JPH10297103A - Information recording medium and oxonol compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable recording characteristics to be maintained over a long period of time and at the same time, especially improve the stability of light resistance by adding either of coloring matter compounds expressed by two different types of specific structural formulae or both of the compounds to a recording layer. SOLUTION: The information recording medium is formed by adding to a recording layer either or both of the two different types of coloring matter compound expressed by formula I and/or formula II [in the formulae, A<1> , A<2> , B<1> and B<2> are substitutents; Y<1> and Z<1> are atomic group required for forming a carbon ring or a heterocycle; E and C are atomic groups required from completing a conjugated double bond ohain; X<1> is =O, =NR or =C(CN)2 ; X<2> is -O, -NR or -C(CN)2 (R is a substituting); L<1> , L<2> , L<3> , L<4> and L<5> are a methine group respectively; M<k+> is an onium ion; m, n, are 0, 1 or 2; x and y are 0 or 1; and k is an integer of 1-10]. Thus it is possible to improve the light resistance while maintaining the degree of modulation and the reflectance at a high level.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an information recording medium on which information can be written using a laser beam having a high energy density, and a dye compound useful for producing the information recording medium.

[0002]

2. Description of the Related Art Conventionally, an information recording medium (optical disc) on which information can be recorded only once by a laser beam is also called a write-once CD (so-called CD-R), and is widely used, for example, as a disc memory for a computer. Have been. C
The basic structure of a DR type optical disk is a transparent disk-shaped substrate made of a polymer or the like, and Te, I
metal or semimetal such as n; or cyanine, metal complex,
A recording layer on which information can be recorded by a laser beam composed of a dye such as a quinone-based dye. Normally, a reflective layer made of gold or the like and a protective layer made of resin are sequentially provided on the recording layer in a laminated state.

Writing (recording) information on an optical disk
Is usually performed by irradiating a laser beam having a wavelength of around 780 nm. The irradiated portion of the recording layer absorbs the light and locally rises in temperature, causing a physical or chemical change (for example, a pit change). Information) is recorded by altering its optical properties. On the other hand, reading (reproduction) of information is also usually performed by irradiating a laser beam having the same wavelength as that of the recording laser beam, and a portion where the optical characteristics of the recording layer have changed (a recording portion due to pit generation or the like). Information is reproduced by detecting a difference in reflectance from a portion that does not change (unrecorded portion).

A recording layer made of a dye can be easily formed by coating instead of a vapor deposition method like a metal, so that it is advantageous in terms of manufacturing cost and further has an advantage such as higher sensitivity than a metal recording layer. Having. However, the dye recording layer generally has problems such as low stability over time against heat or light. Therefore, development of a recording layer that can maintain stable performance against heat or light over a long period of time is desired. However, at present, a recording layer having satisfactory performance has not yet been developed.

Japanese Patent Application Laid-Open No. 63-209959 discloses an information recording medium in which a recording layer comprising an oxonol dye is provided on a substrate. It is described that by using this dye compound, stable recording / reproducing characteristics can be maintained for a long period of time. The publication describes an oxonol dye compound in which ammonium is introduced in the form of a salt in the molecule.

[0006]

According to the study of the present inventors, the information recording medium containing an oxonol dye described in the above publication in the recording layer has a high storage stability and durability against heat (repeated reproduction). Although improved, it has been found that when exposed to light such as sunlight for a long time, poor reproduction is likely to occur, and the light resistance is still insufficient. Accordingly, it is a main object of the present invention to provide an information recording medium having high stability capable of sufficiently maintaining recording characteristics for a long period of time, particularly having high stability in light resistance. Another object of the present invention is to provide a novel oxonol dye compound useful for the production of an information recording medium having high storage stability as described above.

[0007]

According to the research of the present inventors,
By using an onium salt in which a hydrogen atom is not bonded to an onium atom, in particular, a quaternary ammonium salt is introduced into a conventional oxonol-based dye compound, the light resistance is further improved compared to the conventional one. It has been found that an information recording medium having high storage stability can be manufactured.

The present invention relates to an information recording medium having a recording layer on which information can be recorded by a laser beam on a substrate, wherein the recording layer is represented by the following general formula (I-1). An information recording medium comprising a dye compound and / or a dye compound represented by the general formula (I-2).

[0009]

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Wherein A ¹ , A ² , B ¹ and B ² each independently represent a substituent, and Y ¹ and Z ¹ each independently represent an atom necessary for forming a carbocyclic or heterocyclic ring. E and G each independently represent an atomic group necessary to complete a conjugated double bond chain; X ¹ represents ＝ O, ＮＲNR or ＣC (CN) ₂ , X ² Represents -O, -NR or -C (CN) ₂ (where R represents a substituent);
¹ , L ² , L ³ , L ⁴ and L ⁵ each independently represent a methine group which may be substituted, and M ^{k +} represents an onium ion in which a hydrogen atom is not bonded to a positively charged onium atom. And m and n each independently represent 0, 1 or 2, and x
And y each independently represent 0 or 1, and k is 1 to
Represents an integer of 10. ]

The present invention also provides an oxonol compound represented by the general formula (IV-1) or an oxonol compound represented by the general formula (IV-2).

[0012]

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Wherein A ³ , A ⁴ , B ³ and B ⁴ each independently represent a linear, branched or cyclic C 1 -C 18
Alkyl group, alkenyl group having 2 to 18 carbon atoms, alkynyl group having 2 to 18 carbon atoms, aryl group having 6 to 18 carbon atoms, aralkyl group having 7 to 18 carbon atoms, acyl group having 2 to 18 carbon atoms, carbon group An alkylsulfonyl group having 1 to 18 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, and 1 to 18 carbon atoms
Alkylsulfinyl group, an alkoxycarbonyl group having 2 to 18 carbon atoms, an aryloxycarbonyl group having 7 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms,
An aryloxy group having 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, an arylthio group having 6 to 10 carbon atoms,
8 represents an acyloxy group, a sulfonyloxy group, a carbamoyloxy group, an amino group, a carbamoyl group, a sulfamoyl group, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, or a 4- to 7-membered heterocyclic group. May be further substituted with at least one group selected from the group consisting of the above substituents),
Y ² and Z ² are each independently a 4- to 7-membered carbon ring or 4
Represents an atomic group necessary for forming a 7- to 7-membered heterocyclic ring (these rings further include at least one member selected from the group consisting of the substituents represented by A ³ , A ⁴ , B ³ and B ⁴ ) A 6-membered carbon ring or a 4-7-membered heterocyclic ring), L ⁶ ,
L ⁷ , L ⁸ , L ⁹ and L ¹⁰ are each independently A ³ , A
⁴ , a methine group which may be substituted with one or two groups selected from the group consisting of substituents represented by B ³ and B ⁴ , M ²⁺ represents a quaternary ammonium ion, and m
1 and n1 each independently represent 0, 1 or 2. ]

The present invention is preferably in the following modes. (1) In general formula (I-1) or (I-2), M ^{k +}
Is a quaternary ammonium ion. (2) In the general formula (I-1) or (I-2), k
Is 1 to 4. (3) In the general formula (I-1) or (I-2), k
Is 2. (4) In the dye compound represented by the general formula (I-1) or (I-2), M ^{k +} is an onium ion represented by the following general formula (II).

[0015]

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[Wherein, R ¹ and R ² each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R ³ and R ⁴ each independently represent a substituent; , R ¹ and R ³ , R ² and R ⁴ or R ³ and R ⁴ may be connected to each other to form a ring, q1 and r1 each independently represent an integer of 0 to 4, and q1 and When both r1 are 2 or more, a plurality of R ³ and a plurality of R ⁴ may be the same or different from each other. ]

(5) In the dye compound represented by formula (I-1) or (I-2), M ^{k +} is represented by the following formula (III)
Is an onium ion represented by

[0018]

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[In the formula, R ⁵ and R ⁶ each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group; R ⁷ and R ⁸ each independently represent a substituent; , R ⁵ and R ⁶ , R ⁵ and R ⁷ , R ⁶ and R ⁸ or R
⁷ and R ⁸ may be linked to each other to form a ring;
2 and r2 each independently represent an integer from 0 to 4;
When both 2 and r2 are 2 or more, a plurality of R ⁷ and a plurality of R ⁸ may be the same or different from each other. ]

(6) The dye compound represented by the following general formula (IV-
The oxonol compound represented by 1) or the general formula (IV-
An oxonol compound represented by 2).

[0021]

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Wherein A ³ , A ⁴ , B ³ and B ⁴ each independently represent a linear, branched or cyclic C 1 -C 18
Alkyl group, alkenyl group having 2 to 18 carbon atoms, alkynyl group having 2 to 18 carbon atoms, aryl group having 6 to 18 carbon atoms, aralkyl group having 7 to 18 carbon atoms, acyl group having 2 to 18 carbon atoms, carbon group An alkylsulfonyl group having 1 to 18 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, and 1 to 18 carbon atoms
Alkylsulfinyl group, an alkoxycarbonyl group having 2 to 18 carbon atoms, an aryloxycarbonyl group having 7 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms,
An aryloxy group having 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, an arylthio group having 6 to 10 carbon atoms,
8 represents an acyloxy group, a sulfonyloxy group, a carbamoyloxy group, an amino group, a carbamoyl group, a sulfamoyl group, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, or a 4- to 7-membered heterocyclic group. May be further substituted with at least one group selected from the group consisting of the above substituents),
Y ² and Z ² are each independently a 4- to 7-membered carbon ring or 4
Represents an atomic group necessary for forming a 7- to 7-membered heterocyclic ring (these rings further include at least one member selected from the group consisting of the substituents represented by A ³ , A ⁴ , B ³ and B ⁴ ) A 6-membered carbon ring or a 4-7-membered heterocyclic ring), L ⁶ ,
L ⁷ , L ⁸ , L ⁹ and L ¹⁰ are each independently A ³ , A
⁴ , a methine group which may be substituted with one or two groups selected from the group consisting of substituents represented by B ³ and B ⁴ , M ²⁺ represents a quaternary ammonium ion, and m
1 and n1 each independently represent 0, 1 or 2. ]

(7) In the dye compound of the above (6),
M ²⁺ is an ion represented by the following general formula (V).

[0024]

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Wherein R ¹¹ and R ¹² are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, or
And represents an aryl group represented by the formula (IV-
1) or (IV-2), which may be substituted with the substituents represented by A ³ , A ⁴ , B ³ and B ⁴ ), R ¹³ and R ^13
14 independently has the same meaning as the group represented by A ³ , A ⁴ , B ³ and B ⁴ in the formula (IV-1) or (IV-2),
However, R ¹¹ and R ¹³ , R ¹² and R ¹⁴ or R ¹³ and R ¹⁴ may be linked to each other to form a 4- to 7-membered ring, q3 and r
3 independently represents an integer of 0 to 4, and when both q3 and r3 are 2 or more, a plurality of R ¹³ and a plurality of R ¹⁴ may be the same or different from each other. ]

(8) In the dye compound of the above (6),
M ²⁺ is an ion represented by the general formula (VI).

[0027]

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Wherein R ¹⁵ and R ¹⁶ are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, or
And represents an aryl group represented by the formula (IV-
1) or (IV-2), which may be substituted with the substituents represented by A ³ , A ⁴ , B ³ and B ⁴ ), R ¹⁷ and R
¹⁸ independently has the same meaning as the group represented by A ³ , A ⁴ , B ³ and B ⁴ in the formula (IV-1) or (IV-2),
However, R ¹⁵ and R ¹⁶ , R ¹⁵ and R ¹⁷ , R ¹⁶ and R ¹⁸ or R ¹⁷
And R ¹⁸ may be linked to each other to form a 4- to 7-membered ring, and q4 and r4 each independently represent an integer of 0 to 4, and when both q4 and r4 are 2 or more, Multiple R ¹⁷
And a plurality of R ¹⁸ may be the same or different from each other. ]

(9) In the general formula (I-1) or (I-2), m and n are both 1 or m is 0 and n
Is 2, or m is 2 and n is 0. (10) In the general formula (I-1) or (I-2),
X ¹ is ＯO and X ² is —O. (11) A reflective layer is further provided on the recording layer. (12) In the above (11), a protective layer is further provided on the reflective layer.

(13) Formula (IV-1) or (IV-
In the oxonol compound represented by 2), M ²⁺ is an ion represented by the general formula (V).

[0031]

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Wherein R ¹¹ and R ¹² are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, or
And represents an aryl group represented by the formula (IV-
1) or (IV-2), which may be substituted with the substituents represented by A ³ , A ⁴ , B ³ and B ⁴ ), R ¹³ and R ^13
14 independently has the same meaning as the group represented by A ³ , A ⁴ , B ³ and B ⁴ in the formula (IV-1) or (IV-2),
However, R ¹¹ and R ¹³ , R ¹² and R ¹⁴ or R ¹³ and R ¹⁴ may be linked to each other to form a 4- to 7-membered ring, q3 and r
3 independently represents an integer of 0 to 4, and when both q3 and r3 are 2 or more, a plurality of R ¹³ and a plurality of R ¹⁴ may be the same or different from each other. ]

(14) Formula (IV-1) or (IV-
In the oxonol compound represented by 2), M ²⁺ is an ion represented by the general formula (VI).

[0034]

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Wherein R ¹⁵ and R ¹⁶ are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, or
And represents an aryl group represented by the formula (IV-
1) or (IV-2), which may be substituted with the substituents represented by A ³ , A ⁴ , B ³ and B ⁴ ), R ¹⁷ and R
¹⁸ independently has the same meaning as the group represented by A ³ , A ⁴ , B ³ and B ⁴ in the formula (IV-1) or (IV-2),
However, R ¹⁵ and R ¹⁶ , R ¹⁵ and R ¹⁷ , R ¹⁶ and R ¹⁸ or R ¹⁷
And R ¹⁸ may be linked to each other to form a 4- to 7-membered ring, and q4 and r4 each independently represent an integer of 0 to 4, and when both q4 and r4 are 2 or more, Multiple R ¹⁷
And a plurality of R ¹⁸ may be the same or different from each other. ]

(15) Formula (IV-1) or (IV-2)
, M1 and n1 are both 1 or m
1 is 0 and n1 is 2, or m1 is 2 and n1 is 0. (16) In formula (IV-2), the carbon ring or the heterocyclic ring formed by Y ² and Z ² is each independently a pyrazolone ring, a thiobarbituric acid ring, a barbituric acid ring, an indandione ring, or a hydroxy ring. It is a phenalene ring.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION In the information recording medium of the present invention, the recording layer comprises a dye compound represented by the following general formula (I-1) and / or
Alternatively, it is characterized by containing a dye compound represented by the general formula (I-2).

[0038]

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The dye compound used in the information recording medium of the present invention will be described below. The dye compound used in the information recording medium of the present invention comprises an anion part (dye component) and a cation part (onium component). First, the anion portion will be described in detail. In the above formula, A ¹ , A
Examples of the substituent represented by ² , B ¹ and B ² include the following. A substituted or unsubstituted linear chain having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms);
A branched or cyclic alkyl group (eg, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, cyclohexyl, methoxyethyl, ethoxycarbonylethyl, cyanoethyl, diethylaminoethyl, hydroxyethyl, Chloroethyl, acetoxyethyl, trifluoromethyl, etc.);
An alkenyl group having 2 to 18 (preferably 2 to 8 carbon atoms) (eg, vinyl, etc.); an alkynyl group having 2 to 18 (preferably 2 to 8 carbon atoms) (eg, ethynyl, etc.); 6 to 18 (preferably 6 to 10 carbon atoms) substituted or unsubstituted aryl groups (eg, phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-carboxyphenyl, 3,5-dicarboxyphenyl, etc.); Carbon number 7-1
8 (preferably 7 to 12 carbon atoms) substituted or unsubstituted aralkyl group (eg, benzyl, carboxybenzyl, etc.);

C2 to C18 (preferably C2 to C2
8) a substituted or unsubstituted acyl group (eg, acetyl,
Propionyl, butanoyl, chloroacetyl, etc.); a substituted or unsubstituted alkyl or arylsulfonyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) (eg, methanesulfonyl, p-toluenesulfonyl, etc.); To 18 (preferably 1 to 8 carbon atoms) alkylsulfinyl group (eg, methanesulfinyl, ethanesulfinyl, octanesulfinyl and the like); and an alkoxycarbonyl group having 2 to 18 (preferably 2 to 8 carbon atoms) (eg,
Methoxycarbonyl, ethoxycarbonyl, etc.); an aryloxycarbonyl group having 7 to 18 (preferably 7 to 12) carbon atoms (eg, phenoxycarbonyl, 4-methylphenoxycarbonyl, 4-methoxyphenylcarbonyl, etc.); -18 (preferably 1-8 carbon atoms)
Substituted or unsubstituted alkoxy group (e.g., methoxy, ethoxy, n-butoxy, methoxyethoxy, etc.);
A substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms (preferably 6 to 10 carbon atoms) (eg, phenoxy,
-Methoxyphenoxy and the like); an alkylthio group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) (eg, methylthio,
An arylthio group having 6 to 10 carbon atoms (eg, phenylthio and the like);

Having 2 to 18 carbon atoms (preferably having 2 to 2 carbon atoms)
8) a substituted or unsubstituted acyloxy group (eg, acetoxy, ethylcarbonyloxy, cyclohexylcarbonyloxy, benzoyloxy, chloroacetyloxy, etc.); substituted or unsubstituted having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) A substituted sulfonyloxy group (eg, methanesulfonyloxy, etc.); a substituted or unsubstituted carbamoyloxy group having 2 to 18 (preferably 2 to 8 carbon atoms) (eg, methylcarbamoyloxy, diethylcarbamoyloxy, etc.); Unsubstituted amino group or C1
To 18 (preferably 1 to 8 carbon atoms) substituted amino group (eg, methylamino, dimethylamino, diethylamino, anilino, methoxyphenylamino, chlorophenylamino, pyridylamino, methoxycarbonylamino, n-butoxycarbonylamino, phenoxycarbonylamino , Methylcarbamoylamino, phenylcarbamoylamino, ethylthiocarbamoylamino, methylsulfamoylamino, phenylsulfamoylamino, acetylamino, ethylcarbonylamino, ethylthiocarbonylamino, cyclohexylcarbonylamino, benzoylamino, chloroacetylamino, methane Sulfonylamino, benzenesulfonylamino, etc.);

C 1-18 (preferably C 1-18)
8) a substituted or unsubstituted carbamoyl group (eg, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, dimethylcarbamoyl, morpholinocarbamoyl, pyrrolidinocarbamoyl, etc.); unsubstituted sulfamoyl Group or C 1-18 (preferably C 1
To 8) substituted sulfamoyl groups (eg, methylsulfamoyl, phenylsulfamoyl, etc.); halogen atoms (eg, fluorine, chlorine, bromine, etc.); hydroxyl groups; nitro groups; cyano groups; carboxyl groups; Examples, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, imidazole ring, benzimidazole ring,
Indolenine ring, pyridine ring, morpholine ring, piperidine ring, pyrrolidine ring, aminosulfolane ring, furan ring,
A thiophene ring, a pyrazole ring, a pyrrole ring, a chroman ring, and a coumarin ring).

The substituents represented by A ¹ and A ² preferably have a Hammett's substituent constant (σp) value of 0.2 or more. Hammett's substituent constant is, for example, Che
m. Rev .. 91, 165 (1991). Particularly preferred substituents are cyano, nitro, alkoxycarbonyl, acyl, carbamoyl, sulfamoyl, alkylsulfonyl and arylsulfonyl groups.

The substituent represented by B ¹ and B ² is preferably an alkyl group, an aryl group, an alkoxy group, or an amino group.

[-C (= L ¹ )-(E) bonded to Y ^{1
x -C (= X 1) -} ] (. hereinafter, for convenience, referred to as W1) and binds to ^{Z 1 [-C (-L 5)} = (G) y
^{= C (-X 2 -) -} ] ( hereinafter, for convenience, referred to as W2) for in each conjugate state and, carbocyclic or heterocyclic ring formed by the Y ¹ and W1, and Z ¹ and W2 The carbocyclic or heterocyclic ring formed by is considered as one of the resonance structures. Said Y ¹ and W1, and Z ¹ and W
The carbocyclic or heterocyclic ring formed with 2 is preferably a 4- to 7-membered ring, particularly preferably a 5- or 6-membered ring. These rings may further form a condensed ring with another 4- to 7-membered ring. These may have a substituent. Examples of the substituent include A ¹ , A ² , B ¹ and B
Examples of the substituent represented by ² are given. Preferred as a hetero atom forming a heterocyclic ring are B,
N, O, S, Se, and Te. Particularly preferably,
N, O and S. x and y are each independently 0 or 1, and preferably both are 0.

X ¹ is ＝ O, ＮＲNR or ＣC (CN) ₂
Represents X ² is —O, —NR or —C (CN) ₂
Represents R represents a substituent. Examples of the substituent represented by R include those described above as the substituents represented by A ¹ , A ² , B ¹ and B ² . R is preferably an aryl group. Particularly preferred is phenyl. In the present invention, X ¹ is preferably ＝ O, and X ² is preferably —O.

Examples of the carbon ring formed by Y ¹ and W 1 and Z ¹ and W 2 include the following. In the examples, Ra and Rb each independently represent a hydrogen atom or a substituent.

[0048]

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Preferred carbocycles are those represented by A-1 and A-4.

Examples of the heterocyclic ring formed by Y ¹ and W 1 and Z ¹ and W 2 include the following. In the examples, Ra, Rb and Rc each independently represent a hydrogen atom or a substituent.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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Preferred heterocycles are A-5, A-6, A-
It is a heterocycle represented by 7, A-8, A-9 and A-42. Particularly preferred are A-5 (pyrazolone ring), A
-6 (barbituric acid ring), A-7 (thiobarbituric acid ring) and A-42 (benzo [b] thiophen-3-one-1,1-dioxide ring).
The substituents represented by Ra, Rb and Rc are the same as those of A ¹ , A
^2, B ¹ and those exemplified as the substituents represented by B ² and is synonymous. Ra, Rb and Rc may be linked to each other to form a carbocyclic or heterocyclic ring. Examples of the carbocycle include a saturated or unsaturated carbocycle such as a cyclohexyl ring, a cyclopentyl ring, a cyclohexene ring, and a benzene ring. Examples of the heterocycle include a saturated or unsaturated heterocycle such as a piperidine ring, a piperazine ring, a morpholine ring, a tetrahydrofuran ring, a furan ring, a thiophene ring, a pyridine ring, and a pyrazine ring. These carbocycles or heterocycles may further have a substituent. The substituent has, for example, the same meaning as the substituents represented by A ¹ , A ² , B ¹ , or B ² .

The methine groups represented by L ¹ , L ² , L ³ , L ⁴ and L ⁵ are each independently a methine group which may have a substituent. Examples of the substituent include those described above as the substituents represented by A ¹ , A ² , B ¹ and B ² . Preferred substituents are an alkyl group,
An aralkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, an amino group, a carbamoyl group and a heterocyclic group.
The substituents are linked to form a 5- to 7-membered ring (eg, a cyclopentene ring, a 1-dimethylaminocyclopentene ring, a 1-diphenylaminocyclopentene ring, a cyclohexene ring,
-Chlorocyclohexene ring, isophorone ring, 1-morpholinocyclopentene ring, cycloheptene ring). In the present invention, it is preferred that both m and n are 1, or that m is 0 and n is 2, or m is 2 and n is 0.

Next, the cation portion will be described in detail. M ^{k +}
The onium ion represented by is a hydrogen atom that is not bonded to a positively charged onium atom. Examples of the onium ion represented by M ^{k +} include a quaternary ammonium ion, an oxonium ion, a sulfonium ion, a phosphonium ion, a selenonium ion, and an iodonium ion. Preferably, M ^{k +} is not a cyanine dye. Preferred are quaternary ammonium ions.

The quaternary ammonium is generally a tertiary amine (eg, trimethylamine, triethylamine, tributylamine, triethanolamine, N-methylpyrrolidine, N-methylpiperidine, N, N-dimethylpiperazine, triethylenediamine, N, N ', N'
-Tetramethylethylenediamine, etc.) or a nitrogen-containing heterocycle (pyridine ring, picoline ring, 2,2'-bipyridyl ring, 4,4'-bipyridyl ring, 1,10-phenanthroline ring, quinoline ring, oxazole ring, thiazole ring, N-methylimidazole ring, pyrazine ring, tetrazole ring, etc.) can be obtained by alkylation (Menstockkin reaction), alkenylation, alkynylation or arylation.

The quaternary ammonium ion represented by M ^{k +} is preferably a quaternary ammonium ion composed of a nitrogen-containing heterocyclic ring, and particularly preferably a quaternary pyridinium ion.

K represents an integer of 1 to 10. Preferably it is 1-4. Particularly preferably, it is 2.

The onium ion represented by M ^{k +} is most preferably represented by the following formula (II) or (III). These compounds are usually reacted with 2,2'-bipyridyl or 4,4'-bipyridyl with a halide having a desired substituent (see, for example, JP-A No.
JP-A-1-148162) or JP-A-51-148.
It can be easily obtained by an arylation reaction according to the methods described in JP-A-16675 and JP-A-1-96171.

[0063]

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[0064]

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In the formula, R ¹ , R ² , R ⁵ and R ⁶ each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. R ³ , R ⁴ , R ⁷ and R
⁸ each independently represents a substituent (including a substituent atom). R
³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷ and R ⁸ may be linked to each other to form a ring;
¹ and R ³ , R ² and R ⁴ , R ⁵ and R ⁷ , and R ⁶ and R ⁸
May be linked to each other to form a ring. q
1 and q2, and r1 and r2 each represent an integer of 0 to 4, and when q1, q2, r1 and r2 are each 2 or more, a plurality of R ³ , R ⁴ , R ⁷ and R ⁸ are Each may be the same or different.

The alkyl group represented by R ¹ , R ² , R ⁵ and R ⁶ is preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms.
Is a substituted or unsubstituted alkyl group. They are,
It may be linear, branched, or cyclic. Examples of these include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, cyclohexyl, cyclopropyl, and the like.

Examples of the substituent of the alkyl group include the following. A substituted or unsubstituted alkenyl group having 2 to 18 carbon atoms (preferably 2 to 8 carbon atoms) (eg, vinyl);
A substituted or unsubstituted alkynyl group having 18 (preferably 2 to 8 carbon atoms) (eg, ethynyl); a substituted or unsubstituted aryl group having 6 to 10 carbon atoms (eg, phenyl, naphthyl); a halogen atom (eg, F, Cl, Br, etc.); a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) (eg, methoxy, ethoxy); a substituted or unsubstituted aryl having 6 to 10 carbon atoms An oxy group (eg, phenoxy, p-methoxyphenoxy); a substituted or unsubstituted alkylthio group having 1 to 18 (preferably 1 to 8) carbon atoms (eg, methylthio, ethylthio); Or an unsubstituted arylthio group (eg, phenylthio); a substituted or unsubstituted acyl group having 2 to 18 (preferably 2 to 8) carbon atoms (eg, acetyl, propio) Nil);

C1 to C18 (preferably C1 to C18)
8) a substituted or unsubstituted alkylsulfonyl group or arylsulfonyl group (eg, methanesulfonyl, p-
A substituted or unsubstituted acyloxy group having 2 to 18 carbon atoms (preferably 2 to 8 carbon atoms) (eg, acetoxy, propionyloxy);
18 (preferably 2 to 8 carbon atoms) substituted or unsubstituted alkoxycarbonyl group (eg, methoxycarbonyl,
Ethoxycarbonyl); a substituted or unsubstituted aryloxycarbonyl group having 7 to 11 carbon atoms (eg, naphthoxycarbonyl); an unsubstituted amino group, or 1 to 1 carbon atom
18 (preferably 1 to 8 carbon atoms) substituted amino group (eg,
Methylamino, dimethylamino, diethylamino, anilino, methoxyphenylamino, chlorophenylamino, pyridylamino, methoxycarbonylamino, n-
Butoxycarbonylamino, phenoxycarbonylamino, methylcarbamoylamino, ethylthiocarbamoylamino, phenylcarbamoylamino, acetylamino, ethylcarbonylamino, ethylthiocarbamoylamino, cyclohexylcarbonylamino, benzoylamino, chloroacetylamino, methylsulfonylamino);

C1 to C18 (preferably C1 to C1)
8) substituted or unsubstituted carbamoyl group (eg, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, dimethylcarbamoyl, morpholinocarbamoyl, pyrrolidinocarbamoyl); unsubstituted sulfamoyl group Or 1 to 18 carbon atoms (preferably 1 to 18 carbon atoms)
8) a substituted sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl); a cyano group; a nitro group;
Carboxy group; hydroxyl group; heterocyclic group (eg, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, imidazole ring, benzimidazole ring, indolenine ring, pyridine ring, piperidine ring, pyrrolidine ring, morpholine ring, sulfolane ring , Furan ring, thiophene ring, pyrazole ring, pyrrole ring, chroman ring, coumarin ring).

The alkenyl group represented by R ¹ , R ² , R ⁵ and R ⁶ is preferably a substituted or unsubstituted alkenyl group having 2 to 18 carbon atoms, more preferably 2 or more carbon atoms.
To 8 substituted or unsubstituted alkenyl groups, for example, vinyl, allyl, 1-propenyl, 1,3-butadienyl and the like. As the substituent for the alkenyl group, those mentioned above as the substituent for the alkyl group are preferable.

The alkynyl group represented by R ¹ , R ² , R ⁵ and R ⁶ is preferably a substituted or unsubstituted alkynyl group having 2 to 18 carbon atoms, more preferably 2 alkynyl groups.
To 8 substituted or unsubstituted alkynyl groups such as ethynyl and 2-propynyl; As the substituent for the alkynyl group, those described above as the substituent for the alkyl group are preferable.

The aryl group represented by R ¹ , R ² , R ⁵ and R ⁶ is preferably a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, such as phenyl and naphthyl. As the substituent of the aryl group, those described above as the substituent of the alkyl group are preferable. In addition to these, an alkyl group (eg, methyl, ethyl, etc.) is also preferable.

The heterocyclic group represented by R ¹ , R ² , R ⁵ and R ⁶ is a 5- or 6-membered saturated or unsaturated ring composed of a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. And an example thereof is an oxazole ring,
Benzoxazole ring, thiazole ring, benzothiazole ring, imidazole ring, benzimidazole ring, indolenine ring, pyridine ring, piperidine ring, pyrrolidine ring,
Examples include a morpholine ring, a sulfolane ring, a furan ring, a thiophene ring, a pyrazole ring, a pyrrole ring, a chroman ring, and a coumarin ring. The heterocyclic group may be substituted, and in this case, the substituent is preferably those exemplified as the substituent for the alkyl group.

The substituents represented by R ³ , R ⁴ , R ⁷ and R ⁸ have the same meanings as those described above as the substituents represented by A ¹ , A ² , B ¹ and B ² . In the present invention,
The substituent represented by R ³ , R ⁴ , R ⁷ and R ⁸ is preferably a hydrogen atom or an alkyl group. Particularly preferred is a hydrogen atom.

In the present invention, it is preferred that R ⁵ and R ⁶ are linked to each other to form a ring. The formed ring is preferably a 5- to 7-membered ring, more preferably a 6-membered ring. It is also preferred that R ³ and R ⁴ , and R ⁷ and R ⁸ are connected to each other to form a carbocyclic or heterocyclic ring. More preferably a carbocycle, particularly preferably,
R ³ , R ⁴ , R ⁷ and R ⁸ are each a condensed aromatic ring with a pyridine ring to which they are bonded.

In the oxonol compound represented by the general formula (IV-1) or the oxonol compound represented by the general formula (IV-2), A ³ , A ⁴ , B ³ and B ⁴ , Y
² and Z ² , L ⁶ , L ⁷ , L ⁸ , L ⁹ and L ¹⁰ , and m1 and n1 are each represented by the general formula (I-
1) or A ¹ , A ² , B ¹ and B ² , Y ¹ and Z ¹ , L ¹ , L ² , L ³ , L ⁴ and L ^{5 in} the general formula (I-2), and m and n, respectively. It has the same meaning, and the preferred range for each is also the same. Further, in M ²⁺ represented by the general formula (V) or the general formula (VI), R
¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ , and q3, r3, q4 and r4 each represent R ¹ in the aforementioned general formula (II) or general formula (III). , R ² , R
³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ , and q1, r
It has the same meaning as 1, q2 and r2, respectively, and the preferred range also has the same meaning.

The anion part (denoted by “B-”) and the cation part (“C”) of the dye compound represented by formula (I-1) or (I-2) used in the present invention.
− ”) Are specifically described below.

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Preferred specific examples of the compounds used in the present invention are shown in Table 1 below. In Table 1, the compound examples are
It is a combination of an anion part and a cation part. For example, Compound No. 1 and No. This will be described with reference to Example 5. Compound No. 1 [anion moiety (B-
3) / Cation part (C-1)], and compound No. Compound examples represented by 5 [anion part (B-3) / cation part (C-22)] are represented by the following formulas.

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Embedded image In addition, Compound No. 2-No. 4 and Compound No. 6
The same applies to the following compound examples.

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[Table 1] (Part 1)． Compound Compound No. Anion part Cation part No. Anion part Cation part ──────────────────────────────────── 1 B- 3 C- 12 B- 3C-33B-3C-84B-3C-175B-3C-226B-3C-417B-3C-468B-3C-519B-3 C-53 10 B-6 C-111 B-6 C-312 B-6 C-813 B-6 C-17 14 B-6 C-22 15 B-6 C-4116 B-6 C −46 17 B−6 C−51 18 B−6 C−53 19 B−9 C−51 20 B−11 C−51 21 B−20 C−122 B−20 C−323 B−20 C− 824 B-20 C-17 25 B-20 C-22 26 B-20 C-41 27 B-20 C-46 28 B-20 C-51 29 B-2 C-53 30 B-21 C-51 31 B-25 C-51 32 B-27 C-51 33 B-40 C-134 B-40 C-835 B-40 C-5136 B-40 C -53 37 B-41 C-20 38 B-41 C-51 39 B-41 C-53 40 B-42 C-51 ──────────────────── ────────────────

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Table 1 (Part 2) ──────────────────────────────────── Compound Compound No. Anion part Cation part No. Anion part Cation part ４１ 41 B-53 C- 342 B- 53 C-843 B-53 C-17 44 B-53 C-22 45 B-53 C-51 46 B-55 C-51 47 B-61 C-22 48 B-61 C-51 49 B-61 C-53 50 B-62 C-51 51 B-64 C-51 52 B-71 C-153 B-71 C-354 B-71 C-855 B-71 C-1756 B-71 C -22 57 B-71 C-41 58 B-71 C-46 59 B-71 C-51 60 B-71 C-53 61 B-75 C-362 B-75 C-863 B-75 C- 35 64 B-75 C-51 65 B-75 C-53 66 B-76 C-30 67 B- 6 C-51 68 B-78 C- 169 B-78 C- 5170 B-82 C- 371 B-82 C- 51 72 B-83 C- 373 B-83 C- 474 B-83 C-875 B-83 C-21 76 B-83 C-30 77 B-83 C-46 78 B-83 C-51 79 B-83 C-58 80 B-87 C-3} ───────────────────────────────

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Table 1 (Part 3) ──────────────────────────────────── Compound Compound No. Anion part Cation part No. Anion part Cation part ──────────────────────────────────── 81 B- 87 C-30 82 B- 87 C-51 83 B-93 C-384 B-93 C-30 85 B-93 C-51 86 B-97 C-51 87 B-97 C-53 88 B-99 C-51 89 B-99 C-53 90 B-107 C-391 B-107 C-22 92 B-107 C-41 93 B-107 C-46 94 B-107 C-51 95 B-115 C-51 96 B-126 C −51 97 B-134 C−51 98 B−138 C−5199 B−152 C−3 100 B−152 C−51 101 B−155 C−3 102 B−155 C−51 103 B−161 C− 3 104 B-161 C-51 10 B-3 C-74 106 B-21 C-77 107 B-82 C-75 108 B-82 C-85 109 B-115 C-75 110 B-162 C-22 111 B-162 C-75 112 B -162 C-78 113 B-164 C-78 114 B-166 C-77 115 B-167 C-78 116 B-186 C-74 117 B-188 C-74 118 B-192 C-78 119 B- 196 C-78 120 B-198 C-78 121 B-199 C-78 122 B- 75 C-86 123 B- 75 C-87 124 B- 75 C-88 125 B-203 C-75 126 B-203 C-78 127 B-203 C-22 ────────────────────────────────────

The compounds represented by the general formulas (I-1) and (I-2) according to the present invention are represented by the following general formula (VII)
-1) and alkali metal salts (eg, Li salt, Na salt, K salt and the like) of the coloring compound represented by the general formula (VII-2),
A compound having an organic ion as a counter salt such as an ammonium salt (NH ⁴⁺ salt), a triethylammonium salt (Et ₃ NH ⁺ salt), or a tributyl ammonium salt (Bu ₃ NH ⁺ salt); It can be easily synthesized by a salt exchange reaction with the onium salt represented in water or an organic solvent (methanol, ethanol, isopropanol, dimethylformamide, etc.).

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Wherein A ⁵ and A ⁶ , B ⁵ and B ⁶ , Y ³
And Z ³ , and L ¹¹ , L ¹² , L ¹³ , L ¹⁴ and L ¹⁵ ,
X ³ and X ^4, E1 and G1, m3 and n3, and x
1 and y1 are A ¹ , A ² , B ¹ and B in the general formula (I-1) or the general formula (I-2), respectively.
² , Y ¹ and Z ¹ , L ¹ , L ² , L ³ , L ⁴ and L ⁵ , X ¹ and X ² , E and G, m and n, and x and y have the same meanings.

Formula (VIII): M ^{k +} · k / rX ^{-r In the} formula, X ^r- represents an anion, and r is an integer of 1 or more (preferably 1-4, more preferably 1-2). Represent. Examples of the anion include halide ions (Cl ⁻ , B
r ^-, I ^-), sulfonate ion (CH ₃ SO ₃ ^-,
p-toluenesulfonate ion, naphthalene-1,5
-Disulfonate ion), ClO ₄ ⁻ , BF ₄ ⁻ , and PF ₆ ⁻ .

The dye compounds represented by the general formulas (VII-1) and (VII-2) are generally applicable active methylene compounds (eg, pyrazolone, thiobarbituric acid, barbituric acid, indandione) , Hydroxyphenaleon) and a methine source for introducing a methine group or a polymethine group into a methine dye. Details of this type of compound are described in JP-B-39-22069 and JP-B-43-3504.
Nos. 52-38056, 54-38129, 55
Nos. 10059 and 58-35544;
Nos. 99620, 52-92716, 59-168
No. 34, No. 63-316853, and No. 64-408
No. 27, and British Patent Nos. 11333986, U.S. Pat. Nos. 3,247,127, 4042397 and 4,
Nos. 181225, 5213956, and 5260
No. 179 can be referred to. Specifically, for introducing a monomethine group, orthoesters such as ethyl orthoformate and ethyl orthoacetate or N, N-diphenylformamidine hydrochloride and the like, and for introducing a trimethine chain, trimethoxypropene, 1,1, 1,3,3-tetramethoxypropane or malonaldehyde dianyl hydrochloride (or a derivative thereof) and the like, and pentamethine chains are introduced by glutaconaldehyde dianyl hydrochloride or 1- (2,4-dinitrophenyl) ) -Pyridinium chloride (or their derivatives) and the like, respectively.

Hereinafter, synthesis examples of the dye compound represented by the general formula (I-1) or the dye compound represented by the general formula (I-2) will be described.

(Synthesis Example 1) Synthesis of 5 1 g of the following compound a was added to 20 mL of a 0.1 N aqueous sodium hydroxide solution at room temperature, followed by stirring. To this solution, an aqueous solution in which 0.5 g of the following compound b was dissolved in 5 mL of water was added. After stirring at the same temperature for 30 minutes, the precipitated crystals were filtered, washed with water and ethanol, and dried to obtain the desired product, 0.2
3 g were obtained. λmax = 654 nm (in methanol)

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(Synthesis Example 2) Synthesis of 8 0.53 g of the compound a used above was added to 10 mL of a 0.1 N aqueous sodium hydroxide solution at room temperature, followed by stirring. An aqueous solution in which 0.2 g of the following compound c was dissolved in 5 mL of water was added to this solution. After stirring at the same temperature for 30 minutes, the precipitated crystals were filtered, washed with water and ethanol, and dried to obtain 0.4 g of the desired product. λmax = 654 nm (in methanol)

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Synthesis Example 3 Compound no. Synthesis of 9 1.0 g of the compound a used above was suspended in 20 mL of water, and 20 mL of a 0.1 N sodium hydroxide aqueous solution was added thereto.
Was added at room temperature and stirred. The following compound d is added to this solution.
An aqueous solution in which 0.4 g was dissolved in 5 mL of water was added. After stirring at the same temperature for 30 minutes, the precipitated crystals were filtered, washed with water and ethanol, and dried to obtain 0.2 g of the desired product. λ
max = 654 nm (in methanol)

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(Synthesis Example 4) Synthesis of 28 1.0 g of the following compound e was added to 10 mL of methanol, and 0.1 mL of 25% aqueous ammonia was added dropwise at room temperature with stirring. To this solution was added a solution in which 0.5 g of the compound c used above was dissolved in 2 mL of water, and stirring was continued for 30 minutes. The precipitated crystals were filtered, washed with methanol and dried to obtain 0.8 g of the desired product. λmax = 637 nm
(In methanol)

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(Synthesis Example 5) Synthesis of Compound 67 The following compound f (0.55 g) was treated with dimethylformamide (D
MF) dissolved in 10 mL. Further, the compound c used above
0.17 g was added to this solution and stirred at room temperature for 1 hour. Thereafter, 70 mL of water was added, and the precipitated crystals were filtered, washed with methanol and dried to obtain 0.5 g of the desired product. λmax = 607 nm (in methanol)

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(Synthesis Example 6) Synthesis of 71 A solution obtained by dissolving 0.35 g of the compound c used above in 20 mL of methanol was added with stirring while adding 0.93 g of the following compound g to 30 mL of methanol, and stirring was continued for 2 hours. The precipitated crystals were filtered, washed with methanol and dried to obtain 0.9 g of the desired product. λmax = 63
3 nm (in methanol)

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(Synthesis Example 7) Synthesis of 86 1.0 g of the following compound h was added to methanol, and 0.35 mL of triethylamine was further added and dissolved. To this solution, 0.46 g of the compound c used above was added, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were filtered, washed with methanol and dried to obtain 0.85 g of the desired product. λmax = 6
61 nm (in methanol)

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(Synthesis Example 8) Synthesis of 89 The following compound i1.1 g was dissolved in 2.5 mL of a 1 N aqueous sodium hydroxide solution. 0.46 g of the compound d used above was added to this solution, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were filtered, washed with methanol and dried to obtain 0.9 g of the desired product. λmax = 652 nm (in methanol)

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(Synthesis Examples 9 to 11) 45, 4
Compounds 6 and 98 were also synthesized by the same operation as in Synthesis Example 2 or Synthesis Example 4. The maximum absorption wavelength of the synthesized compound in methanol is shown below. Compound No. 45: λmax = 654 (nm) Compound No. 45 46: λmax = 674 (nm) Compound No. 46 98: λmax = 603 (nm)

(Synthesis Example 12) Synthesis of 1 2.6 g of the compound a used above was dissolved in 50 mL of a 0.1 N aqueous sodium hydroxide solution. 0.8 g of tetramethylammonium bromide was added to this solution, and
Stirred for hours. The precipitated crystals were collected by filtration, washed with water and dried to obtain 2.45 g of the desired product. λmax = 654 nm (in methanol)

(Synthesis Examples 13 to 15) 3,6
In Examples 7 and 8, synthesis was carried out in the same manner as in Synthesis Example 12 using the corresponding quaternary ammonium bromide instead of tetramethylammonium bromide. The maximum absorption wavelength (λma) of each synthesized compound in methanol
x) was 654 (nm) in all cases.

(Synthesis Example 16) Synthesis of 99 1.3 g of the following compound j was added to 10 mL of methanol, and 0.15 mL of 25% aqueous ammonia was added dropwise at room temperature with stirring. To this solution was added 1.4 g of tetrabutylammonium bromide, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were collected by filtration, washed with methanol, and dried to obtain the target compound, 0.1.
2 g were obtained. λmax = 671 nm (in methanol)

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Synthesis Example 17 Compound no. Synthesis of 100 1.3 g of the compound j used above was added to 10 mL of methanol, and 0.15 mL of 25% aqueous ammonia was added dropwise at room temperature with stirring. Into this solution was added the compound c used above.
A solution prepared by dissolving 0.38 g in methanol (20 mL) was added, and stirring was continued for 2 hours. The precipitated crystals were separated by filtration, washed with methanol and dried to obtain 0.7 g of the desired product. λmax = 671 nm (in methanol)

Synthesis Example 18 Compound no. Synthesis of 102 In the same manner as in Synthesis Example 17, except that the following compound k1.1 g was used instead of compound j, 0.45 g of the desired product was obtained. λmax = 655 nm (in methanol)

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(Synthesis Example 19) Synthesis of 106 1.0 g of the following compound 1 (L) was added to 10 ml of methanol.
Was further dissolved by adding 0.2 ml of triethylamine. A solution prepared by dissolving 0.3 g of the following compound m in 10 ml of methanol was added to this solution, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were filtered, washed with methanol and dried to obtain 0.6 g of the desired product. λmax = 636 nm (in methanol)

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(Synthesis Example 20) Synthesis of 107 1.6 g of the compound used above was added to 20 ml of methanol, and 0.5 ml of triethylamine was further added and dissolved. To this solution was added the following compound n1g in methanol 5m
The resulting mixture was stirred at room temperature for 1 hour. The precipitated crystals were filtered, washed with methanol and dried to obtain 1.6 g of the desired product. λmax = 640 nm (in dimethylformamide)

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(Synthesis Example 21) Synthesis of Compound (109)
In addition, 1 ml of triethylamine was further added and dissolved. To this solution, a solution in which 1.5 g of the compound n used above was dissolved in 5 ml of methanol was added. Further, 50 ml of methanol was gradually added to the reaction solution, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were filtered, washed with methanol and dried to obtain 3 g of the desired product. λmax = 707 nm
(In dimethylformamide)

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Synthesis Example 22 Compound no. Synthesis of 112 The following compound p3.5g was added to methanol 50ml,
Further, 1.5 ml of triethylamine was added and dissolved.
2.5 g of the following compound q was added to this solution in 10 m of methanol.
The solution dissolved in 1 was added. The precipitated crystals are filtered,
After washing with methanol and drying, 4.4 g of the desired product was obtained.
λmax = 661 nm (in dimethylformamide)

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Synthesis Example 23 Compound no. Synthesis of 115 2.3 g of the target product was obtained in the same manner as in Synthesis Example 22 except that 4.6 g of the following compound r was used instead of the compound p. λmax = 655 nm (in methanol)

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Synthesis Example 24 Compound no. Synthesis of 116 0.3 g of the following compound s in 5 ml of dimethylformamide
And 15 ml of methanol, and 1.2 ml of tributylamine was further added dropwise thereto while stirring. After stirring at room temperature for 30 minutes, the following compound t0.
30 g was added, and stirring was continued for 2 hours. The precipitated crystals were filtered, washed with methanol and dried to obtain 0.25 g of the desired product. λmax = 606 nm (in dimethylformamide)

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(Synthesis Example 25) Synthesis of 117 0.32 g of the following compound u was added to methanol, and 1.2 ml of tributylamine was further added and dissolved. To this solution, 0.28 g of the compound t used above was added, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were filtered, washed with methanol and dried to obtain 0.22 g of the desired product. λmax = 6
09 nm (in dimethylformamide)

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The compound represented by formula (I-1) or the compound represented by formula (I-2) according to the present invention may be used alone or in combination of two or more. You may. Further, the compound represented by the general formula (I-1) and the compound represented by the general formula (I-2) may be used in combination. Alternatively, the compound according to the present invention may be used in combination with a dye compound other than these.

The information recording medium of the present invention has the general formula (I)
-1) and / or general formula (I-2)
A recording layer containing a dye compound represented by the formula (1) is provided on a substrate. In the information recording medium of the present invention, it is preferable that a reflective layer is further provided on the recording layer, and a protective layer is further provided on the reflective layer. The information recording medium of the present invention can be manufactured, for example, by the method described below. The substrate can be arbitrarily selected from various materials used as a substrate of a conventional information recording medium. As a substrate material, for example,
Glass; polycarbonate; acrylic resins such as polymethyl methacrylate; vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymer; epoxy resins; amorphous polyolefins and polyesters; Good. Note that these materials can be used in the form of a film or a rigid substrate. Among the above materials, polycarbonate is preferred from the viewpoints of moisture resistance, dimensional stability, cost, and the like.

An undercoat layer may be provided on the surface of the substrate on which the recording layer is provided, for the purpose of improving flatness, improving adhesive strength, preventing deterioration of the recording layer, and the like. Examples of the material of the undercoat layer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleic anhydride copolymer, polyvinyl alcohol, N-methylol acrylamide, styrene / vinyl toluene copolymer, and chlorosulfonation. Polymeric substances such as polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate, etc .; and silane coupling agents And other surface modifiers.
The undercoat layer is formed by dissolving or dispersing the above substances in an appropriate solvent to prepare a coating solution, and then applying the coating solution to the substrate surface by a coating method such as spin coating, dip coating, or extrusion coating. can do. The thickness of the undercoat layer is generally in the range of 0.005 to 20 μm, preferably in the range of 0.01 to 10 μm.

Further, it is preferable that irregularities (grooves) indicating information such as tracking grooves or address signals are formed on the substrate (or undercoat layer). This groove is preferably formed directly on the substrate at the time of injection molding or extrusion molding of a resin material such as polycarbonate. Further, the formation of the groove may be performed by providing a pre-groove layer. As a material for the pregroove layer, a mixture of at least one monomer (or oligomer) of acrylic acid monoester, diester, triester and tetraester and a photopolymerization initiator can be used. The formation of the pre-groove layer is performed, for example, by first forming a precisely formed master (stamper).
A mixture of the above-mentioned acrylate and the polymerization initiator is applied thereon, and the substrate is further placed on the application liquid layer.Then, the application layer is cured by irradiating ultraviolet rays through the substrate or the matrix. To fix the substrate and the coating layer. Next, it can be obtained by peeling the substrate from the matrix.

The thickness of the pre-groove layer is generally 0.05
１００100 μm, preferably 0.1-50 μm
m. Pregroove depth is 300-200
It is preferably in the range of 0 °, and its half width is
It is preferably in the range of 0.2 to 0.9 μm. By setting the depth of the pre-groove layer in the range of 1500 to 2000 °, sensitivity can be improved without substantially lowering the reflectance, which is particularly preferable. Therefore, such an optical disk (an optical disk having a recording layer made of the dye of the general formula (I-1) or (I-2) on a deep pregroove substrate and a reflective layer formed thereon) is
The high sensitivity enables recording with a low laser power, which makes it possible to use an inexpensive semiconductor laser or extend the service life of the semiconductor laser.

On the surface of the substrate (or the undercoat layer) (on the surface of the groove if formed), the compound of the present invention represented by the general formula (I-1) and / or A recording layer made of the dye compound represented by the general formula (I-2) is provided. The recording layer may contain various compounds known as a singlet oxygen quencher in order to further improve light resistance. Representative examples of the quencher include metal complexes, diimmonium salts, aminium salts represented by general formulas (III), (IV) and (V) described in JP-A-3-224793.
There may be mentioned, for example, the nitroso compounds disclosed in JP-A No. 0287 and JP-A-2-300288.

The recording layer is formed by dissolving the dye compound according to the present invention and, if desired, a quencher, a binder and the like in a solvent to prepare a coating solution, and then applying this coating solution to the substrate surface to form a coating film. And then drying. Examples of the solvent for the coating solution for forming the dye recording layer include esters such as butyl acetate and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone;
Chlorinated hydrocarbons such as dichloroethane and chloroform; amides such as dimethylformamide; hydrocarbons such as cyclohexane; ethers such as tetrahydrofuran, ethyl ether and dioxane; ethanol, n-propanol, isopropanol, n-butanol and diacetone alcohol. Alcohols such as 2,2,3,3-tetrafluoropropanol; and glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol monomethyl ether. The above solvents can be used alone or in combination of two or more in consideration of the solubility of the compound used. Various additives such as an antioxidant, a UV absorber, a plasticizer, and a lubricant may be further added to the coating solution according to the purpose.

When a binder is used, examples of the binder include natural organic high molecular substances such as gelatin, cellulose derivatives, dextran, rosin and rubber; and hydrocarbon-based substances such as polyethylene, polypropylene, polystyrene and polyisobutylene. Resins; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride / polyvinyl acetate copolymer; acrylic resins such as polymethyl acrylate and polymethyl methacrylate; polyvinyl alcohol, chlorinated polyethylene, epoxy resin, Synthetic organic polymers such as butyral resins, rubber derivatives, and initial condensates of thermosetting resins such as phenol / formaldehyde resins can be given. When a binder is used in combination as a material for the recording layer, the amount of the binder used is generally 10 parts by weight or less, preferably 5 parts by weight or less based on 1 part by weight of the dye compound. The concentration of the coating solution thus prepared is generally in the range of 0.01 to 10% by weight, preferably in the range of 0.1 to 5% by weight.

Examples of the coating method include a spray method, a spin coating method, a dipping method, a roll coating method, a blade coating method, a doctor roll method, and a screen printing method. The recording layer may be a single layer or a multilayer. The thickness of the recording layer is generally in the range from 20 to 500 nm, preferably in the range from 50 to 300 nm. The recording layer may be provided not only on one side of the substrate but also on both sides.

On the recording layer, a reflection layer is provided for the purpose of improving the reflectance at the time of reproducing information. The light-reflective substance, which is the material of the reflection layer, is a substance having a high reflectance with respect to laser light.
i, Zr, Hf, V, Nb, Ta, Cr, Mo, W, M
n, Re, Fe, Co, Ni, Ru, Rh, Pd, I
r, Pt, Cu, Ag, Au, Zn, Cd, Al, G
a, In, Si, Ge, Te, Pb, Po, Sn, Bi
Metal and semimetal or stainless steel. Of these, preferred are Cr, N
i, Pt, Cu, Ag, Au, Al and stainless steel. These substances may be used alone, or in combination of two or more kinds, or as an alloy. The reflective layer can be formed on the recording layer by, for example, vapor deposition, sputtering, or ion plating of the above-mentioned reflective substance. The thickness of the reflective layer is generally in the range of 10 to 300 nm, preferably 50 to 300 nm.
The range is 200 nm.

It is preferable that a protective layer is provided on the reflective layer for the purpose of physically and chemically protecting the recording layer and the like. This protective layer may be provided on the side of the substrate where the recording layer is not provided for the purpose of enhancing the scratch resistance and the moisture resistance. As a material used for the protective layer, for example, S
Examples thereof include inorganic substances such as iO, SiO ₂ , MgF ₂ , SnO ₂ , and Si ₃ N _4; and organic substances such as a thermoplastic resin, a thermosetting resin, and a UV-curable resin. The protective layer can be formed, for example, by laminating a film obtained by extrusion of a plastic on an adhesive layer on a reflective layer and / or on a substrate. Alternatively, it may be provided by a method such as vacuum deposition, sputtering, or coating.
In the case of a thermoplastic resin or a thermosetting resin, it can also be formed by dissolving in an appropriate solvent to prepare a coating solution, applying the coating solution, and drying. In the case of a UV-curable resin, it can also be formed by preparing a coating solution as it is or by dissolving it in an appropriate solvent, applying the coating solution, and irradiating with UV light to cure. Various additives such as an antistatic agent, an antioxidant, and a UV absorber may be added to these coating solutions according to the purpose. The thickness of the protective layer is generally in the range from 0.1 to 100 μm.

The information recording medium of the present invention may be a single plate having the above-described configuration, or two substrates having the above-mentioned configuration may be faced to each other such that the recording layer is on the inside, and an adhesive or the like may be used. By using the bonding method, a bonding type recording medium can be manufactured. Alternatively, an air sandwich type recording medium is manufactured by bonding a substrate having the above configuration to at least one of two disk-shaped substrates via a ring-shaped inner spacer and a ring-shaped outer spacer. be able to. The information recording medium of the present invention can be manufactured by the above method. The thus obtained optical disk having extremely high reflectance and excellent recording / reproducing characteristics also has improved light resistance. That is, since the information recording medium of the present invention has a high reflectance of about 70%, it can be reproduced by a commercially available CD player. Therefore, an optical disk having high reflectance and excellent light resistance can be obtained.

The information recording method of the present invention is performed, for example, as follows using the above-mentioned information recording medium. First, the information recording medium is set at a constant linear velocity (1.2 for the CD format).
While rotating at a constant angular velocity, recording light such as semiconductor laser light is irradiated from the substrate side. By this light irradiation, a cavity is formed at the interface between the recording layer and the reflective layer (the cavity is formed by deformation of the recording layer or the reflective layer,
It is considered that the information is recorded when the substrate is overlaid or deformed, or when the refractive index changes due to discoloration or change in the association state of the recording layer. 500 nm to 850 as recording light
A semiconductor laser beam having an oscillation wavelength in the range of nm is used. The wavelength of this laser beam is preferably 5
It is not less than 00 nm and not more than 800 nm. And CD-R
Suitable laser beam wavelengths are in the range of 770 to 790 nm. Reproduction of information recorded as described above is performed by irradiating a semiconductor laser beam having the same wavelength as at the time of recording from the substrate side while rotating the information recording medium at the same constant linear speed as above, and detecting the reflected light. Can be performed.

[0183]

EXAMPLES Examples and comparative examples of the present invention will be described below.

[Example 1] 3 g of the oxonol dye compound (Compound No. 1) of the present invention
It was dissolved in 100 mL of 3,3-tetrafluoropropanol to obtain a coating solution for forming a recording layer. This coating solution is applied to the surface of a spiral pregroove (track pitch: 1.7 μm).
m, groove width: 0.4 μm, groove depth: 0.16
μm) was applied by spin coating to a pregroove surface of a polycarbonate substrate (diameter: 120 mm, thickness: 1.2 mm) formed by injection molding to form a recording layer. The thickness of the recording layer is about 200 n in the pre-groove.
m.

Au was sputtered on the recording layer to a thickness of about 1
A 00 nm metal reflective layer was formed. UV on the reflective layer
A curable resin (UV-curing agent SD-220, Dainippon Ink and Chemicals, Inc.) is applied, and the layer thickness is 7 μm by irradiating ultraviolet rays.
Was formed. Through the above steps, an information recording medium (hereinafter, a sample) according to the present invention was obtained.

Examples 2 to 15 The procedure of Example 1 was repeated, except that the oxonol dye compound according to the present invention shown in Table 2 was used in the same amount in place of the oxonol dye compound (Compound No. 1). An information recording medium according to the present invention was obtained in the same manner as in Example 1.

Comparative Example 1 In Example 1, instead of the oxonol dye compound (Compound No. 1), the following cyanine dye compound in which the dye component was a cation part and the anion part was a perchlorate ion (Comparative Compound An information recording medium for comparison was obtained in the same manner as in Example 1, except that the same amount of A) was used.

[0188]

Embedded image

[Comparative Example 2] In Example 1, instead of the oxonol dye compound (Compound No. 1), the following oxonol dye compound having an ammonium salt substituted with three ethyl groups in the cation portion (Comparative Example 1) Compound B)
Was used in the same manner as in Example 1 except that the same amount was used to obtain an information recording medium for comparison.

[0190]

Embedded image

[Comparative Example 3] In Example 1, instead of the oxonol dye compound (Compound No. 1), the following oxonol dye compound having an ammonium salt substituted with three ethyl groups in the cation portion (Comparative Example 1) Compound C)
Was used in the same manner as in Example 1 except that the same amount was used to obtain an information recording medium for comparison.

[0192]

Embedded image

Comparative Example 4 Example 1 was repeated except that the following oxonol dye compound having an ammonium salt in the cation portion (Comparative Compound D) was used in place of the oxonol dye compound (Compound No. 1). In the same manner as in Example 1, an information recording medium for comparison was obtained.

[0194]

Embedded image

[Comparative Example 5] In Example 1, the following oxonol dye compound having an ammonium salt substituted with three ethyl groups in the cation portion instead of the oxonol dye compound (Compound No. 1) was used. Compound E)
Was used in the same manner as in Example 1 except that the same amount was used to obtain an information recording medium for comparison.

[0196]

Embedded image

[Evaluation of Information Recording Medium] (1) Degree of Modulation The information recording medium was irradiated with a semiconductor laser beam having a wavelength of 780 nm, and while tracking the pregroove, the recording laser power was set at a constant linear velocity of 1.4 m / sec. Was varied in the range of 4 to 9 mW, and 3T and 11T EFM signals were recorded.
Reproduction was performed with a laser power of 0.5 mW, and the modulation degrees of 3T and 11T at the optimum recording power were determined. (2) Reflectance The reflectance of the pre-groove (non-recording area) at the above-mentioned optimum recording power at the time of reproduction was determined. (3) Light resistance The information recording medium recorded as described above has a Xe lamp (1
(40,000 lux) for 18 hours or 36 hours, and the degree of modulation and reflectance after irradiation were measured in the same manner as described above. Further, the presence or absence of color of the information recording medium after irradiation was visually inspected from the following viewpoints. AA: No fading. BB: The color has faded but the color remains, which is within the allowable range. CC: Little color remains. Table 2 shows the obtained evaluation results.

[0198]

[Table 4]

[0199]

[Table 5]

From the results shown in Table 2, the samples according to the present invention having the recording layer containing the oxonol compound into which the quaternary ammonium ion was introduced (Examples 1 to 18)
In the case of (1), a comparative sample having a recording layer containing a conventionally well-known cyanine dye (Comparative Example 1)
And a tertiary ammonium salt (Comparative Examples 2, 3 and 5) and a comparative sample (Comparative Examples 2 to 5) having a recording layer containing an oxonol compound obtained by introducing an ammonium salt (Comparative Example 4). Thus, it can be seen that the change in the degree of modulation is relatively small even after irradiation with the Xe lamp, and the light resistance is high. In particular, in the case of a sample having a recording layer containing an oxonol compound having a divalent cation moiety (Examples 3 to 15 and Examples 17 to 26), it is found that the light resistance is remarkably improved.

[0201]

By using the above-mentioned dye compound in which an onium ion in which a hydrogen atom is not bonded to an onium atom having a positive charge is introduced as a cation component, it is possible to maintain a high degree of modulation and reflectivity, and particularly to secure light resistance. An information recording medium with significantly improved properties can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 239/60 C07D 239/60 261/12 261/12 277/36 277/36 327/06 327/06 333/64 333/64 401/06 231 401/06 231 239 239 403/06 231 403/06 231 403/14 209 403/14 209 405/14 239 405/14 239 471/04 106 471/04 106C 108 108A 513/04 355 513 / 04 355 C09B 23/00 C09B 23/00 G G11B 7/24 516 G11B 7/24 516

Claims (16)

[Claims] An information recording medium comprising a substrate and a recording layer on which information can be recorded by a laser beam is provided.
An information recording medium, wherein the recording layer contains a dye compound represented by the following general formula (I-1) and / or a dye compound represented by the following general formula (I-2). Embedded image [Wherein, A ¹ , A ² , B ¹ and B ² each independently represent a substituent, and Y ¹ and Z ¹ each independently represent an atomic group necessary for forming a carbocyclic or heterocyclic ring. , E and G
Each independently represents an atomic group required to complete a conjugated double bond chain, and X ¹ represents ＝ O, ＮＲNR or ＝ C (C
N) ₂ , wherein X ² is -O, -NR or -C (CN)
₂ (where R represents a substituent), L ¹ , L ² , L
³ , L ⁴ and L ⁵ each independently represent a methine group which may be substituted, M ^{k +} represents an onium ion in which a hydrogen atom is not bonded to a positively charged onium atom, and m and n are Each independently represents 0, 1 or 2, x and y each independently represent 0 or 1, and k represents an integer of 1-10. ] 2. The information recording medium according to claim 1, wherein M ^{k +} is a quaternary ammonium ion. 3. The information recording medium according to claim 1, wherein k is 2. 4. The information recording medium according to claim 1, wherein M ^{k +} is an onium ion represented by the general formula (II). Embedded image [Wherein, R ¹ and R ² each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group; R ³ and R ⁴ each independently represent a substituent;
¹ and R ³ , R ² and R ⁴ or R ³ and R ⁴ may be mutually connected to form a ring, and q1 and r1 each independently represent 0
It represents to 4 integer, and if both q1 and r1 are 2 or more, plural R ³ and plural R ⁴ are each may be different even from each other the same. ] 5. The information recording medium according to claim 1, wherein M ^{k +} is an onium ion represented by the general formula (III). Embedded image [Wherein, R ⁵ and R ⁶ each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group; R ⁷ and R ⁸ each independently represent a substituent;
⁵ and R ⁶ , R ⁵ and R ⁷ , R ⁶ and R ⁸ or R ⁷ and R ⁸ may be mutually connected to form a ring, and q 2 and r 2 each independently represent an integer of 0 to 4 And when both q2 and r2 are 2 or more, a plurality of R ⁷ and a plurality of R ⁸ may be the same or different from each other. ] 6. The information recording medium according to claim 1, wherein the dye compound is an oxonol compound represented by the following general formula (IV-1) or an oxonol compound represented by the following general formula (IV-2). Embedded image [Wherein A ³ , A ⁴ , B ³ and B ⁴ are each independently a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, An alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and 7 carbon atoms
-18 aralkyl group, C 2-18 acyl group, C 1-18 alkylsulfonyl group, C 6-18
Arylsulfonyl group, an alkylsulfinyl group having 1 to 18 carbon atoms, an alkoxycarbonyl group having 2 to 18 carbon atoms, an aryloxycarbonyl group having 7 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a 6 to 18 carbon atoms Aryloxy group, an alkylthio group having 1 to 18 carbon atoms, an arylthio group having 6 to 10 carbon atoms, an acyloxy group having 2 to 18 carbon atoms, a sulfonyloxy group, a carbamoyloxy group,
Represents an amino group, a carbamoyl group, a sulfamoyl group, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, or a 4- to 7-membered heterocyclic group (these substituents are further selected from the group consisting of the above substituents) Optionally substituted with at least one group selected), Y ² and Z ²
Each independently represents an atomic group necessary for forming a 4- to 7-membered carbocyclic or 4- to 7-membered heterocyclic ring (these rings are further represented by the above-mentioned A ³ , A ⁴ , B ³ and B ⁴⁾ May be substituted with at least one group selected from the group consisting of substituted substituents, and may be condensed with a 4- to 7-membered carbon ring or a 4- to 7-membered heterocyclic ring), L ⁶ , L ⁷ , L ⁸ , L
⁹ and L ¹⁰ are each independently A ³ , A ⁴ , B ³ and B
⁴ represents a methine group which may be substituted with one or two groups selected from the group consisting of substituents, wherein M ²⁺ is
And m1 and n1 each independently represent 0, 1 or 2. ] 7. The information recording medium according to claim 6, wherein M ²⁺ is an ion represented by the following general formula (V). Embedded image [Wherein, R ¹¹ and R ¹² each independently represent a carbon number of 1 to 18
Represents an alkyl group of 2 to 18 carbon atoms, an alkenyl group of 2 to 18 carbon atoms, an alkynyl group of 2 to 18 carbon atoms, or an aryl group of 6 to 18 carbon atoms (these groups are represented by the formula (IV-1) or (IV
-2) may be substituted with the substituents represented by A ³ , A ⁴ , B ³ and B ⁴ ), R ¹³ and R ¹⁴ each independently represent the formula (IV-1) or (IV IV-2) of a ^3, a ^4, B
Has the same meaning as the groups represented by ³ and B ⁴ , provided that R ¹¹ and R
¹³ , R ¹² and R ¹⁴ or R ¹³ and R ¹⁴ are each linked to each other to form 4
May form a 7-membered ring, q3 and r3 each independently represent an integer of 0-4, and when both q3 and r3 are 2 or more, a plurality of R ¹³ and a plurality of R ¹⁴ They may be the same or different. ] 8. The information recording medium according to claim 6, wherein M ²⁺ is an ion represented by the general formula (VI). Embedded image [Wherein, R ¹⁵ and R ¹⁶ each independently represent a carbon number of 1 to 18
Represents an alkyl group of 2 to 18 carbon atoms, an alkenyl group of 2 to 18 carbon atoms, an alkynyl group of 2 to 18 carbon atoms, or an aryl group of 6 to 18 carbon atoms (these groups are represented by the formula (IV-1) or (IV
-2) may be substituted by the substituents represented by A ³ , A ⁴ , B ³ and B ⁴ ), R ¹⁷ and R ¹⁸ are each independently the above-mentioned formula (IV-1) or ( IV-2) of a ^3, a ^4, B
³ and B ⁴ have the same meaning as the group represented by the proviso, R ¹⁵ and R ^16, R ¹⁵ and R ^17, R ¹⁶ and R ¹⁸ or R ¹⁷ and R ¹⁸ 4 to 7 membered ring, each linked to each other And q4
And r4 each independently represent an integer of 0 to 4, q4 and r4
Are both 2 or more, a plurality of R ¹⁷ and a plurality of R ¹⁸
May be the same or different from each other. ] 9. m and n are both 1 or m
The information recording medium according to claim 1, wherein is 0 and n is 2, or m is 2 and n is 0. 10. The information recording medium according to claim 1, wherein X ¹ is ＯO, and X ² is —O. 11. The information recording medium according to claim 1, wherein a reflective layer is further provided on the recording layer. 12. An oxonol compound represented by the general formula (IV-1) or an oxonol compound represented by the general formula (IV-2). Embedded image [Wherein A ³ , A ⁴ , B ³ and B ⁴ are each independently a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, An alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and 7 carbon atoms
-18 aralkyl group, C 2-18 acyl group, C 1-18 alkylsulfonyl group, C 6-18
Arylsulfonyl group, an alkylsulfinyl group having 1 to 18 carbon atoms, an alkoxycarbonyl group having 2 to 18 carbon atoms, an aryloxycarbonyl group having 7 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a 6 to 18 carbon atoms Aryloxy group, an alkylthio group having 1 to 18 carbon atoms, an arylthio group having 6 to 10 carbon atoms, an acyloxy group having 2 to 18 carbon atoms, a sulfonyloxy group, a carbamoyloxy group,
Represents an amino group, a carbamoyl group, a sulfamoyl group, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, or a 4- to 7-membered heterocyclic group (these substituents are further selected from the group consisting of the above substituents) Optionally substituted with at least one group selected), Y ² and Z ²
Each independently represents an atomic group necessary for forming a 4- to 7-membered carbocyclic or 4- to 7-membered heterocyclic ring (these rings are further represented by the above-mentioned A ³ , A ⁴ , B ³ and B ⁴⁾ May be substituted with at least one group selected from the group consisting of substituted substituents, and may be condensed with a 4- to 7-membered carbon ring or a 4- to 7-membered heterocyclic ring), L ⁶ , L ⁷ , L ⁸ , L
⁹ and L ¹⁰ are each independently A ³ , A ⁴ , B ³ and B
⁴ represents a methine group which may be substituted with one or two groups selected from the group consisting of substituents, wherein M ²⁺ is
And m1 and n1 each independently represent 0, 1 or 2. ] 13. The oxonol compound according to claim 9, wherein M ²⁺ is an ion represented by the general formula (V). Embedded image [Wherein, R ¹¹ and R ¹² each independently represent a carbon number of 1 to 18
Represents an alkyl group of 2 to 18 carbon atoms, an alkenyl group of 2 to 18 carbon atoms, an alkynyl group of 2 to 18 carbon atoms, or an aryl group of 6 to 18 carbon atoms (these groups are represented by the formula (IV-1) or (IV
-2) may be substituted with the substituents represented by A ³ , A ⁴ , B ³ and B ⁴ ), R ¹³ and R ¹⁴ each independently represent the formula (IV-1) or (IV IV-2) of a ^3, a ^4, B
Has the same meaning as the groups represented by ³ and B ⁴ , provided that R ¹¹ and R
¹³ , R ¹² and R ¹⁴ or R ¹³ and R ¹⁴ are each linked to each other to form 4
May form a 7-membered ring, q3 and r3 each independently represent an integer of 0-4, and when both q3 and r3 are 2 or more, a plurality of R ¹³ and a plurality of R ¹⁴ They may be the same or different. ] 14. The oxonol compound according to claim 9, wherein M ²⁺ is an ion represented by the general formula (VI). Embedded image [Wherein, R ¹⁵ and R ¹⁶ each independently represent a carbon number of 1 to 18
Represents an alkyl group of 2 to 18 carbon atoms, an alkenyl group of 2 to 18 carbon atoms, an alkynyl group of 2 to 18 carbon atoms, or an aryl group of 6 to 18 carbon atoms (these groups are represented by the formula (IV-1) or (IV
-2) may be substituted by the substituents represented by A ³ , A ⁴ , B ³ and B ⁴ ), R ¹⁷ and R ¹⁸ are each independently the above-mentioned formula (IV-1) or ( IV-2) of a ^3, a ^4, B
³ and B ⁴ have the same meaning as the group represented by the proviso, R ¹⁵ and R ^16, R ¹⁵ and R ^17, R ¹⁶ and R ¹⁸ or R ¹⁷ and R ¹⁸ 4 to 7 membered ring, each linked to each other And q4
And r4 each independently represent an integer of 0 to 4, q4 and r4
Are both 2 or more, a plurality of R ¹⁷ and a plurality of R ¹⁸
May be the same or different from each other. ] 15. The oxonol compound according to claim 12, wherein both m1 and n1 are 1, or m1 is 0 and n1 is 2, or m1 is 2 and n1 is 0. 16. In the general formula (IV-2), the carbocyclic or heterocyclic ring formed by Y ² and Z ² is each independently:
The oxonol compound according to claim 12, which is a pyrazolone ring, a thiobarbituric acid ring, a barbituric acid ring, an indandione ring, or a hydroxyphenaleon ring.