JPH10324065A - Information recording medium and method for recording information - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a DVD-R type information recording medium having improved light resistance and durability without impairing recording/reproducing characteristics and a method for recording information. SOLUTION: The heat mode type recording medium comprises a recording layer having a combination of organic dye and organic oxidizer so that they become a specific potential difference, a combination of them so that they become a specific potential difference or a combination of a dye compound having a specific chemical structure and organic oxidizer having a predetermined reducing potential on a surface of a transparent disc-like board having a pregroove including a track pitch of 0.6 to 0.9 μm and formed thereon at a side provided with the pregroove. A laser beam having a wavelength of 600 to 700 nm is emitted to the medium to record information on the medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a heat mode type information recording medium and an information recording method capable of writing (recording) and reading (reproducing) information by using a laser beam having a high energy density. In particular, the present invention relates to a heat mode type information recording medium such as a write-once digital video disk (DVD-R) suitable for recording information using visible laser light.

[0002]

2. Description of the Related Art Conventionally, there has been known an information recording medium (write-once type optical disk, so-called CD-R type optical disk) on which information can be recorded only once by a laser beam. A typical structure of an optical disk of this type is such that a recording layer made of an organic dye, a reflective layer made of a metal such as gold, and a protective layer made of a resin are laminated in this order on a transparent disk-shaped substrate. The recording of information on the optical disk is performed by irradiating near-infrared laser light (usually laser light having a wavelength of around 780 nm) to locally heat-deform the recording layer to form pits. . On the other hand, reading (reproducing) information is usually performed by irradiating a laser beam having the same wavelength as the recording laser beam to reflect a portion where the recording layer is heated and deformed (recorded portion) and a portion where the recording layer is not deformed (unrecorded portion). It does this by detecting differences in rates.

In recent years, with the spread of personal computers and the like, an information recording medium having a higher recording density has been demanded. In order to increase the recording density, it is effective to reduce the diameter of the laser beam to be irradiated. It is theorized that laser light with a shorter wavelength can be reduced in diameter, which is advantageous for higher density. Is known. Therefore, the development of an optical disk for recording and reproducing using a laser beam having a wavelength shorter than 780 nm, which is generally used conventionally, is being promoted. For example, a write-once digital video
An optical disk called a disk (so-called DVD-R) has been proposed. This optical disc has a track pitch of C
The diameter of the pre-groove of 0.8 μm narrower than 1.6 μm of DR is 120 mm, or the diameter is 80 m.
m on a transparent disc-shaped substrate, a recording layer made of a dye, and usually two discs each further provided with a light reflection layer and a protective layer on the recording layer, or discs having substantially the same dimensions as the discs It is manufactured so as to have a structure in which the recording layer and the protective substrate are bonded together with an adhesive with the recording layer inside. DVD-Rs use visible laser light (normally 600 nm to 7 nm).
By irradiating a laser beam having a wavelength in the range of 00 nm), recording and reproduction are performed, and recording at a higher density than that of a CD-R type optical disc can be performed.

Conventionally, in a CD-R type optical disk, as a dye compound contained in a recording layer thereof, for example, a dicarbocyanine dye having a benzoindolenine skeleton (having a methine chain of 5) having absorption in the near infrared region. ) And tricarbocyanine dyes (7 methine chains) are advantageously used (JP-A-64-40382, JP-A-64-40382).
No. 40387). Further, in order to improve the light fastness, a combination of a singlet oxygen quencher with a cyanine dye as described above is generally used as an anti-fading agent. For example, as such an anti-fading agent, a nitroso compound (JP-A-2-300288), a diimmonium compound (US Pat. No. 4,656,612), and a nickel complex (JP-A-4-146189) are well known. ing.

JP-A-63-64794 proposes an information recording medium having a recording layer containing a cyanine dye and an electron-accepting compound and having improved light fastness. As a specific example, a tricarbocyanine dye having a benzoindolenine skeleton or the like (seven methine chains) is described as a cyanine dye. Cyanoquinodimethane (TCNQ) and tetracyanoethylene have been described.

[0006]

SUMMARY OF THE INVENTION The present inventor has proposed the above DV
In the production of DR, the performance when a conventional cyanine dye for CD-R and a general anti-fading agent were combined was examined. As a result, in the DVD-R, it was found that sufficient light fastness could not be obtained with a combination of a conventional cyanine dye and a conventional general anti-fading agent. It is generally known that the maximum absorption wavelength of a dye becomes longer as the spread of the pi-electron system, which causes light absorption, becomes larger. In particular, in the case of cyanine-based dyes conventionally used in many optical discs, the longer the conjugated methine chain, the longer the wavelength. Therefore, in a DVD-R in which the wavelength of the recording / reproducing laser beam is shorter than that of the CD-R, it is necessary to shorten the absorption maximum wavelength of the dye in accordance with the wavelength of the laser beam. It is effective to shorten the wavelength. However, since the characteristics of the cyanine dye having a shorter wavelength also change, in order to maintain high light fastness in the obtained DVD-R, a color fading inhibitor used in combination with the cyanine dye may be used. Consideration is important.

An object of the present invention is to provide a DVD-R type information recording medium having improved light resistance and durability without impairing the recording / reproducing characteristics, and a method of recording information using the same.

[0008]

According to the study of the present inventors,
Organic dye and organic oxidizing agent, especially organic dye and reduction potential −
In the case of a combination with an organic oxidant that is nobler than 0.6 V, a combination is made so that the oxidation potential of the organic dye and the reduction potential of the organic oxidant have a fixed relationship, or the maximum absorption wavelength of the organic dye and the organic oxidant. Are combined with each other so as to have a certain relationship, or when a cyanine dye having a specific structure is used as an organic dye, a DVD having significantly improved light fastness and durability without impairing recording / reproducing characteristics. It has been found that an -R type information recording medium can be manufactured.

Here, the value of the reduction potential of the organic oxidant means the potential at which the organic oxidant is reduced by the injection of electrons at the cathode in voltammetry, while the oxidation potential of the organic dye is the organic potential of the organic dye. The potential at which the dye emits electrons at the anode in voltammetry and is oxidized. The oxidation potential and the reduction potential can be accurately measured by this voltammetry method. That is, tetra-n-ethylammonium perchlorate is used as a supporting electrolyte.
In acetonitrile containing 1M, an organic oxidant 1 × 10 ⁻³
The voltammogram of M is measured, and it can be obtained as a half-wave potential obtained from this. Note that platinum is used as a working electrode, and a saturated calomel electrode (SCE) is used as a reference electrode, and the measurement is performed at 25 ° C.

According to the present invention, the track pitch is set to 0.6 to 0.1.
A heat-mode information recording medium in which a recording layer containing an organic dye and an organic oxidant is provided on a surface of a transparent disk-shaped substrate on which a pre-groove of 9 μm is formed on a side on which the pre-groove is provided. .

In the present invention, the track pitch is 0.6
An organic dye and an organic oxidant having a reduction potential of no less than -0.6 volts are contained on the surface of the transparent disc-shaped substrate on which the pregroove of ~ 0.9 µm is formed on the side where the pregroove is provided. The difference between the oxidation potential b volts of the organic dye and the reduction potential a volts of the organic oxidant is 0.5 <ba <1.4.
There is also a heat mode type information recording medium provided with a recording layer that is combined so as to satisfy the relational expression.

Further, according to the present invention, the track pitch is 0.6 to
On the surface of the transparent disk-shaped substrate on which the pre-groove of 0.9 μm is formed, the surface on the side where the pre-groove is provided contains an organic dye and an organic oxidant whose reduction potential is more noble than -0.6 volts, There is also an information recording medium having a recording layer that is combined so that the absorption maximum wavelength of the organic oxidant is at least 50 nm shorter than the absorption maximum wavelength of the organic dye.

Further, according to the present invention, the track pitch is set to 0.1.
On the surface of the transparent disc-shaped substrate on which the pregroove of 6 to 0.9 μm is formed, the cyanine dye represented by the following general formula (B) and the reduction potential are −
There is also an information recording medium having a recording layer containing an organic oxidant noble than 0.6 volt. General formula (B):

[0014]

Embedded image [Wherein, Z ¹ and Z ² each independently represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring;
³⁰ and R ³¹ represents an alkyl group independently, L ^3, L
⁴ , L ⁵ , L ⁶ and L ⁷ each independently represent a methine group,
n1 and n2 each independently represent 0, 1 or 2, p and q each independently represent 0 or 1, M1 represents a charge neutralizing counter ion, and m1 represents a charge neutralizing molecule. Represents a number of 0 or more required for. ]

Further, according to the present invention, the track pitch is set to 0.1.
An organic dye and an organic oxidant having a reduction potential of no less than -0.6 volts are coated on the surface of the transparent disc-shaped substrate on which the pregroove of 6 to 0.9 μm is formed on the side where the pregroove is provided. And the difference between the oxidation potential b volts of the organic dye and the reduction potential a volts of the organic oxidant is 0.5 <ba <1.
The two laminated bodies provided with the recording layers combined so as to satisfy the relational expression 4 are arranged such that the recording layers are on the inside,
Alternatively, there is also a heat mode type information recording medium in which one of the laminates and the disc-shaped protective plate are joined so that the recording layer is on the inside.

Further, according to the present invention, the track pitch is set to 0.1.
An organic dye and an organic oxidant having a reduction potential of no less than -0.6 volts are coated on the surface of the transparent disc-shaped substrate on which the pregroove of 6 to 0.9 μm is formed on the side where the pregroove is provided. Including, two recording layers provided with a recording layer combined such that the absorption maximum wavelength of the organic oxidant is 50 nm or more shorter than the absorption maximum wavelength of the organic dye, the recording layer and the inner layer There is also a heat mode type information recording medium in which one of the laminates and a disk-shaped protective plate are joined so that the recording layer is on the inside.

Further, according to the present invention, the track pitch is set to 0.1.
On the surface of the transparent disc-shaped substrate on which the pregroove of 6 to 0.9 μm is formed, the cyanine dye represented by the following general formula (B) and the reduction potential are −
The two laminates provided with a recording layer containing an organic oxidant noble than 0.6 volts, such that the recording layer is on the inside,
Alternatively, there is also a heat mode type information recording medium in which one of the laminates and the disc-shaped protective plate are joined so that the recording layer is on the inside. General formula (B):

[0018]

Embedded image [Wherein, Z ¹ and Z ² each independently represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring;
³⁰ and R ³¹ represents an alkyl group independently, L ^3, L
⁴ , L ⁵ , L ⁶ and L ⁷ each independently represent a methine group,
n1 and n2 each independently represent 0, 1 or 2, p and q each independently represent 0 or 1, M1 represents a charge neutralizing counter ion, and m1 represents a charge neutralizing molecule. Represents a number of 0 or more required for. ]

According to the present invention, the information recording medium described above has a thickness of 600 nm to 700 nm (preferably 620 nm to 6 nm).
There is also an information recording method in which information is recorded by irradiating a laser beam having a wavelength of 80 nm, more preferably 630 nm to 650 nm).

The present invention is preferably in the following modes. (1) The oxidation potential b volt of the organic dye is 0.5 <b <
1.2 (more preferably 0.6 <b <1.1, especially 0.6 <b <1.0, most preferably 0.7 <b <
1.0). (2) The reduction potential a volt of the organic oxidant is -0.6 <a
<0.6 (more preferably -0.3 <a <0.3, particularly -0.2 <a <0.2, most preferably -0.1
<B <0.2). (3) The difference between the oxidation potential b volt of the organic dye and the reduction potential a volt of the organic oxidant is 0.8 <ba <1.2 (more preferably, 0.8 <ba <1.0. ) Is satisfied. (4) The absorption maximum wavelength of the organic oxidant is shorter than the absorption maximum wavelength of the organic dye by 50 nm or more (preferably 100 nm).
nm or more and 300 nm or less on the short wavelength side, more preferably 1 nm or less.
It is on the short wavelength side of 50 nm or more and 250 nm or less, most preferably on the short wavelength side of 150 nm or more and 200 nm or less.

(5) The organic oxidizing agent is a compound represented by the following general formula (A). General formula (A):

[0022]

Embedded image

[Wherein, X ¹ and X ² each independently represent an oxygen atom, a sulfur atom, a ＮＲNR ¹ group, or a ＣＲCR ² R ³ group, and m and n are 0 such that m + n ≧ 2. And R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and L ¹ and L ² each independently represent a divalent linking group. (6) More preferably, the organic oxidizing agent is a compound represented by the following general formula (AI). General formula (AI):

[0024]

Embedded image Wherein, X ¹¹ and X ¹² each independently represent an oxygen atom, a sulfur atom, = NR ⁸ group, or = a CR ⁹ R ¹⁰ group, R ^8, R
⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent;
¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent, and R ¹¹ and R ¹² , or R ¹³ and R ¹⁴ may be connected to each other to form an unsaturated condensed ring. (7) The organic oxidizing agent is particularly preferably a compound represented by the following general formula (A-II). General formula (A-II):

[0025]

Embedded image [Wherein, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a substituent, and R ¹⁵ and R ¹⁶ , and R ¹⁷ and R ¹⁸ are each linked to form an unsaturated fused ring You may. (8) The organic oxidizing agent is most preferably a compound represented by the following general formula (A-III). General formula (A-III):

[0026]

Embedded image [Wherein, R ¹⁹ represents a halogen atom, a cyano group, an alkoxy group, an alkylthio group, an amide group, a sulfonamide group, a ureido group, an acyl group, or an alkoxycarbonyl group, and R ²⁰ represents a hydrogen atom or a substituent. And m4 is 1
When m4 or 4-m4 represents an integer of 2 or more, a plurality of R ¹⁹ or a plurality of R ²⁰ may be different from each other. (9) In the above (8), the organic oxidizing agent is a compound represented by the following formula.

[0027]

Embedded image (10) It is most preferable that the organic oxidizing agent is a compound represented by the following general formula (A-IV). General formula (A-IV):

[0028]

Embedded image [Wherein, R ²¹ represents a hydrogen atom or a substituent, and m5 represents 0
Represents 6 integer, when m5 represents an integer of 2 or more, plural R ⁴² may be different from each other. (11) In the above (10), the organic oxidizing agent is a compound represented by the following formula.

[0029]

Embedded image (12) The cyanine dye is a compound represented by the following general formula (BI). General formula (BI):

[0030]

Embedded image [Wherein, Z ¹¹ and Z ²² each independently represent an atomic group required for forming a benzene ring, a naphthalene ring, a pyrazine ring or a quinoxaline ring, which may have a substituent, and X ³ and X ⁴ each independently represents an oxygen atom, a sulfur atom, —C (R ³⁴ ) (R ³⁵ ) —, or —N (R ³⁶ ) —, and R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ Each independently represents an alkyl group having 1 to 8 carbon atoms which may be substituted, and R ³⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent. An aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heterocyclic group,
^Represents a carbamoyl group having 1 to 8 carbon atoms or a halogen atom, M2 ^m2- represents an anion, and m2 represents 1 or 2. (13) A light reflecting layer made of metal is further provided on the recording layer. (14) The disc-shaped substrate has a diameter of 120 ± 3 mm and a thickness of 0.6 ± 0.1 mm, or a diameter of 80 ± 3 mm and a thickness of 0.6 ± 0.1 mm.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION The information recording medium of the present invention has a recording layer containing an organic dye and an organic oxidizing agent on a transparent disk-shaped substrate on which a pregroove having a track pitch of 0.6 to 0.9 μm is formed. Having. The organic oxidizing agent used in the present invention is a compound whose reduction potential a (V) is more noble than -0.6V. The reduction potential a (V) of the organic oxidant is -0.6 <a <
0.6 (more preferably -0.3 <a <0.3, especially -0.2 <a <0.2, most preferably -0.1
<B <0.2). On the other hand, the oxidation potential a (V) of the organic dye is 0.5 <b <1.2 (more preferably, 0.6 <b <1.1, particularly 0.6 <b <
1.0, and most preferably 0.7 <b <1.0.

In the present invention, the specific organic oxidizing agent and the organic dye as described above are combined with the oxidation potential a of the organic dye.
(V) and the reduction potential b (V) of the organic oxidant are 0.
5 <ba <1.4 (preferably 0.8 <ba <
1.2, more preferably 0.8 <b−a <1.0).

In the present invention, the above-mentioned specific organic oxidizing agent and the organic dye are combined with each other so that the absorption maximum wavelength of the organic oxidizing agent is at least 50 nm shorter than the absorption maximum wavelength of the organic dye (preferably, , 100 nm or more, 300 nm or less, more preferably 150 nm or more, 250 nm
Below the short wavelength side, most preferably 150 nm or more, 200
(nm or shorter wavelength side).

Further, in the present invention, the above-mentioned specific organic oxidizing agent is used in combination with a cyanine dye represented by the following general formula (B) as an organic dye.

The organic oxidizing agent and the organic dye used in the present invention will be described below. First, the organic oxidizing agent will be described. As the organic oxidizing agent, a carbocyclic or heterocyclic compound having a plurality of exocyclic double bonds is preferable. Examples of the atoms constituting the ring include nitrogen, oxygen, sulfur, and selenium in addition to carbon. In the present invention, the organic oxidizing agent is preferably a compound represented by the following general formula (A).

[0036]

Embedded image

In the formula, X ¹ and X ² each independently represent an oxygen atom, a sulfur atom, a ＮＲNR ¹ group, or a ＣＲCR ² R ³ group. m and n represent an integer of 0 to 3 such that m + n ≧ 2. R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent. L ¹ and L ² each independently represent a divalent linking group.

Hereinafter, the organic oxidizing agent represented by formula (A) will be described in detail. In the general formula (A), m and n
Are preferably 1. The above R ¹ , R ² and R
^The substituent represented by ³ is a halogen atom, or a substituent formed by combining a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. Examples of the substituent include an alkyl group, an alkenyl group, an aralkyl group, an aryl group,
Heterocyclic group, cyano group, nitro group, mercapto group, hydroxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyloxy group, amino group,
Alkylamino group, amide group, sulfonamide group, sulfamoylamino group, alkoxycarbonylamino group,
Alkoxysulfonylamino group, ureido group, thioureido group, acyl group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group, alkylsulfinyl group, sulfamoyl group, carboxyl group (including salt),
And sulfo groups (including salts). These may be further substituted with these substituents.

Examples of the substituents represented by R ¹ , R ² and R ³ will be described in more detail. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. The alkyl group is an alkyl group having 1 to 18 carbon atoms (preferably having 1 to 6 carbon atoms), which may have a linear, branched or cyclic substituent.
Ethyl, propyl, isopropyl, t-butyl, cyclopentyl, cyclohexyl, 2-hydroxyethyl, 3
-Hydroxypropyl, 4-hydroxybutyl, 3-methoxypropyl, 2-aminoethyl, acetamidomethyl, 2-acetamidoethyl, carboxymethyl, 2-
Examples thereof include carboxyethyl, 2-sulfoethyl, ureidomethyl, 2-ureidoethyl, carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl, pentyl, hexyl, octyl, decyl, undecyl, dodecyl, hexadecyl, and octadecyl. The alkenyl group is a linear, branched or cyclic alkenyl group having 2 to 18 (preferably 2 to 6) carbon atoms, for example, vinyl, allyl, 1-propenyl, 2-
Pentenyl, 1,3-butadienyl, 2-octenyl,
3-Dodecenyl can be mentioned.

The aralkyl group is an aralkyl group having 7 to 10 carbon atoms, such as benzyl. The aryl group has 6 carbon atoms which may have a substituent.
And 10 to 10 aryl groups, for example, phenyl, naphthyl, p-dibutylaminophenyl, and p-methoxyphenyl. A heterocyclic group is composed of a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom.
A 6-membered saturated or unsaturated heterocyclic group, and the number of heteroatoms and the kind of element constituting the ring may be one or more. For example, furyl, benzofuryl, pyranyl, pyrrolyl, imidazolyl , Isoxazolyl, pyrazolyl, benzotriazolyl, pyridyl, pyrimidyl, pyridazinyl, thienyl, indolyl, quinolyl,
Examples include phthalazinyl, quinoxalinyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, piperidyl, piperazinyl, indolinyl, and morpholinyl.

The alkoxy group is an alkoxy group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, -Methoxyethoxy, 2-methanesulfonylethoxy, pentyloxy,
Hexyloxy, octyloxy, undecyloxy,
Dodecyloxy, hexadecyloxy and octadecyloxy can be mentioned. The aryloxy group is an aryloxy group which may have a substituent having 6 to 10 carbon atoms, and examples thereof include phenoxy and p-methoxyphenoxy. The alkylthio group has 1 carbon atom.
To 18 (preferably 1 to 6 carbon atoms) alkylthio groups such as methylthio, ethylthio, octylthio, undecylthio, dodecylthio, hexadecylthio, and octadecylthio. The arylthio group is an arylthio group having 6 to 10 carbon atoms which may have a substituent, and examples thereof include phenylthio and 4-methoxyphenylthio. The acyloxy group is an acyloxy group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and examples thereof include acetoxy, propanoyloxy, pentanoyloxy, octanoyloxy, dodecanoyloxy, and octadecanoyloxy. it can.

The alkylamino group is an alkylamino group having 1 to 18 carbon atoms (preferably having 1 to 6 carbon atoms), for example, methylamino, dimethylamino, diethylamino, dibutylamino, octylamino, dioctylamino, undecyl Amino can be mentioned. The amide group is an amide group having 1 to 18 carbon atoms (preferably having 1 to 6 carbon atoms), for example, acetamido, acetylmethylamino, acetyloctylamino, acetyldecylamino, acetylundecylamino, acetyloctadecylamino, and propa. Examples include noylamino, pentanoylamino, octanoylamino, octanoylmethylamino, dodecanoylamino, dodecanoylmethylamino, and octadecanoylamino. The sulfonamide group is a sulfonamide group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), such as methanesulfonamide, ethanesulfonamide, propylsulfonamide, -Methoxyethylsulfonamide, 3-aminopropylsulfonamide, 2-acetamidoethylsulfonamide, octylsulfonamide, and undecylsulfonamide.

The alkoxycarbonylamino group is an alkoxycarbonylamino group having 2 to 18 carbon atoms (preferably having 2 to 6 carbon atoms), for example, methoxycarbonylamino, ethoxycarbonylamino, octyloxycarbonylamino, undecyloxycarbonyl Amino can be mentioned. An alkoxysulfonylamino group is
It is an alkoxysulfonylamino group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and examples thereof include methoxysulfonylamino, ethoxysulfonylamino, octyloxysulfonylamino, and undecyloxysulfonylamino. The sulfamoylamino group is
A sulfamoylamino group having 0 to 18 carbon atoms (preferably 0 to 6 carbon atoms), for example, methylsulfamoylamino, dimethylsulfamoylamino, ethylsulfamoylamino, propylsulfamoylamino, octyl Sulfamoylamino and undecylsulfamoylamino can be mentioned.

The ureido group is a ureido group which may have a substituent having 1 to 18 carbon atoms (preferably, 1 to 6 carbon atoms). Examples thereof include ureido, methylureido, N,
N-dimethylureide, octylureide and undecylureide can be mentioned. The thioureido group is a thioureido group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), for example, thioureido, methylthioureido, N, N-dimethylthioureido, octylthio Ureido and undecylthioureide. The acyl group has 1 to 18 carbon atoms.
It is an acyl group (preferably having 1 to 6 carbon atoms) such as acetyl, benzoyl, octanoyl, decanoyl, undecanoyl and octadecanoyl. The alkoxycarbonyl group is an alkoxycarbonyl group having 2 to 18 carbon atoms (preferably having 2 to 6 carbon atoms), and examples thereof include methoxycarbonyl, ethoxycarbonyl, octyloxycarbonyl, and undecyloxycarbonyl.

The carbamoyl group is a carbamoyl group which may have a substituent having 1 to 18 carbon atoms (preferably, 1 to 6 carbon atoms), for example, carbamoyl, N, N-
Dimethylcarbamoyl, N-ethylcarbamoyl, N-
Octylcarbamoyl, N, N-dioctylcarbamoyl and N-undecylcarbamoyl can be mentioned. The alkylsulfonyl group is an alkylsulfonyl group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), for example, methanesulfonyl, ethanesulfonyl, 2-chloroethanesulfonyl, octanesulfonyl And undecanesulfonyl. The alkylsulfinyl group is an alkylsulfinyl group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and examples thereof include methanesulfinyl, ethanesulfinyl, and octanesulfinyl. The sulfamoyl group has 0 to 18 carbon atoms (preferably 0 carbon atoms).
To 6) which may have a substituent, for example, sulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, octylsulfamoyl,
Dioctylsulfamoyl and undecylsulfamoyl can be mentioned.

L ¹ and L ² each independently represent a divalent linking group. Here, the divalent linking group is composed of a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and X ¹ , X
² together with the carbon atom to which it is attached forms a 4- to 8-membered ring. Specific examples of L ¹ and L ² include —C (R ⁴ ) (R
^{5) -, - C (R} 6) =, - N (R 7) -, - N =, - O-,
And a divalent linking group constituted by combining -S-. Here, R ⁴ , R ⁵ , R ⁶ and R ⁷
Each independently represents a hydrogen atom or a substituent, the details of which are the same as those described above for R ¹ , R ² and R ³ . Further, the 4- to 8-membered ring may form a saturated or unsaturated condensed ring, and examples of the condensed ring include a cycloalkyl ring, an aryl ring and a hetero ring. It has the same meaning as that described for R ¹ , R ² and R ³ .

The above 4- to 8-membered ring will be described in more detail. Examples of the four-membered ring include cyclobutanedione, cyclobutenedione, and benzocyclobutenequinone. Examples of 5-membered rings include cyclopentanedione, cyclopentenedione, cyclopentanedione,
Cyclopentenetrione, indandione, indantrione, tetrahydrofurandion, tetrahydrofurantrione, tetrahydropyrroledione, tetrahydropyrroletrione, tetrahydrothiophenedione,
Tetrahydrothiophenetrione can be mentioned. Examples of 6-membered rings include benzoquinone, quinomethane,
Quinodimethane, quinoneimine, quinonediimine, thiobenzoquinone, dithiobenzoquinone, naphthoquinone, anthraquinone, dihydrochromementione, dihydropyridinedione, dihydropyrazinedione, dihydropyrimidinedione, dihydropyridazinedione, dihydrophthalazinedion, dihydroisoquinolinedione, tetrahydroquinolinetrione Can be.

Examples of the 7-membered ring include cycloheptanedione, cycloheptanetrione, azacycloheptanetrione, diazacycloheptanetrione, oxocycloheptanetrione, dioxocycloheptanetrione, and oxoazacycloheptanetrione. it can. Examples of 8-membered rings include cyclooctanedione, cyclooctanetrione, azacyclooctanetrione, diazacyclooctanetrione, oxocyclooctanetrione, dioxocyclooctanetrione, oxoazacyclooctanetrione, cyclooctenedione, cyclooctanedione, and cyclooctanedione. Examples thereof include dienedione and dibenzocyclooctenedione. L ¹ and L ² are X ¹ and X ²
As a ring formed jointly with the carbon atom to which
Preferably it is a 6-membered ring.

The organic oxidizing agent is more preferably a compound represented by the following general formula (AI).

[0050]

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In the formula, X ¹¹ and X ²² each independently represent an oxygen atom, a sulfur atom, ＮＲNR ⁸ , or ＣＲCR ⁹ R ¹⁰ .
R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent. = NR ⁸ and = CR ⁹ R ¹⁰ represented by X ¹¹ and X ²² are each represented by X in the general formula (A).
^It has the same meaning as ＝ NR ¹ and ＣＲCR ² R ³ represented by ¹ and X ² , and the preferred range is also the same. R ⁸ ,
The substituents represented by R ⁹ and R ¹⁰ have the same meanings as the substituents represented by R ¹ , R ² and R ³ in formula (A), and the preferred ranges are also the same. R ¹¹ , R ¹² ,
R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent. When R ¹¹ and R ¹² , or R ¹³ and R ¹⁴ are a substituent at the same time, they may be connected to each other to form an unsaturated condensed ring. The unsaturated condensed ring may have a substituent, and examples of the substituent include the same as those described above for R ^{1 to} R ³ .

Preferably, X ¹¹ and X ²² each independently represent an oxygen atom or a ＝ CR ⁹ R ¹⁰ group, more preferably both an oxygen atom or both a ＣＲCR ⁹ R ¹⁰ group. Here, R ⁹ and R ¹⁰ are preferably each independently a halogen atom, a cyano group, an acyl group, an alkoxycarbonyl group, or an alkylsulfonyl group. X
^The case where both ¹¹ and X ²² are oxygen atoms will be described. When X ¹¹ and X ²² are both oxygen atoms, R ¹¹ , R
^12, more preferably at least two R ¹³ and R ¹⁴ is an electron withdrawing group. Here, the electron-withdrawing group means a substituent having a positive Hammett σp value, and specifically,
Examples include a halogen atom, a cyano group, a nitro group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, and an alkylsulfinyl group. Particularly preferred combinations when X ¹¹ and X ²² are both oxygen atoms are R ¹¹ , R ¹² , R ¹³ and R
¹⁴ is each independently a hydrogen atom, an alkyl group, a halogen atom, a cyano group, a nitro group, an alkoxy group, an alkylthio group, an amino group, an alkylamino group, an amide group, a sulfonamide group, a sulfamoylamino group, an alkoxycarbonylamino Group, an alkoxysulfonylamino group, a ureido group, a thioureido group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an alkylsulfinyl group, and a sulfamoyl group, wherein at least two of them are electron-withdrawing groups. It is.

The most preferred combination is R ¹¹ ,
R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom,
To 6 alkyl groups, halogen atoms, cyano groups, 1 carbon atoms
-C6 alkoxy group, C1-6 alkylthio group,
An amide group having 1 to 6 carbon atoms, a sulfonamide group having 1 to 6 carbon atoms, an ureido group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, 1 carbon atom Or a carbamoyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, and an alkylsulfinyl group having 1 to 6 carbon atoms, at least two of which are a halogen atom, a cyano group, an alkylsulfonyl group or an alkylsulfinyl group.

When both X ¹¹ and X ²² are ＝ CR ⁹ R ¹⁰ groups, the organic oxidizing agent is particularly preferably a compound represented by the following formula (A-II).

[0055]

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In the formula, R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ each independently have the same meaning as that described for R ^{11 to} R ¹⁴ .

The organic oxidizing agent is most preferably a compound represented by the following formula (A-III) or (A-IV).

[0058]

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In the formula, R ¹⁹ represents a halogen atom, a cyano group, an alkoxy group, an alkylthio group, an amide group, a sulfonamide group, a ureido group, an acyl group, or an alkoxycarbonyl group. R ²⁰ has the same meaning as described in R ^{1 to} R ³ . m4 represents an integer of 1 to 4,
When m4 or 4-m4 represents an integer of 2 or more, a plurality of R ³¹ and a plurality of R ³² may be the same or different.

[0060]

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In the formula, R ²¹ represents a hydrogen atom or a substituent. Here, the substituent means the same as described for R ^{1 to} R ³ . m5 represents an integer of 0 to 6, and when m5 represents an integer of 2 or more, a plurality of R ^{21 s} may be the same or different.

In the general formula (A-III), R ¹⁹ and R ²⁰
Preferred combinations are described below. R ¹⁹ is a halogen atom, a cyano group, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 1 to 8 carbon atoms, or an alkoxycarbonyl group having 2 to 6 carbon atoms, and R ²⁰ is a hydrogen atom, 1 to 6 carbon atoms. preferably the combination is a alkyl group, and most preferred combination is a R ¹⁹ is an alkoxy group having 1 to 6 carbon atoms, and R ²⁰
Is a hydrogen atom.

The organic oxidizing agent represented by the general formula (A-III) is particularly preferably a compound represented by the following formula.

[0064]

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In the general formula (A-IV), R ²¹ is preferably a hydrogen atom, an alkyl group, a halogen atom, a cyano group, an alkoxy group, an alkylthio group, an amide group, a sulfonamide group, a ureido group, or an acyl group. And more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an amide group having 1 to 6 carbon atoms A sulfonamide group having 1 to 6 carbon atoms, a ureido group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, particularly preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorine atom, It is a chlorine atom, a bromine atom, a cyano group, or an alkoxy group having 1 to 6 carbon atoms, and most preferably a hydrogen atom.

Specific examples of the organic oxidizing agent used in the present invention are described below.

[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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Compounds represented by the general formula (A) are described, for example, in J. Chem. Soc. Perkin Trans. 1,611 (1992), Synth
It can be easily synthesized according to a general synthesis method such as esis, 546 (1971). In addition, the following synthesis examples and methods based thereon can also be used. Synthesis Example According to the following formula, the exemplified compound (A-22) according to the present invention was synthesized.

[0085]

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Synthesis of (A-22a) 1,4-dibromo-2,5-difluorobenzene 2.7
2 g, potassium iodide 24.9 g, copper iodide 9.53 g, and HMPA (hexamethylphosphoric triamide) 3
0 ml were mixed and heated to 150-160 ° C under nitrogen. After completion of the reaction, a diluted hydrochloric acid solution and ether were poured into the reaction solution, and a copper salt was filtered, followed by extracting an organic layer. The organic layer was washed with aqueous sulfite, dried over sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain 2.93 g of (A-22a) as yellow crystals.

Synthesis of (A-22b) 3.66 g of (A-22a), 2.64 of malononitrile
g, sodium hydride 1.44 g, and bistriphenylphosphine palladium chloride 0.21 g in THF.
(Tetrahydrofuran) (60 ml) was added, and the mixture was heated under reflux for 12 hours. After completion of the reaction, the reaction solution was poured into 1N hydrochloric acid, and a white precipitate was separated by filtration and dried to obtain 2.68 g of a white solid (A-22b).

Synthesis of (A-22) 100 ml of water was added to 3.36 g of (A-22b), and an excessive amount of bromine water was slowly added dropwise to the suspension. After standing overnight, the resulting red precipitate was filtered off, washed with cold water and dissolved in 60 ml of methylene chloride. The solution was dried over sodium sulfate, treated with activated carbon, and the solvent was distilled off. As a result, yellow crystals 3.11 of the target compound (A-22) were obtained.
g was obtained.

According to the following formula, the exemplified compound (A-
58) was synthesized.

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Synthesis of (A-58a) 25.0 g of chloranil was dissolved in 60 ml of acetonitrile, and ammonia gas was continuously introduced into the suspension. The obtained tea solid was collected by filtration, water and then acetonitrile 100
and then dried under reduced pressure (A-58a) 19.6
g was obtained. Synthesis of (A-58) (A-58a) 2.1 g, lauric chloride 4.4
g, and 2.8 ml of triethylamine in 100 ml of DMF.
Then, the mixture was heated at 70 ° C. After heating for 7 hours, the mixture was poured into 300 ml of cold water and extracted with ethyl acetate. After drying over sodium sulfate, the mixture was concentrated, and recrystallized from acetonitrile to obtain 1.7 g of yellow crystals of the target compound (A-58).

The organic oxidizing agent represented by the general formula (A) may be used alone or in combination with another known quencher. Typical examples of the combined quencher include metal complexes represented by the general formulas (III), (IV) and (V) described in JP-A-3-224793, diimmonium salts, aminium salts, and JP-A-2-224. Japanese Patent Application Publication No. 300287 and JP-A-2-30028
And the nitroso compound described in Japanese Patent Publication No. 8 (Kokai) No. 8 can be mentioned. Particularly preferred as a combined quencher are a metal complex (for example, PA-1006 (Mitsui Toatsu Fine Co., Ltd.)) or a diimmonium salt (for example, IRG-023, IRG-022 (all Nippon Kayaku Co., Ltd.)) And most preferred are diimmonium salts. These quenchers can be used in combination of two or more depending on the purpose.

The amount of the organic oxidizing agent represented by the general formula (A) is preferably in the range of 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, based on 100 parts by weight of the organic dye. More preferably, it is particularly preferably in the range of 1 to 25 parts by weight, most preferably 1 to 10 parts by weight. The added amount of the quencher is 100 organic dyes.
It is preferably in the range of 1 to 100 parts by weight relative to parts by weight, more preferably in the range of 1 to 50 parts by weight,
It is particularly preferably in the range of 1 to 25 parts by weight, and most preferably in the range of 1 to 10 parts by weight.

Next, the organic dye used in the present invention will be described. Examples of usable organic dyes include, for example, cyanine dyes, merocyanine dyes, phthalocyanine dyes, oxonol dyes, pyrylium dyes, thiopyrylium dyes, triarylmethane dyes, polymethine dyes, squarium dyes, and azurenium dyes Pigment,
Examples include naphthoquinone dyes, anthraquinone dyes, indophenol dyes, indoaniline dyes, aminium / diimmonium dyes, and pyran dyes. In the present invention, it is preferable to use a symmetric or asymmetric cyanine dye represented by the following general formula (B).

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In the formula, Z ¹ and Z ² each independently represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. R ³⁰ and R ³¹ each independently represent an alkyl group. L ³ , L ⁴ , L ⁵ , L ⁶ and L ⁷ each independently represent a methine group. n1 and n2 each independently represent 0, 1 or 2. p and q each independently represent 0 or 1. M1
Represents a charge neutralizing counter ion, and m1 represents a number of 0 or more necessary to neutralize the charge in the molecule.

The cyanine dye represented by formula (B) will be described in detail below. Z ¹ and Z ² each independently represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. p and q each independently represent 0 or 1. p and q are preferably both 0.
The nucleus formed by Z ¹ and Z ² includes 3,3-
Dialkyl indolenine nucleus, 3,3-dialkyl benzoindolenine nucleus, thiazole nucleus, benzothiazole nucleus,
Naphthothiazole nucleus, thiazoline nucleus, oxazole nucleus,
Benzoxazole nucleus, naphthoxazole nucleus, oxazoline nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, selenazoline nucleus, tellurazole nucleus, benzotellurazole nucleus, naphthotellurazole nucleus, tellrazoline nucleus, imidazole nucleus, benzimidazole nucleus, Naphthoimidazole nucleus, pyridine nucleus, quinoline nucleus,
Examples include an isoquinoline nucleus, an imidazo [4,5-b] quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus. The 5- or 6-membered nitrogen-containing heterocyclic ring mentioned here may have a substituent, if possible. Here, the substituent may be R ¹ described in the general formula (A). , R ² and R ³ .

Examples of the above substituents will be described in more detail. The alkyl group has 1 to 18 carbon atoms (preferably, 1 to 18 carbon atoms).
8) a linear, branched or cyclic alkyl group which may have a substituent, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl,
Mention may be made of 2-hydroxyethyl, 4-carboxybutyl, hexyl, octyl, benzyl and phenethyl. The alkenyl group is a linear, branched or cyclic alkenyl group having 2 to 18 carbon atoms (preferably 2 to 8 carbon atoms), for example, vinyl, allyl, 1-propenyl,
Mention may be made of 2-pentenyl, 1,3-butadienyl, and 2-octenyl.

The aralkyl group is an aralkyl group having 7 to 10 carbon atoms, such as benzyl. The aryl group is an aryl group which may have a substituent having 6 to 10 carbon atoms, for example, phenyl, naphthyl, 4-carboxyphenyl, 3-carboxyphenyl, 3,5-dicarboxyphenyl, Mention may be made of methanesulfonamidophenyl and 4-butanesulfonamidophenyl. A heterocyclic group is a carbon atom,
A 5- or 6-membered saturated or unsaturated heterocyclic group composed of a nitrogen atom, an oxygen atom or a sulfur atom, wherein the number of heteroatoms constituting the ring and the kind of element are one or more; For example, an oxazole ring, a benzoxazole ring, a 5-carboxybenzoxazole ring,
Examples thereof include a thiazole ring, an imidazole ring, a pyridine ring, a sulfolane ring, a furan ring, a thiophene ring, a pyrazole ring, a pyrrole ring, a chroman ring, and a coumarin ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. The alkoxy group has 1 to 18 carbon atoms (preferably 1 to 18 carbon atoms).
And 8) an alkoxy group, for example, methoxy, ethoxy, propoxy, and butoxy.
The aryloxy group is an aryloxy group which may have a substituent having 6 to 10 carbon atoms, and examples thereof include phenoxy and p-methoxyphenoxy. The alkylthio group is an alkylthio group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include methylthio and ethylthio. The arylthio group is an arylthio group having 6 to 10 carbon atoms, for example, phenylthio. The acyloxy group is an acyloxy group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include acetoxy, propanoyloxy, pentanoyloxy, and octanoyloxy.

The alkylamino group is an alkylamino group having 1 to 18 carbon atoms (preferably having 1 to 8 carbon atoms), and examples thereof include methylamino, dimethylamino, diethylamino, dibutylamino and octylamino. The amide group is an amide group having 1 to 18 carbon atoms (preferably, 1 to 8 carbon atoms), and includes, for example, acetamido, propanoylamino, pentanoylamino, octanoylamino, octanoylmethylamino, and benzamide. be able to. The sulfonamide group is a sulfonamide group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) and includes, for example, methanesulfonamide, ethanesulfonamide, propylsulfonamide, butanesulfonamide, and benzenesulfonamide. be able to. The alkoxycarbonylamino group is an alkoxycarbonylamino group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include methoxycarbonylamino and ethoxycarbonylamino. The alkoxysulfonylamino group has 1 to 1 carbon atoms.
8 (preferably 1 to 8 carbon atoms) alkoxysulfonylamino group, for example, methoxysulfonylamino,
And ethoxysulfonylamino.

The sulfamoylamino group has 0 to 1 carbon atoms.
8 (preferably having 0 to 8 carbon atoms) a sulfamoylamino group which may have a substituent, for example, methylsulfamoylamino, dimethylsulfamoylamino, ethylsulfamoylamino, propylsulfamoyl Amino and octylsulfamoylamino can be mentioned. The ureido group is a ureido group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include ureide, methylureide, N, N-dimethylureide, and octylureide. Can be mentioned. The thioureido group is a thioureido group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include thioureido, methylthioureido, N, N-dimethylthioureido, and octylthio. Ureido can be mentioned. The acyl group has 1 to 1 carbon atoms.
An acyl group having 8 (preferably 1 to 8 carbon atoms), for example, acetyl, benzoyl, and propanoyl. The alkoxycarbonyl group has 1 to 1 carbon atoms.
It is an alkoxycarbonyl group having 8 (preferably 1 to 8 carbon atoms), and examples thereof include methoxycarbonyl, ethoxycarbonyl, and octyloxycarbonyl.

The carbamoyl group is a carbamoyl group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include carbamoyl, N, N-dimethylcarbamoyl and N- Ethylcarbamoyl can be mentioned. The alkyl or arylsulfonyl group is an alkyl or arylsulfonyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include methanesulfonyl, ethanesulfonyl and benzenesulfonyl. The alkylsulfinyl group is an alkylsulfinyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include methanesulfinyl, ethanesulfinyl, and octanesulfinyl. The sulfamoyl group is a sulfamoyl group which may have a substituent having 0 to 18 carbon atoms (preferably 0 to 8 carbon atoms), for example, sulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, and butylsulfamoyl. Moyl, octylsulfamoyl, and phenylsulfamoyl can be mentioned.

Z ¹ and Z ² are preferably a substituted or unsubstituted 3,3-dialkylindolenine nucleus or 3,3-dialkylbenzoindolenine nucleus.

R ³⁰ and R ³¹ each independently represent an alkyl group. The alkyl group represented by R ³⁰ and R ³¹ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms). Has the same meaning as the substituents for the nitrogen-containing heterocyclic ring, and the preferred range is also the same.
Preferably, it is an unsubstituted alkyl group or an alkyl group substituted with an aryl group, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, an amide group, a sulfonamide group, an alkoxycarbonyl group, a carboxyl group, or a sulfo group. Examples of these include methyl, ethyl, propyl, butyl, isobutyl, 2-ethylhexyl, octyl, benzyl, 2-phenylethyl, 2-
Hydroxyethyl, 3-hydroxypropyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl, 2-methoxyethyl, 2
-(2-methoxyethoxy) ethyl, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- (3-sulfopropoxy) ethyl, 2-
Examples include hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl, 2-acetoxyethyl, carbomethoxymethyl, and 2-methanesulfonylaminoethyl.

The methine groups represented by L ³ , L ⁴ , L ⁵ , L ⁶ and L ⁷ are each independently an unsubstituted or substituted methine group. It has the same meaning as that described for the substituent, and the preferred range is also the same. When the compound has a substituent, the substituents may be connected to each other to form a 5- to 7-membered ring, or a ring may be formed with an auxiliary chromophore. Here, as the 5- to 7-membered ring, for example, a cyclopentene ring, 1-dimethylaminocyclopentene ring, 1-diphenylaminocyclopentene ring, cyclohexene ring, 1-chlorocyclohexene ring, isophorone ring, 1-morpholinocyclopentene ring, and cycloheptene ring Can be mentioned. n1
And n2 are such that n1 is 0 and n2 is 1, or n2
It is preferable that 1 is 2 and n2 is 0.

M1 represents a charge balancing counter ion. M1 may be a cation or an anion. Examples of the cation include an alkali metal ion such as a sodium ion, a potassium ion, and a lithium ion; and an organic ion such as a tetraalkylammonium ion and a pyridinium ion. The anion may be either an inorganic anion or an organic anion, such as a halogen anion (eg, a fluorine ion, a chloride ion, a bromine ion, an iodine ion), a sulfonate ion (eg, methanesulfonic acid ion, trifluoromethane ion). Sulfonate ion,
Methyl sulfate ion, p-toluenesulfonic acid ion, p
-Chlorobenzenesulfonic acid ion, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion, etc.), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate Ion, picrate ion,
Acetate ion, a metal complex ion represented by the following formula:

[0108]

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And a phosphate ion (for example, hexafluorophosphate ion, a phosphate ion represented by the following formula:

[0110]

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The following can be mentioned. m1 is a number required to balance the charges (0 or more, preferably a number of 0 to 4)
And 0 when a salt is formed in the molecule. The compound represented by the general formula (B) may form a bis-type structure by combining two kinds on any carbon atom.

The organic dye is preferably a cyanine dye represented by the following general formula (BI).

[0113]

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In the formula, Z ¹¹ and Z ²² each independently represent an atomic group necessary for forming an optionally substituted benzene ring, naphthalene ring, pyrazine ring or quinoxaline ring. X ³ and X ⁴ each independently represent an oxygen atom, a sulfur atom, —C (R ³⁴ ) (R ³⁵ ) —, or —N (R ³⁶ ) —. It represents an ^{R 32, R 33, R 34} , R 35 and R ³⁶ each independently represent an alkyl group having 1 to 8 carbon atoms. R ³⁷ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heterocyclic group, a halogen atom, or a carbamoyl group having 1 to 8 carbon atoms. Wherein, if possible, they may have a substituent.
M2 ^m2- represents an anion and m2 is 1 or 2
Represents

The cyanine dye compound represented by the formula (BI) is more preferably a compound comprising the following combinations. X ³ and X ⁴ are each independently an oxygen atom, —C (R ³⁴ ) (R ³⁵ ) — or —N (R ³⁶ ) —, and R ³² and R ³³ are each independently unsubstituted or alkoxy. 1 or a carbon number substituted with an alkylthio group
6, R ³⁴ , R ³⁵ and R ³⁶ are each independently an unsubstituted alkyl group having 1 to 6 carbon atoms, and R ³⁷ is a hydrogen atom or a carbon atom which may have a substituent. 1 to 6 alkyl groups, phenyl groups, pyridyl groups, pyrimidyl groups, succinimide groups, benzoxazole groups or halogen atoms, and Z ¹¹ and Z ²² each independently represent an unsubstituted benzene ring, naphthalene ring or quinoxaline ring. An atomic group necessary to form a benzene ring substituted with one or two groups selected from a methyl group, a chlorine atom, a fluorine atom, a methoxy group and an ethoxy group. , M2 is a perchlorate ion, a hexafluorophosphate ion, a metal complex ion represented by the following formula:

[0116]

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[0117]

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The following combination is preferable. General formula (B
In -I), the most preferred combination is X ³
And X ⁴ are both —C (R ³⁴ ) (R ³⁵ ) — or both —N
(R ³⁶⁾ - a is, independently each R ³² and R ^33, (preferably, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group) unsubstituted alkyl group is, R ^34,
R ³⁵ and R ³⁶ are each independently a methyl group or an ethyl group, R ³⁷ is a hydrogen atom, a methyl group, an ethyl group, a chlorine atom or a bromine atom, and Z ¹¹ and Z ²² are both unsubstituted benzene rings. , A naphthalene ring or a quinoxaline ring.

Specific examples of the organic dye represented by formula (B) according to the present invention are described below.

[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0129]

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[0130]

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The compound represented by the general formula (B) is
FM Hemer, Heterocyclic Compounds-Cyanine Soy and And
Related Compounds (Heterocyclic Compounds)
-Cyanine Dyes and Related Compounds), John Wiley & Sons, New York, London, 1964; Heterocyclic Compounds, by D.M. Sturmer Special topics in
Heterocyclic chemistry
(ounds-Specialtopics in heterocyclic chemistry)
, Chapter 18, Section 14, 482-515, John Wiley & Sons
New York, London, 1977; "Rod's Chemistry of Carbon Compounds (Rodd '
s Chemistry of Carbon Compounds) '' 2nd.Ed.vol.IV, p
artB, 1977, Chapter 15, Chapters 369-422,
It can be synthesized according to the method described in Elsevir Science Publishing Company Inc., New York, and the like.

The information recording medium of the present invention comprises a recording layer containing the organic dye and an organic oxidant, particularly a recording layer in which the organic dye and the organic oxidant are combined in a specific relationship. It is provided on a surface of a transparent disk-shaped substrate on which a pre-groove of 0.6 to 0.9 μm is formed, on a surface where the pre-groove is provided. In the information recording medium of the present invention, it is preferable that a light reflecting layer is further provided on the recording layer, and a protective layer can be further provided on the light reflecting layer.

Specifically, the information recording medium of the present invention preferably has the following aspects. (1) The organic dye and the organic oxidizing agent have a specific relationship on the surface of the transparent disc-shaped substrate on which the pregroove is formed on which the pregroove having a track pitch of 0.6 to 0.9 μm is formed. An information recording medium obtained by joining two laminated bodies provided with recording layers combined with each other so that each recording layer is located inside. (2) The specific relationship between the organic dye and the organic oxidant is formed on the surface of the transparent disc-shaped substrate on which the pregroove is formed on which the pregroove having a track pitch of 0.6 to 0.9 μm is formed. An information recording medium obtained by joining a laminated body provided with a recording layer combined with a disc-shaped protective plate so that the recording layer is on the inside. Note that, also in the above embodiment, it is preferable that a light reflection layer is provided on the recording layer. Further, a protective layer may be further provided on the light reflecting layer.

A method for manufacturing the information recording medium of the present invention will be described. The information recording medium of the present invention is basically a CD-R type except that a substrate on which a pre-groove having a narrower track pitch is formed than a CD-R is used in order to achieve a higher recording density. It can be manufactured using a material used for manufacturing an information recording medium. That is, DV
For a DR information recording medium, two laminates in which a recording layer, a reflective layer, and, if desired, a protective layer are sequentially formed on a substrate are formed, and these are joined with an adhesive with the recording layer inside. Alternatively, it can be manufactured by bonding the laminated body and a disk-shaped protective substrate having substantially the same dimensions as the substrate of the laminated body with an adhesive in the same manner.

The information recording medium of the present invention can be manufactured, for example, by the following method. The substrate (including the protective substrate) can be arbitrarily selected from various materials used as a substrate of a conventional information recording medium. As the substrate material, for example, glass; polycarbonate; acrylic resin such as polymethyl methacrylate;
Examples thereof include polyvinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymer; epoxy resins; amorphous polyolefins and polyesters, and these may be used in combination if desired. Among the above materials, polycarbonate is preferred from the viewpoints of moisture resistance, dimensional stability, cost, and the like. The disc-shaped substrate that can be used for the information recording medium of the present invention has a diameter of 1 according to the DVD-R standard.
20 ± 3 mm and 0.6 ± 0.1 mm in thickness, or 80 ± 3 mm in diameter and 0.6 ± 0.1 in thickness
mm. Especially, the diameter is 120 ± 3m
It is preferable to use a disc-shaped substrate having a thickness of 0.6 ± 0.1 mm.

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, and preventing the recording layer. Examples of the material of the undercoat layer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleic anhydride copolymer, polyvinyl alcohol, N-methylolacrylamide, styrene / vinyltoluene copolymer, and chlorosulfonate. 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 the like. 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.

It is preferable that tracking grooves or irregularities (pre-grooves) representing information such as address signals are formed on the substrate (or undercoat layer). This pregroove is preferably formed directly on the substrate when injection molding or extrusion molding of a resin material such as polycarbonate. The pre-groove may be formed 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. For the formation of the pre-groove layer, for example, first, a mixed solution composed of the above-mentioned acrylate ester and the polymerization initiator was applied on a precisely formed master (stamper), and further, a substrate was placed on this coating solution layer. Thereafter, the coating 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 pregroove layer is generally 0.05 to
In the range of 100 μm, preferably 0.1 to 50 μm
Range.

The depth of the pregroove is 300 to 2000 mm.
Is preferable, and the half-value width is in the range of 0.1.
It is preferably in the range of 2 to 0.9 μm. By setting the depth of the pre-groove layer in the range of 1500 to 2000 °, the sensitivity can be improved without substantially lowering the reflectance, which is particularly preferable. Therefore, such an optical disk (an optical disk in which a recording layer and a reflective layer of a dye are formed on a deep pre-groove substrate) has high sensitivity, so that recording can be performed with a low laser power, and thereby an inexpensive semiconductor laser can be used. There is an advantage that the semiconductor laser can be used or the service life of the semiconductor laser can be extended.

On the substrate, a dye recording layer is provided. As described above, the dye recording layer contains an organic dye and an organic oxidizing agent in a combination that has a specific relationship.

The recording layer is formed by the above-mentioned dye, organic oxidizing agent,
Further, if desired, a quencher, a binder or the like may be dissolved in a solvent to prepare a coating solution, and then the coating solution may be applied to the substrate surface to form a coating film and then dried. Examples of the solvent for the dye layer coating liquid include esters such as butyl acetate and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chloroform; amides such as dimethylformamide. Hydrocarbons such as cyclohexane; ethers such as tetrahydrofuran, ethyl ether and dioxane; alcohols such as ethanol, n-propanol, isopropanol, n-butanol and diacetone alcohol; fluorines such as 2,2,3,3-tetrafluoropropanol Solvents: glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol monomethyl ether; Can. The above solvents can be used alone or in combination of two or more kinds in consideration of the solubility of the dye to be 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.

Examples of the binder include natural organic high molecular substances such as gelatin, cellulose derivatives, dextran, rosin and rubber; and hydrocarbon resins such as polyethylene, polypropylene, polystyrene and polyisobutylene, polyvinyl chloride and polyvinyl chloride. Vinylidene chloride, vinyl resins such as polyvinyl chloride / polyvinyl acetate copolymer, acrylic resins such as polymethyl acrylate and polymethyl methacrylate, polyvinyl alcohol, chlorinated polyethylene,
Examples include synthetic organic polymers such as epoxy resins, butyral resins, rubber derivatives, and initial condensates of thermosetting resins such as phenol / formaldehyde resins. 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. The concentration of the coating solution thus prepared is generally 0.01 to 10% by weight.
And preferably in the range of 0.1 to 5% by weight.

[0142] Examples of the coating method include a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, and a screen printing method. The recording layer may be a single layer or a multilayer. The thickness of the recording layer is generally in the range from 20 to 500 nm, preferably in the range from 50 to 300 nm.

It is preferable that a light reflecting layer is provided on the recording layer for the purpose of improving the reflectance at the time of reproducing information. The light-reflective substance, which is the material of the light-reflective layer, is a substance having a high reflectivity to laser light, and examples thereof include Mg, Se, Y, Ti, Zr, Hf, V, Nb, and T.
a, Cr, Mo, W, Mn, Re, Fe, Co, Ni,
Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Z
n, Cd, Al, Ga, In, Si, Ge, Te, P
Metals and semi-metals such as b, Po, Sn, and Bi, or stainless steel. Of these, preferred are Cr, Ni, Pt, Cu, Ag, A
u, Al and stainless steel. These substances may be used alone, or in combination of two or more kinds, or may be used as an alloy. Particularly preferably, it is Au. The light reflecting layer can be formed on the recording layer by, for example, vapor deposition, sputtering, or ion plating of the light reflecting substance. The thickness of the light reflecting layer is generally in the range of 10 to 300 nm, preferably 50 to 200 nm.

A protective layer can be provided on the light reflecting layer for the purpose of physically and chemically protecting the recording layer and the like. This protective layer can also be provided on the side of the substrate on which the recording layer is not provided for the purpose of improving the scratch resistance and moisture resistance. Examples of the material used for the protective layer include Si
Examples include inorganic substances such as O, 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, they can also be formed by dissolving these in an appropriate solvent to prepare a coating solution, applying the coating solution, and drying. In the case of a UV-curable resin, it is also possible to form a coating solution without using a solvent or by dissolving in an appropriate solvent to prepare a coating solution, applying the coating solution, and irradiating with UV light to cure. Can be. 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.

Through the above steps, a laminate in which a recording layer, a light reflecting layer, and, if desired, a protective layer are provided on a substrate can be manufactured. A DV having two recording layers is prepared by preparing two laminates as described above and bonding them together with an adhesive so that each recording layer is on the inside.
A DR information recording medium can be manufactured. Further, the obtained laminated body, a disk-shaped protective substrate having substantially the same dimensions as the substrate of the laminated body, and an adhesive such that the recording layer is on the inside are bonded to each other so that a DV having a recording layer only on one side is provided.
A DR information recording medium can be manufactured.

The information recording method of the present invention is performed, for example, as follows using the information recording medium. First,
The semiconductor laser is rotated from the substrate side while rotating the information recording medium at a constant linear speed (in the case of a CD format, a single speed of 1.2 to 14 m / sec) or at a constant angular speed, or while rotating at a high speed of twice or more. Irradiate light for recording such as light. By this light irradiation, a cavity is formed at the interface between the recording layer and the reflective layer (the cavity is formed by deforming the recording layer or the reflective layer, or by deforming both layers), or the substrate is thinned. It is considered that information is recorded when the refractive index is changed due to deformation of the recording layer or discoloration of the recording layer or a change in the association state. The recording light is usually 500
nm to 850 nm (preferably 500 nm to 800 n
A semiconductor laser beam having a wavelength in the range of m) is used. In the DVD-R type information recording medium of the present invention, 600 to 700 nm (preferably 620 to 680 nm).
laser light (visible laser light) having a wavelength in the range of 630 nm to 650 nm is particularly suitable. The information recorded as described above is reproduced by irradiating a semiconductor laser beam from the substrate side while rotating the information recording medium at the same constant linear speed as described above or at a high speed of 2 times or more. Then, it can be performed by detecting the reflected light.

[0147]

EXAMPLES Examples and comparative examples of the present invention will be described below. [Example 1] The cyanine dye [B-6] according to the present invention.
(Oxidation potential: 0.905 V, absorption maximum wavelength: 548 n
m) and an organic oxidizing agent shown in Table 1 below as a discoloration preventing agent;
Alternatively, a nickel complex a represented by the following formula was dissolved in a solvent of 2,2,3,3-tetrafluoropropanol, respectively, to prepare a coating solution for forming a recording layer. The addition amount of the anti-fading agent was 10% by weight based on the dye. The concentration of the obtained coating solution was 2.5% by weight. Spray this coating solution onto a spiral pre-groove (track pitch:
0.8 μm, pre-groove width: 0.4 μm, pre-groove depth: 0.15 μm) formed by injection molding a polycarbonate substrate (diameter: 120 mm, thickness: 0.1 μm).
6 mm) on the pre-group side surface by spin coating to form a recording layer (thickness (within group): about 200
nm). Next, Au was sputtered on the recording layer to form a light reflecting layer having a thickness of about 100 nm, and a laminate in which the recording layer and the light reflecting layer were provided in this order on the substrate was formed. Separately, a transparent polycarbonate substrate (disk-shaped protective substrate) (diameter: 120 mm, thickness: 0.6 mm) was prepared. Then, the laminate obtained above and the disc-shaped protective substrate were joined using an adhesive (manufactured by Three Bond) so that the recording layer was on the inside (thickness: 1.2 mm). Through the above steps, a DVD-R type information recording medium according to the present invention was obtained.

Nickel complex a

Embedded image

[Evaluation as Information Recording Medium] A semiconductor laser having a wavelength of 635 nm was condensed on these samples with a lens having an NA of 0.6, a linear velocity of 3.68 m / s, and a modulation frequency of 4 M
The signal was recorded at Hz, the signal was reproduced at a laser power of 8 mW, and the degree of modulation was measured. Xe lamp (140,000 lux) for 12 hours (h), 24 hours (h), or 3 hours
Irradiation was performed for 6 hours (h), and then the modulation degree of the recording / reproducing signal was measured. Table 1 shows the evaluation results.

[0150]

[Table 1]

[0151]

[Table 2]

From the results shown in Table 1, in the case of the sample in which the cyanine dye according to the present invention and the specific organic oxidizing agent according to the present invention were combined, the cyanine dye according to the present invention and the conventional fading were used. It can be seen that the recording / reproducing characteristics are all excellent as compared with the sample combined with the nickel complex a which is the inhibitor, and that the performance after irradiation with the Xe lamp is extremely small, and the light resistance is remarkably improved.

[Example 2] In Example 1, instead of the cyanine dye [B-6], the cyanine dyes B-1, B-24, B-40, B-54 and B-5 according to the present invention were used.
6, B-66, B-70 or B-72 were used in the same manner except that the organic oxidizing agent represented by the general formula (A) according to the present invention was replaced with the same amount as the anti-fading agent. Thus, a DVD-R type information recording medium according to the present invention was manufactured. The oxidation potential and the absorption maximum wavelength of the cyanine dye are shown in Table 2 below.

[0154]

[Table 3] Table 2 ──────────────────────────────────── Cyanine dye Oxidation potential (V) Absorption Maximum wavelength (nm) ──────────────────────────────────── B-1 0.890 542 B- 24 0.925 572 B-40 0.900 542 B-54 0.905 559 B-56 0.885 562 B-66 0.870 586 B-70 0.605 652 B-72 0.875 586 ─────────────────────────────────

When a test similar to that of Example 1 was performed on the obtained sample, the same result as that of Example 1 was obtained.

Example 3 In Example 1, the cyanine dye [B-6] was replaced by a cyanine dye represented by the general formula (B) shown in Table 3 or a heptamethine cyanine dye represented by the following formula: A DVD-R type information recording medium was produced in the same manner as in Example 1, except that c was replaced by an equal weight and an organic oxidizing agent represented by the general formula (A) shown in Table 3 was used as an anti-fading agent. Then, the obtained sample was irradiated with a Xe lamp (140,000 lux) for 12 hours (h). Thereafter, the remaining amount of the cyanine dye was measured with an ultraviolet-visible spectrometer. Table 3 shows the results.

Heptamethine cyanine dye c

[0158]

Embedded image

[0159]

[Table 4]

[0160]

[Table 5]

From the results shown in Table 3 above, in the case of the sample in which the cyanine dye according to the present invention and the organic oxidizing agent represented by the general formula (A) were combined, the deterioration of the dye was observed even after irradiation with a Xe lamp. It can be seen that the amount is significantly suppressed. In particular, the difference between the oxidation potential of the cyanine dye and the reduction potential of the organic oxidant (b-
In the case of a sample in which a) was in the range of 0.5 <ba <1.4, the amount of the residual dye was large, and thus it was found that the sample had good light fastness.

[0162]

According to the present invention, the recording / reproducing characteristics can be improved by combining the organic dye and the organic oxidizing agent contained in the recording layer so that the potential difference, the absorption maximum wavelength, and / or the specific chemical structure of each other have a specific relationship. It is possible to manufacture a DVD-R type information recording medium having high light resistance and high durability even after recording without any loss.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G11B 7/24 516 G11B 7/24 516 561 561N B41M 5/26 W

Claims (19)

[Claims] 1. A recording comprising an organic dye and an organic oxidizing agent on a surface of a transparent disc-shaped substrate on which a pregroove having a track pitch of 0.6 to 0.9 μm is formed, on a side on which the pregroove is provided. A heat mode information recording medium provided with a layer. 2. An organic dye and a reduction potential of -0.6 on a surface of a transparent disc-shaped substrate having a pregroove having a track pitch of 0.6 to 0.9 .mu.m on which the pregroove is provided. An organic oxidant that is nobler than volts, and the difference between the oxidation potential b volt of the organic dye and the reduction potential a volt of the organic oxidant satisfies the relational expression 0.5 <ba <1.4. A heat mode type information recording medium provided with a recording layer combined as described above. 3. An organic dye having an oxidation potential b volt of 0.5 <0.5
3. The information recording medium according to claim 2, wherein b <1.2. 4. The information recording medium according to claim 2, wherein the organic oxidizing agent is a compound represented by the following general formula (A). General formula (A): [Wherein, X ¹ and X ² each independently represent an oxygen atom, a sulfur atom, a ＮＲNR ¹ group, or a ＣＲCR ² R ³ group, and m and n are 0 to 3 such that m + n ≧ 2. Represents an integer, R
¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and L ¹ and L ² each independently represent a divalent linking group. ] 5. The information recording medium according to claim 2, wherein the organic dye is a cyanine dye represented by the following general formula (B). General formula (B): [Wherein, Z ¹ and Z ² each independently represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring;
³⁰ and R ³¹ represents an alkyl group independently, L ^3, L
⁴ , L ⁵ , L ⁶ and L ⁷ each independently represent a methine group,
n1 and n2 each independently represent 0, 1 or 2, p and q each independently represent 0 or 1, M1 represents a charge neutralizing counter ion, and m1 represents a charge neutralizing molecule. Represents a number of 0 or more required for. ] 6. An organic dye and a reduction potential of -0.05 μm are formed on a surface of a transparent disk-shaped substrate having a pre-groove having a track pitch of 0.6 to 0.9 μm, on which the pre-groove is provided. An information recording medium having a recording layer comprising an organic oxidant nobler than 6 volts and being combined so that the absorption maximum wavelength of the organic oxidant is at least 50 nm shorter than the absorption maximum wavelength of the organic dye. . 7. The information recording medium according to claim 6, wherein the absorption maximum wavelength of the organic oxidant is shorter than the absorption maximum wavelength of the organic dye by 100 nm or more and 300 nm or less. 8. The information recording medium according to claim 6, wherein the organic oxidizing agent is a compound represented by the following general formula (A). General formula (A): [Wherein, X ¹ and X ² each independently represent an oxygen atom, a sulfur atom, a ＮＲNR ¹ group, or a ＣＲCR ² R ³ group, and m and n are 0 to 3 such that m + n ≧ 2. Represents an integer, R
¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and L ¹ and L ² each independently represent a divalent linking group. ] 9. The information recording medium according to claim 6, wherein the organic dye is a cyanine dye represented by the following general formula (B). General formula (B): [Wherein, Z ¹ and Z ² each independently represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring;
³⁰ and R ³¹ represents an alkyl group independently, L ^3, L
⁴ , L ⁵ , L ⁶ and L ⁷ each independently represent a methine group,
n1 and n2 each independently represent 0, 1 or 2, p and q each independently represent 0 or 1, M1 represents a charge neutralizing counter ion, and m1 represents a charge neutralizing molecule. Represents a number of 0 or more required for. ] 10. A track pitch of 0.6 to 0.9 μm.
The surface of the transparent disk-shaped substrate on which the pregroove is formed is provided with a cyanine dye represented by the following general formula (B) and a reduction potential nobleer than -0.6 volts. An information recording medium having a recording layer containing an organic oxidant. General formula (B): [Wherein, Z ¹ and Z ² each independently represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring;
³⁰ and R ³¹ represents an alkyl group independently, L ^3, L
⁴ , L ⁵ , L ⁶ and L ⁷ each independently represent a methine group,
n1 and n2 each independently represent 0, 1 or 2, p and q each independently represent 0 or 1, M1 represents a charge neutralizing counter ion, and m1 represents a charge neutralizing molecule. Represents a number of 0 or more required for. ] 11. An organic oxidizing agent represented by the following general formula (AI)
The information recording medium according to claim 10, which is a compound represented by the formula: General formula (AI): Wherein, X ¹¹ and X ¹² each independently represent an oxygen atom, a sulfur atom, = NR ⁸ group, or = represents CR ⁹ R ¹⁰ group, R ^8, R
⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent;
¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent, and R ¹¹ and R ¹² , and R ¹³ and R ¹⁴ may be connected to each other to form an unsaturated condensed ring. ] 12. An organic oxidizing agent represented by the following general formula (A-II)
The information recording medium according to claim 10, which is a compound represented by the formula: General formula (A-II): [Wherein, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a substituent, and R ¹⁵ and R ¹⁶ , and R ¹⁷ and R ¹⁸ are each linked to form an unsaturated fused ring You may. ] 13. A cyanine dye represented by the following general formula (B-
The information recording medium according to claim 10, which is a compound represented by I). General formula (BI): [Wherein, Z ¹¹ and Z ²² each independently represent an atomic group required for forming a benzene ring, a naphthalene ring, a pyrazine ring or a quinoxaline ring, which may have a substituent, and X ³ and X ⁴ each independently represents an oxygen atom, a sulfur atom, —C (R ³⁴ ) (R ³⁵ ) —, or —N (R ³⁶ ) —, and R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ Each independently represents an alkyl group having 1 to 8 carbon atoms which may be substituted, and R ³⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent. An aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heterocyclic group,
^Represents a carbamoyl group having 1 to 8 carbon atoms or a halogen atom, M2 ^m2- represents an anion, and m2 represents 1 or 2. ] 14. A track pitch of 0.6 to 0.9 μm.
An organic dye and an organic oxidant having a reduction potential of no less than -0.6 volts on the surface of the transparent disc-shaped substrate on which the pregroove is formed, on the side where the pregroove is provided; Oxidation potential b volts and reduction potential a of organic oxidants a
The two laminated bodies provided with the recording layers combined so that the difference from the bolts satisfies the relational expression of 0.5 <ba <1.4 such that the recording layers are on the inside, or An organic dye and a reduction potential of -0.6 volts are more noble on the surface of the transparent disc-shaped substrate on which the pregroove is formed on which a pregroove having a track pitch of 0.6 to 0.9 μm is formed. An organic oxidizing agent, wherein the difference between the oxidation potential b volts of the organic dye and the reduction potential a volts of the organic oxidizing agent is 0.5 volt.
A heat obtained by joining a laminate provided with a recording layer combined so as to satisfy the relational expression of <ba <1.4 and a disk-shaped protective plate such that the recording layer is on the inside. Mode type information recording medium. 15. A track pitch of 0.6 to 0.9 μm.
A transparent disk-shaped substrate having the pre-groove formed thereon, on the surface on the side where the pre-groove is provided, containing an organic dye and an organic oxidizing agent having a reduction potential of no less than -0.6 volts; The maximum absorption wavelength of the agent, the two laminated body provided with the recording layer combined so as to be at least 50 nm shorter wavelength side than the absorption maximum wavelength of the organic dye so that the recording layer is inside, or Track pitch is 0.6-0.
An organic dye and an organic oxidizing agent having a reduction potential of no less than -0.6 volts are provided on the surface of the transparent disc-shaped substrate on which the 9 μm pre-groove is formed, on the side where the pre-groove is provided. A laminated body provided with a recording layer that is combined so that the absorption maximum wavelength of the oxidizing agent is at least 50 nm shorter than the absorption maximum wavelength of the organic dye, and a disc-shaped protective plate, the recording layer being the inner side A heat mode type information recording medium which is bonded to each other. 16. A track pitch of 0.6 to 0.9 μm.
The surface of the transparent disk-shaped substrate on which the pregroove is formed is provided with a cyanine dye represented by the following general formula (B) and a reduction potential nobleer than -0.6 volts. A transparent disk on which a pre-groove with a track pitch of 0.6 to 0.9 μm is formed such that two recording layers provided with a recording layer containing an organic oxidant are provided on the inner side of the recording layer. A recording layer containing a cyanine dye represented by the following general formula (B) and an organic oxidant having a reduction potential of no less than -0.6 volts is provided on the surface of the substrate on which the pregroove is provided. A heat mode type information recording medium in which the laminated body, the disc-shaped protective plate, and the recording layer are bonded to each other so as to be inside. General formula (B): [Wherein, Z ¹ and Z ² each independently represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring;
³⁰ and R ³¹ represents an alkyl group independently, L ^3, L
⁴ , L ⁵ , L ⁶ and L ⁷ each independently represent a methine group,
n1 and n2 each independently represent 0, 1 or 2, p and q each independently represent 0 or 1, M1 represents a charge neutralizing counter ion, and m1 represents a charge neutralizing molecule. Represents a number of 0 or more required for. ] 17. The information recording medium according to claim 1, further comprising a metal light-reflecting layer provided on the recording layer. 18. A disk-shaped substrate having a diameter of 120 ± 3.
The information recording medium according to any one of claims 1 to 17, wherein the thickness is 0.6 ± 0.1 mm in mm and the diameter is 80 ± 3 mm and the thickness is 0.6 ± 0.1 mm. . 19. An information recording method, comprising: irradiating the information recording medium according to claim 1 with laser light having a wavelength of 600 nm to 700 nm to record information.