim 8. ), R ¹
And R ^2, R ² and R ^3, R ³ and bonded R ⁴ each independently is a hydrocarbon ring substituted optionally also be 5-7 membered ring, or 5-6 optionally substituted membered The optical recording medium according to claim 6 or 7, which may form a heterocyclic ring. 10. In the general formula [II], R ⁵ is a hydrogen atom,
An optionally substituted linear or branched alkyl group having 1 to 18 carbon atoms, an optionally substituted cyclic alkyl group having 3 to 18 carbon atoms, an optionally substituted aryl group having 6 to 24 carbon atoms, substituted An aralkyl group having 7 to 20 carbon atoms,
A heterocyclic group which may be substituted, a cyano group, a hydroxy group,
—NR ⁷ R ⁸ (R ⁷ and R ⁸ are each independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 18 carbon atoms, or an optionally substituted aryl having 6 to 24 carbon atoms. Group, an optionally substituted aralkyl group having 7 to 20 carbon atoms, or an optionally substituted heterocyclic group), -COR ⁹ (R ⁹ is an optionally substituted straight chain having 1 to 18 carbon atoms or A branched alkyl group, an optionally substituted aryl group having 6 to 24 carbon atoms,
It represents an optionally substituted aralkyl group having 7 to 20 carbon atoms or an optionally substituted heterocyclic group. ) Is represented, The optical recording medium of any one of Claims 6 thru | or 9 characterized by the above-mentioned. 11. An optical recording method, wherein information is recorded on the optical recording medium according to any one of claims 1 to 10 by using a laser beam having a wavelength of 350 nm to 530 nm.