JP2001318447A - Recording medium, information recording method and device, information reproducing method and device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a recording medium capable of providing a produced signal having a high S-N ratio by utilizing the emission of fluorescence. SOLUTION: The recording medium 10 is formed by supporting a recording layer 12 comprising a material which is converted to a fluorescent material when irradiated with recording light of a prescribed wavelength λ1 and then emits fluorescence when irradiated with excitation light of a wavelength λ2 on a base 11.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium, and more particularly, to a recording medium having a recording layer formed from a substance that changes into a fluorescent substance when irradiated with light of a predetermined wavelength.

[0002] The present invention also relates to an information recording method and apparatus using the above-described recording medium, and an information reproducing method and apparatus.

[0003]

2. Description of the Related Art Heretofore, by irradiating a recording layer with light such as a laser beam or the like that has been finely focused, a local change in the properties of a material constituting the recording layer is caused, and image information and computer / Various recording media for recording information such as data are provided. As this type of recording medium,
Although what can record only one information at one point on the recording layer such as a so-called CD-R disc has been mainly used, recently, a plurality of information can be multiplex-recorded at one point on the recording layer,
Recording media that enable high-density recording have also been developed.

[0004] As one of the recording media as described above, a recording medium having a recording layer formed of a fluorescent substance is also known. In a conventional recording medium of this type, when a recording layer made of a fluorescent substance is irradiated with recording light, when the recording light-irradiated portion is subsequently irradiated with excitation light as reproduction light, the fluorescence intensity is higher than that of the recording light non-irradiated portion. Generally, information is recorded / reproduced by utilizing the characteristic that light is attenuated or the fluorescence wavelength changes.

[0005]

However, when information is recorded / reproduced by the above-described mechanism, even when the recording light non-irradiated portion of the recording medium is irradiated with the excitation light, the intensity of the recording light irradiated portion is not equal to that of the recording light irradiated portion. Although the wavelength is different, fluorescence is generated, and this fluorescence acts as a background, so that it is difficult to obtain a reproduced signal having a high S / N.

Accordingly, an object of the present invention is to provide a recording medium capable of obtaining a high S / N reproduction signal by utilizing fluorescence emission.

Another object of the present invention is to provide an information recording method and apparatus capable of recording information on such a recording medium.

It is a further object of the present invention to provide an information reproducing method and apparatus capable of obtaining a high S / N reproduction signal from such a recording medium.

[0009]

The recording medium according to the present invention is made of a substance which changes into a fluorescent substance when irradiated with recording light having a predetermined wavelength λ1, and then emits fluorescence when irradiated with excitation light having a wavelength λ2. The recording layer is supported on a support.

In the recording medium according to the present invention, the recording light wavelength λ1 and the excitation light wavelength λ2 may be equal to each other or different from each other.

Further, it is desirable that the support does not emit fluorescence having the same wavelength as the fluorescence emitted by the fluorescent substance when irradiated with the excitation light having the wavelength λ2.

Preferably, the support is made of a dielectric material, and a metal film is formed on one surface thereof, and the recording layer is formed thereon. The metal film is preferably made of gold or silver.

The support is desirably formed of a material transparent to the excitation light having the wavelength λ2.

The substance that forms the recording layer of the recording medium of the present invention, that is, a substance that changes into a fluorescent substance when irradiated with recording light of a predetermined wavelength λ1, and then emits fluorescence when irradiated with excitation light of wavelength λ2. It is possible to suitably use (1) a compound having such properties by itself or (2) a substance having such properties by a combination of a plurality of compounds.

The former is, for example, a compound [F
L] is a compound in which the generation of fluorescence is suppressed by protecting a part of the functional groups with a protecting group [PR]-, and is represented by the following general formula (I). In the case of the compound represented by the general formula (I), the wavelength λ1, the excitation light wavelength λ2, and the fluorescence wavelength λ3, which change into a fluorescent substance, are all different from each other.

Formula (I) [FL]-[PR] In the formula (I), [FL] represents a compound residue that emits fluorescence, and [PR] represents [FL] by irradiating [FL] with light. Represents a group capable of leaving from

Specific examples of the compound represented by formula (I) are shown below.

[0018]

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Embedded image The latter includes a combination of a chemical species that emits fluorescence and a chemical species that quenches fluorescence, and is represented by the following general formula (II). In the case of the compound represented by the general formula (II), the wavelength λ1 which changes into a fluorescent substance and the excitation light wavelength λ2 are equal to each other, and the fluorescent wavelength λ3 is different from them.

General formula (II) [FL] + [Q] In this formula (II), [FL] represents a chemical species that emits fluorescence.
[Q] represents a chemical species that quenches fluorescence.

A compound represented by the following general formula (II-1) is preferable as the chemical species [FL] of the general formula (II), and a compound represented by the following general formula (I-1) is preferable as the chemical species [Q].
It is a compound represented by I-2).

[0021]

Embedded image In the formula, Z ¹ and Z ² each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, and R ³⁰ and R ³¹
Each independently represents an alkyl group or an aryl group,
L ³ , L ⁴ , L ⁵ , L ⁶ and L ⁷ each independently represent a substituted or unsubstituted methine group (however, when a substituent is present on L ^{3 to} L ⁷ , they are linked to each other to form a ring; May be formed), p and q each independently represent 0 or 1, and n
1 and n2 each independently represent 0, 1 or 2;
Represents an anion, and m1 represents a number necessary to maintain charge balance.

Next, the symmetric or asymmetric cyanine dye represented by formula (II-1) will be described.
In the general formula (II-1), the nucleus formed by Z ¹ and Z ² includes a 3,3-dialkylindolenine nucleus,
3-dialkylbenzoindolenine 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, naphtho Tellurazole nucleus, tellurazoline nucleus, imidazole nucleus, benzimidazole nucleus, naphthimidazole nucleus, pyridine nucleus, quinoline nucleus, isoquinoline nucleus, imidazo [4,5-
b] A quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, a pyrimidine nucleus and the like.

The 5- or 6-membered nitrogen-containing heterocyclic ring mentioned here may have a substituent, if possible.
Here, examples of the substituent include the same substituents as those described for R ¹ , R ^2, and R ³ in General Formula (II-2) described below.

Examples of the above substituents will be described in more detail.

The alkyl group is an alkyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) which may have a linear, branched or cyclic substituent.
Ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, 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 having 2 to 8 carbon atoms), for example, vinyl, allyl, 1-propenyl, 2-pentenyl, , 3-butadienyl, and 2-
Octenyl can be mentioned.

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 , 4-methanesulfonamidophenyl, and 4-butanesulfonamidophenyl.

The heterocyclic group is a 5- or 6-membered saturated or unsaturated heterocyclic group composed of a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. One or more kinds of elements may be used, for example, an oxazole ring, a benzoxazole ring,
5-carboxybenzoxazole ring, thiazole ring,
Examples include 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 is an alkoxy group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include 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 having 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, such as 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 includes, for example, methylamino, dimethylamino, diethylamino, dibutylamino and octylamino.

The amide group is an amide group having 1 to 18 carbon atoms (preferably having 1 to 8 carbon atoms), for example, acetamido, propanoylamino, pentanoylamino, octanoylamino, octanoylmethylamino, and Benzamide can be mentioned.

The sulfonamide group is a sulfonamide group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), such as methanesulfonamide, ethanesulfonamide,
Mention may be made of propylsulfonamide, butanesulfonamide, and benzenesulfonamide.

The alkoxycarbonylamino group is an alkoxycarbonylamino group having 1 to 18 carbon atoms (preferably having 1 to 8 carbon atoms), and examples thereof include methoxycarbonylamino and ethoxycarbonylamino.

The alkoxysulfonylamino group is an alkoxysulfonylamino group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include 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 includes, for example, ureido, methylureido, N, N
-Dimethylureide and octylureide.

The thioureido group is a thioureido group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), for example, thioureido, methylthioureido, N, N-dimethylthioureido. And octylthioureido.

The acyl group is an acyl group having 1 to 18 carbon atoms (preferably having 1 to 8 carbon atoms), and examples thereof include 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 includes, for example, 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), for example, methanesulfonyl,
Ethane sulphonyl and benzene sulphonyl can be mentioned.

The alkylsulfinyl group has 1 to 1 carbon atoms.
It is an alkylsulfinyl group having 8 (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, Butylsulfamoyl, 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 straight-chain, branched-chain or cyclic alkyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms); 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,
-Sulfobutyl, 2- (3-sulfopropoxy) ethyl, 2-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. The substituent has the same meaning as that described above, 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-
Examples thereof include a dimethylaminocyclopentene ring, a 1-diphenylaminocyclopentene ring, a cyclohexene ring, a 1-chlorocyclohexene ring, an isophorone ring, a 1-morpholinocyclopentene ring, and a cycloheptene ring.

Preferably, n1 and n2 are either n1 is 0 and n2 is 1, or n1 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 alkali metal ions such as sodium ion, potassium ion and lithium ion, and organic ions such as tetraalkylammonium ion and 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), and a sulfonate ion (eg, a methanesulfonic acid ion). , Trifluoromethanesulfonate 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:

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

Embedded image Can be mentioned.

M1 is the number required to balance the charges (0
(Preferably 0 to 4), and 0 when a salt is formed in the molecule. p and q each independently represent 0 or 1. p and q are preferably both 0.

The compound represented by formula (II-1) may form a bis-type structure by bonding two kinds on any carbon atom.

The compound of the general formula (II-1) is preferably a cyanine dye represented by the following general formula (II-1-1).

[0061]

Embedded image The cyanine dye compound represented by the general formula (II-1-1) is more preferably a compound having the following combination.

X ³ and X ⁴ are each independently an oxygen atom,
-C ( ^R34 ) ( ^R35 )-or -N ( ^R36 )-
R ³² and R ³³ are each independently an unsubstituted or alkyl group having 1 to 6 carbon atoms substituted with an alkoxy group or an alkylthio group, and R ³⁴ , R ³⁵ and R
³⁶ are each independently an unsubstituted alkyl group having 1 to 6 carbon atoms, and R ³⁷ may have a hydrogen atom or a substituent;
An alkyl group having 1 to 6 carbon atoms, a phenyl group, a pyridyl group,
A pyrimidyl group, a succinimide group, a benzoxazole group or a halogen atom; Z ¹¹ and Z ²² each independently represent an atomic group necessary for forming an unsubstituted benzene ring, a naphthalene ring or a quinoxaline ring, or a methyl group; An atomic group necessary for forming a benzene ring substituted with one or two groups selected from a chlorine atom, a fluorine atom, a methoxy group or an ethoxy group, and M2 is a perchlorate ion, a hexafluorophosphate ion A metal complex ion represented by the following formula:

Embedded image Or a sulfonate ion represented by the following formula:

Embedded image Are preferred. m2 represents the valence of M2.

In the general formula (II-1-1),
A preferred combination is X³ And X⁴Is simultaneously -C
(R³⁴) (R³⁵)-Or simultaneously -N (R³⁶)-
And R³²And R³³Are each independently an unsubstituted
Alkyl group (preferably methyl group, ethyl group, propyl
Group, isopropyl group, butyl group)³⁴, R
³⁵And R³⁶Are each independently a methyl group or an ethyl group.
R³⁷Is hydrogen atom, methyl group, ethyl group, chlorine atom
Or a bromine atom;¹¹And Z²²Is not replaced at the same time
A benzene, naphthalene or quinoxaline ring
It is an atomic group necessary to form.

Specific examples of the fluorescent compound represented by the formula (II-1) used in the present invention are described below.

[0065]

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Embedded image The compound represented by the general formula (II-1) is described in "FM Hemmer", "Heterocyclic Compounds-Cyanine, Heterocyclic Compounds-Cyanine".
Dyes and Related Compounds), John Willie
John Wiley & Sons, New York, London, 1964; DM Sturmer, "Heterocyclic.
Heterocyclic Compounds- Special Topics in Heterocyclic Compounds
Special topics in heterocyclic chemistry)
Chapter 8, Section 14, 482-515, John Wiley & Sons, Inc.-New York, London, 1977; "Rodd's Chemistry"
of Carbon Compounds) '' 2nd.Ed.vol.IV, partB, 197
Seventh Edition, Chapter 15, Chapters 369-422, Elsevier
Science Public Company, Inc. (Elsevir
Science Publishing Company Inc.), New York, and the like.

In the present invention, the compound represented by the general formula (II-
A recording layer composed of a combination of the chemical species emitting fluorescence represented by 1) and the chemical species quenching fluorescence represented by the following general formula (II-2) is more preferable.

[0067]

Embedded image In the formula, m and n each independently represent an integer of 0 to 2, and X ¹ ,
X ² represents ＮＲNR ¹ or ＣＲCR ² R ³ (R ¹ ,
R ² and R ³ represent a substituent), L ¹ and L ² each independently represent a divalent linking group.

Hereinafter, the chemical species (II-2) for quenching the fluorescence used in the present invention will be described.

In the general formula (II-2), it is preferred that m and n are both 1.

X ¹ and X ² are ＮＲNR ¹ or ＣＲCR ²
Representing the R ^3. The substituent represented by R ¹ , R ² and R ³ is a halogen atom, a carbon atom, an oxygen atom,
A substituent obtained by combining a nitrogen atom or a sulfur atom, specifically, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a halogen atom, a cyano group, a nitro group, a nitro group, a mercapto group, and a 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, Examples thereof include a carboxyl group (including a salt) and a sulfo group (including a salt). 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.

The alkyl group is an alkyl group having 1 to 18 carbon atoms (preferably 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 carbon atoms (preferably having 2 to 6 carbon atoms), for example, vinyl, allyl, 1-propenyl, 2-pentenyl, , 3-butadienyl, 2-octenyl and 3-dodecenyl.

The aralkyl group is an aralkyl group having 7 to 10 carbon atoms, such as benzyl.

The aryl group is an aryl group having 6 to 10 carbon atoms which may have a substituent, and examples thereof include phenyl, naphthyl, p-dibutylaminophenyl and p-methoxyphenyl.

The heterocyclic group is a 5- or 6-membered saturated or unsaturated heterocyclic group composed of a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. One or more kinds of elements may be used, for example, furyl, benzofuryl, pyranyl, pyrrolyl, imidazolyl, isoxazolyl, pyrazolyl, benzotriazolyl, pyridyl, pyrimidyl, pyridazinyl, thienyl, indolyl, quinolyl, phthalazinyl,
Examples thereof include quinoxalinyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, piperidyl, piperazinyl, indolinyl, and morpholinyl.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

The alkoxy group is an alkoxy group which may have a substituent having 1 to 18 carbon atoms (preferably having 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 is an alkylthio group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and examples thereof include methylthio, ethylthio, octylthio, undecylthio, dodecylthio, hexadecylthio and octadecylthio.

The arylthio group is an arylthio group which may have a substituent having 6 to 10 carbon atoms, and examples thereof include phenylthio and 4-methoxyphenylthio.

The acyloxy group is an acyloxy group having 1 to 18 carbon atoms (preferably having 1 to 6 carbon atoms) and includes, for example, acetoxy, propanoyloxy, pentanoyloxy, octanoyloxy, dodecanoyloxy and octadecanoyloxy. Can be mentioned.

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,
Examples include acetyldecylamino, acetylundecylamino, acetyloctadecylamino, propanoylamino, 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 having 1 to 6 carbon atoms), for example, methanesulfonamide, ethanesulfonamide, Amide,
Examples thereof include 2-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.

The alkoxysulfonylamino group is an alkoxysulfonylamino group having 1 to 18 carbon atoms (preferably having 1 to 6 carbon atoms), for example, methoxysulfonylamino, ethoxysulfonylamino, octyloxysulfonylamino, undecyloxysulfonyl. Amino can be mentioned.

The sulfamoylamino group has 0 to 1 carbon atoms.
8 (preferably 0 to 6 carbon atoms) sulfamoylamino group, for example, methylsulfamoylamino, dimethylsulfamoylamino, ethylsulfamoylamino, propylsulfamoylamino, octylsulfamoylamino And undecylsulfamoylamino.

The ureido group is a ureido group which may have a substituent having 1 to 18 carbon atoms (preferably having 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. Octylthioureido and undecylthioureide.

The acyl group is an acyl group having 1 to 18 carbon atoms (preferably having 1 to 6 carbon atoms), and examples thereof include acetyl, benzoyl, octanoyl, decanoyl, undecanoyl and octadecanoyl.

The alkoxycarbonyl group has 2 to 1 carbon atoms.
It is an alkoxycarbonyl group having 8 (preferably 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 has 1 to 18 carbon atoms.
It is an alkylsulfonyl group (preferably having 1 to 6 carbon atoms) which may have a substituent, and examples thereof include methanesulfonyl, ethanesulfonyl, 2-chloroethanesulfonyl, octanesulfonyl, and undecanesulfonyl.

The alkylsulfinyl group has 1 to 1 carbon atoms.
It is an alkylsulfinyl group having 8 (preferably 1 to 6 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 6 carbon atoms), for example, sulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, Octylsulfamoyl, dioctylsulfamoyl and undecylsulfamoyl can be mentioned.

L¹ And L² Is independently divalent concatenation
Represents a group. Here, the divalent linking group means a carbon atom, nitrogen
Atom, oxygen atom or sulfur atom, X
¹ , X ²Is a 4- to 8-membered ring in cooperation with the carbon atom to which is attached
Is composed.

L¹ , And L² Is a specific example of -C
(R⁴) (R⁵)-, -C (R⁶) =, -N (R⁷) −, −
2 constituted by combining N =, -O- and -S-
And a valent linking group. Where R⁴ , R
⁵ , R⁶ And R⁷ Are each independently a hydrogen atom or
And the details thereof are described in the above R.¹ , R² , R³At
Synonymous with what was described. Also, this 4- to 8-membered ring
It may form a saturated or unsaturated condensed ring.
Examples of the fused ring include a cycloalkyl ring, an aryl ring and
Can be a heterocyclic ring.¹
 , R² , R ³ This is synonymous with the one described in.

The 4- to 8-membered ring will be described in more detail.

Examples of the four-membered ring include cyclobutanedione, cyclobutenedione and benzocyclobutenequinone.

Examples of the 5-membered ring include cyclopentanedione, cyclopentenedione, cyclopentanedione,
Cyclopentenetrione, indandione, indantrione, tetrahydrofurandion, tetrahydrofurantrione, tetrahydropyrroledione, tetrahydropyrroletrione, tetrahydrothiophenedione,
Tetrahydrothiophenetrione can be mentioned.

Examples of the 6-membered ring include benzoquinone, quinomethane, quinodimethane, quinoneimine, quinonediimine, thiobenzoquinone, dithiobenzoquinone, naphthoquinone, anthraquinone, dihydrochromementione, dihydropyridinedione, dihydropyrazinedione, dihydropyrimidinedione, dihydropyridazinedione, Examples thereof include dihydrophthalazinedione, dihydroisoquinolinedione, and tetrahydroquinolinetrione.

Examples of the 7-membered ring include cycloheptanedione, cycloheptanetrione, azacycloheptanetrione, diazacycloheptanetrione, oxocycloheptanetrione, dioxocycloheptanetrione, and oxoazacycloheptanetrione. it can.

Examples of the 8-membered ring include cyclooctanedione, cyclooctanetrione, azacyclooctanetrione, diazacyclooctanetrione, oxocyclooctanetrione, dioxocyclooctanetrione, oxoazacyclooctanetrione, and cyclooctenedione. , Cyclooctadienedione and dibenzocyclooctenedione.

The ring formed by L ¹ and L ² together with the carbon atom to which X ¹ and X ² are bonded is preferably a 6-membered ring.

The chemical species that quench the fluorescence is more preferably a compound represented by the following formula (II-2-1).

[0107]

Embedded image = NR ⁸ represented by X ¹¹ and X ²² , and = C
R ⁹ R ¹⁰ is ＮＲNR ¹ and ＣＲCR ² R represented by X ¹ and X ² in the general formula (II-2), respectively.
^It is synonymous with ³ , and its preferable range is also the same. The substituents represented by R ⁸ , R ⁹ and R ¹⁰ have the same meanings as the substituents represented by R ¹ , R ² and R ³ in formula (II-2), and the preferred range is also the same. Are identical.

Each of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently represents a hydrogen atom or a substituent. When R ¹¹ and R ¹² or R ¹³ and R ¹⁴ simultaneously serve as a substituent, 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 ones as described in the above 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 an oxygen atom or a ＝ CR ⁹ R ¹⁰ group at the same time. 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.

The case where X ¹¹ and X ²² are simultaneously oxygen atoms will be described.

X¹¹, X²²Are simultaneously oxygen atoms
If R¹¹, R¹², R¹³And R ¹⁴At least 2
More preferably, one is an electron-withdrawing group. Here
A child-withdrawing group is a substituent having a positive Hammett σp value.
Means, specifically, halogen atom, cyano group, nitro
Group, acyl group, alkoxycarbonyl group, carbamoyl
Group, alkylsulfonyl group, and alkylsulfinyl
Groups.

When X ¹¹ and X ²² are simultaneously an oxygen atom, a particularly preferred combination is R ¹¹ ,
R ¹² , R ¹³ and R ¹⁴ each independently represent 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 sulfa Moylamino group, alkoxycarbonylamino group, alkoxysulfonylamino group, ureido group, thioureido group, acyl group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group, alkylsulfinyl group, and sulfamoyl group, at least two of which are This is the case with an electron-withdrawing group.

The most preferred combination is
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent 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 having 1 to 6 carbon atoms. Group, amide group having 1 to 6 carbon atoms, 1 to 6 carbon atoms
A sulfonamide group, a 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, a carbamoyl group having 1 to 6 carbon atoms, and a 1 to 6 carbon atoms
And at least two of them are a halogen atom, a cyano group, an alkylsulfonyl group or an alkylsulfinyl group.

X ¹¹ and X ²² simultaneously = CR ⁹ R ¹⁰
When it is a group, the chemical species that quench the fluorescence is particularly preferably a compound represented by the following general formula (II-2-2).

[0115]

Embedded image 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 chemical species that quench the fluorescence is most preferably a compound represented by the following formula (II-2-3) or (II-2-4).

[0117]

Embedded image

Embedded image In Formula (II-2-3), 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 for R ^{1 to} R ³ . m4 represents an integer of 1 to 4, and 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.

In the general formula (II-2-4), R ²¹ represents a hydrogen atom or a substituent. Here, the substituent is the aforementioned R ¹
It means the same as those described in the ~R ^3. m5
Represents an integer of 0 to 6, and when m5 represents an integer of 2 or more, each of a plurality of R ²¹ may be the same or different.

In formula (II-2-3), preferred combinations of R ¹⁹ and R ²⁰ will be described.

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, A combination that is an alkyl group having 1 to 6 is preferable, and a most preferable combination is that R ¹⁹ is an alkoxy group having 1 to 6 carbon atoms and R ²⁰ is a hydrogen atom.

The chemical species for quenching the fluorescence represented by the general formula (II-2-3) is particularly preferably a compound represented by the following formula.

[0122]

Embedded image In the general formula (II-2-4), 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, more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Halogen atom, cyano group, alkoxy group having 1 to 6 carbon atoms, 1 carbon atom
Alkylthio group of 1 to 6, amide group of 1 to 6 carbon atoms, sulfonamide group of 1 to 6 carbon atoms, ureido group of 1 to 6 carbon atoms, acyl group of 1 to 6 carbon atoms, particularly preferably,
It is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorine atom, 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 chemical species that quench the fluorescence used in the present invention are described below.

[0124]

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Embedded image The compound represented by the general formula (II-2) is described, for example, in J. Che.
m. Soc. Perkin Trans. 1, 611 (1992), Synthesis, 546
It can be easily synthesized according to a general synthesis method such as (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.

[0126]

Embedded image 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 refluxed under heating for 12 hours. After completion of the reaction, the reaction solution was poured into 1N hydrochloric acid, and the 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) according to the present invention was synthesized.

[0130]

Embedded image 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) 2.1 g of (A-58a), 4.4 g of lauric chloride
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 chemical species that quench fluorescence represented by the general formula (II-2) may be used alone or in combination with other known quencher.

A typical example of the quencher to be combined is a compound represented by the general formula (II) described in JP-A-3-224793.
Metal complexes, diimmonium salts, aminium salts represented by I), (IV) or (V);
And the nitroso compounds described in JP-A-7-300 and JP-A-2-300288. Particularly preferred quenchers to be combined are metal complexes (for example, PA-1006 (Mitsui Toatsu Fine Co., Ltd.)) or diimmonium salts (for example, IRG-
023 and IRG-022 (Nippon Kayaku Co., Ltd.), and the most preferred are diimmonium salts. These quenchers can be used in combination of two or more depending on the purpose.

The amount of the chemical species for quenching fluorescence represented by the general formula (II-2) is preferably in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the fluorescent species. More preferably in the range of from 50 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.

The amount of the quencher to be added is preferably in the range of 1 to 100 parts by weight, more preferably in the range of 1 to 50 parts by weight, and particularly preferably in the range of 100 parts by weight of the fluorescent species. Is in the range of 1 to 25 parts by weight, most preferably in the range of 1 to 10 parts by weight.

As another preferable combination of the chemical species represented by the general formula (II), [FL] is an anion represented by the following general formula (II-3), and [Q] is the following general formula: Formula (II-4)
And cations represented by The anion represented by II-3 is represented by the following general formula.

[0137]

Embedded image [Wherein, Za and Zb each independently represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring,
¹ and R ² each independently represent an alkyl group or an aryl group, and L ¹ , L ² , L ³ , L ⁴ and L ⁵
Each independently represents a substituted or unsubstituted methine group (however, when there is a substituent on L ^{1 to} L ⁵ , they may be linked to each other to form a ring), and n is an integer of 1 or more Represents
j represents 0, 1 or 2, and k represents 0 or 1. Examples of the 5- or 6-membered nitrogen-containing heterocycle (nucleus) represented by Za and Zb include, for example, a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a thiazoline nucleus, an oxazole nucleus, a benzooxazole nucleus, and a naphthoxazole nucleus. , Oxazoline nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, selenazoline nucleus, tellurazole nucleus, benzotellurazole nucleus, naphthotellurazole nucleus, tellurazoline nucleus, imidazole nucleus, benzimidazole nucleus, naphthimidazole nucleus, pyridine nucleus, Examples include a quinoline nucleus, an isoquinoline nucleus, an imidazo [4,5-b] quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus.

Among these, a benzothiazole nucleus, an imidazole nucleus, a naphthoimidazole nucleus, a quinoline nucleus, an imidazo [4,5-b] quinoxaline nucleus, a thiadiazole nucleus, a tetrazole nucleus and a pyrimidine nucleus are preferred.

A benzene ring and a naphthoquinone ring may be further condensed on these rings.

The above 5- or 6-membered nitrogen-containing heterocyclic ring may have a substituent. Examples of preferred substituents (atoms) include a halogen atom, a substituted or unsubstituted alkyl group,
An aryl group can be mentioned. As the halogen atom, a chlorine atom is preferable. The alkyl group has 1 carbon atom.
~ 6 linear alkyl groups are preferred. Examples of the substituent of the alkyl group include an alkoxy group (eg, methoxy) and an alkylthio group (eg, methylthio). As the aryl group, phenyl is preferred.

The alkyl group represented by R ¹ and R ² may have a substituent, and is preferably a straight-chain having 1 to 18 carbon atoms (more preferably 1 to 8, particularly 1 to 6). A cyclic, cyclic or branched alkyl group.

The aryl group represented by R ¹ and R ² may have a substituent, and preferably has 6 carbon atoms.
And aryl groups which may have 18 to 18 substituents.

Preferred examples of the substituents on the alkyl group or the aryl group represented by R ¹ and R ² include the following.

A substituted or unsubstituted aryl group having 6 to 18 carbon atoms (for example, phenyl, chlorophenyl, anisyl, toluyl, 2,4-di-t-amyl, 1-naphthyl), an alkenyl group (for example, vinyl, 2-methylvinyl), alkynyl group (eg, ethynyl, 2-methylethynyl, 2-phenylethynyl), halogen atom (eg, F, Cl, Br, I), cyano group, hydroxyl group, carboxyl group, acyl group ( For example, acetyl, benzoyl, salicyloyl, pivaloyl), alkoxy group (eg, methoxy, butoxy, cyclohexyloxy), aryloxy group (eg, phenoxy, 1-naphthoxy), alkylthio group (eg, methylthio, butylthio, benzylthio, 3- Methoxypropylthio), arylthio groups (eg, , Phenylthio, 4-chlorophenylthio), an alkylsulfonyl group (e.g.,
Methanesulfonyl, butanesulfonyl), arylsulfonyl group (for example, benzenesulfonyl, paratoluenesulfonyl), carbamoyl group having 1 to 10 carbon atoms,
An amide group having 1 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, a heterocyclic group (for example, pyridyl, thienyl,
Heteroaromatic rings such as furyl, thiazolyl, imidazolyl, and pyrazolyl, and aliphatic heterocycles such as pyrrolidine, piperidine, morpholine, pyran, thiopyran, dioxane, and dithiolane rings).

In the present invention, the above R ¹ and R ²
Is an unsubstituted carbon atom having 1 to 8 carbon atoms (preferably,
A linear alkyl group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms, or an alkoxy group (particularly, methoxy)
Alternatively, it is preferably a linear alkyl group having 1 to 8 carbon atoms (preferably 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms) substituted with an alkylthio group (particularly methylthio).

The methine groups represented by L ^{1 to} L ⁵ may have a substituent. Examples of preferred substituents include
Examples of the preferred substituents of the alkyl group having 1 to 18 carbon atoms, the aralkyl group, and the alkyl group or the aryl group represented by R ¹ and R ² can be given. Among them, an alkyl group (eg, methyl), an aryl group (eg, phenyl), a halogen atom (eg, Cl, Br), and an aralkyl group (eg, benzyl) are preferable.

In the present invention, j and k are each independently 0
Or 1 is preferable.

The substituents on L ^{1 to} L ⁵ may be linked to each other to form a ring. The preferred number of ring members is a 5- or 6-membered ring, and two or more of these rings may be condensed. The linking position depends on the number of methine chains formed. For example, when the methine chain formed by L ^{1 to} L ⁵ is a pentamethine chain, the preferred linking position is L
¹ and L ³ , L ² and L ⁴ , and L ³ and L ⁵ . When a double condensed ring is formed, the linking position is L ¹
To be ^{L 3} and ^{L 5.} Also in this case, L ¹ and R
¹ , L ⁵ and R ² , and further L ³ and R ² may be linked to each other to form a ring, and the number of ring members is preferably 5
It is a membered or six-membered ring.

In the present invention, the ring formed by the substituents on L ^{1 to} L ⁵ is preferably a cyclohexene ring.

Among the cyanine dye cations represented by the general formula (II-3), the cations represented by the following general formula (II-3-1) are more preferable.

[0151]

Embedded image [Wherein, Z ¹ and Z ² each independently represent an atomic group necessary for forming an indolenine nucleus or a benzoindolenine nucleus, and R ¹ and R ² each independently represent an alkyl group or an aryl group. And R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group, and L ¹ , L ² ,
L ³ , L ⁴ and L ⁵ each independently represent a substituted or unsubstituted methine group (however, when there is a substituent on L ^{1 to} L ⁵ , they may be linked to each other to form a ring) ), N represents an integer of 1 or more, j represents 0, 1 or 2, and k represents 0
Or represents 1. The indolenine nucleus or benzoindolenine nucleus represented by Z ¹ and Z ² may have a substituent.
Examples of the substituent (atom) include a halogen atom and an aryl group. As the halogen atom, a chlorine atom is preferable. As the aryl group, phenyl is preferable.

The above R³ , R⁴ , R⁵ And R⁶ In table
The alkyl group preferably has 1 to 18 carbon atoms.
It is a linear, branched, or cyclic alkyl group. Ma
R ³ And R⁴ , And R⁵ And R⁶ Are connected to each other
A ring may be formed.

The alkyl group represented by R ³ , R ⁴ , R ⁵ and R ⁶ may have a substituent. Preferred examples of the substituent include those exemplified as preferred substituents of the alkyl group or aryl group represented by R ¹ and R ² .

In the present invention, R ³ , R ⁴ , R ⁵
And the alkyl group represented by R ⁶ is preferably a linear unsubstituted alkyl group having 1 to 6 carbon atoms (particularly, methyl or ethyl).

In the general formula (II-3-1), R¹Passing
And R² , L¹ , L² , L³ , L ⁴ And L⁵ , J and
And k and n are as described in the general formula (II-3)
Represents the same meaning. Also preferred examples of them are
The same as described in the general formula (II-3)
You.

-(SO ₃ ⁻ ) _{n + 1} of (SO ₃ ⁻ )
The group is preferably bonded to the terminals of R ¹ and R ^{2 in} the general formulas (II-3) and (II-3-1).

Hereinafter, specific examples of the formula (II-3) of the present invention will be listed.

[0158]

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Embedded image The cation represented by II-4 is represented by the following general formula.

[0159]

Embedded image In the formula, R ₅ and R ₆ each independently represent a substituent,
R ₇ and R ₈ each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group, and 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, r and s each independently represent an integer of 0 to 4, and when r and s are 2 or more, Multiple r and s
May be the same or different from each other.

The alkyl group represented by R ₇ and R ₈ is preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. is there. These may be linear, branched, or cyclic. Examples of these include methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, t-butyl, n-hexyl,
Neopentyl, cyclohexyl, adamantyl, cyclopropyl and the like.

Examples of the substituent of the alkyl group include the following.

C2 to C18 (preferably C2 to C18)
8) a substituted or unsubstituted alkenyl group (eg, vinyl); a substituted or unsubstituted alkynyl group having 2 to 18 (preferably 2 to 8) carbon atoms (eg, ethynyl); A substituted or unsubstituted aryl group (eg,
Phenyl, naphthyl); halogen atom (eg, F, Cl,
Br, etc.); C1-18 (preferably C1-8)
A substituted or unsubstituted alkoxy group (eg, methoxy,
Ethoxy); a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms (eg, phenoxy, p-methoxyphenoxy); a substituted or unsubstituted alkylthio group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) (Eg, methylthio, ethylthio); a substituted or unsubstituted arylthio group having 6 to 10 carbon atoms (eg, phenylthio); 2 carbon atoms
To 18 (preferably 2 to 8 carbon atoms) substituted or unsubstituted acyl group (eg, acetyl, propionyl); 1 to 18 (preferably 1 to 8 carbon atoms) substituted or unsubstituted alkylsulfonyl group Or an arylsulfonyl group (eg, methanesulfonyl, p-toluenesulfonyl); a substituted or unsubstituted acyloxy group having 2 to 18 (preferably 2 to 8) carbon atoms (eg, acetoxy,
A substituted or unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms (preferably 2 to 8 carbon atoms) (eg, methoxycarbonyl, ethoxycarbonyl); a substituted or unsubstituted aryloxy group having 7 to 11 carbon atoms A carbonyl group (eg, naphthoxycarbonyl); an unsubstituted amino group or a substituted amino group having 1 to 18 (preferably 1 to 8) carbon atoms (eg, methylamino, dimethylamino, diethylamino, anilino, methoxyphenyl) Amino, chlorophenylamino, pyridylamino, methoxycarbonylamino, n-butoxycarbonylamino, phenoxycarbonylamino, methylcarbamoylamino, ethylthiocarbamoylamino, phenylcarbamoylamino, acetylamino, ethylcarbonylamino, ethylthio Carbamoylamino, cyclohexyl carbonylamino, benzoylamino, chloroacetyl amino, methylsulfonylamino); 1 the number of carbon atoms
18 (preferably 1 to 8 carbon atoms) substituted or unsubstituted carbamoyl group (eg, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, dimethylcarbamoyl, morpholinocarbamoyl, pyrrolidino) Carbamoyl); an unsubstituted sulfamoyl group, or having 1 to 1 carbon atoms
18 (preferably 1 to 8 carbon atoms) substituted sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl); cyano group; 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 ₇ and R ₈ is preferably a substituted or unsubstituted alkenyl group having 2 to 18 carbon atoms, more preferably a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms. , 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 ₇ and R ₈ is preferably a substituted or unsubstituted alkynyl group having 2 to 18 carbon atoms, more preferably a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms. Yes, for example, ethynyl, 2-propynyl and the like.

As the substituent for the alkynyl group, those described above as the substituent for the alkyl group are preferable.

The aralkyl group represented by R ₇ and R ₈ is preferably a substituted or unsubstituted aralkyl group having 7 to 18 carbon atoms, for example, benzyl, methylbenzyl and the like.

The aryl group represented by R ₇ and R ₈ is preferably a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, and examples include phenyl and naphthyl.

As the substituent for the aryl group, those described above as the substituent for the alkyl group are preferable. In addition to these,
Alkyl groups (eg, methyl, ethyl, etc.) are also preferred.

The heterocyclic group represented by R ₇ and R ₈ is a 5- or 6-membered saturated or unsaturated heterocyclic ring composed of a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, Examples of these include an oxazole ring, a benzoxazole ring, a thiazole ring, a benzothiazole ring, an imidazole ring, a benzimidazole ring, an indolenine ring, a pyridine ring, a piperidine ring, a pyrrolidine ring, a morpholine ring, a sulfolane ring, a furan ring, and thiophene. Ring, pyrazole ring, pyrrole ring, chroman ring, and 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 ₅ and R ₆ have the same meaning as the above-mentioned substituents for the alkyl group. In addition to these, an alkyl group (eg, methyl, ethyl, etc.) can also be mentioned.

In the present invention, the substituent represented by R ₅ and R ₆ is preferably a hydrogen atom or an alkyl group. Particularly preferred is a hydrogen atom.

The partial structure represented by the general formula (II-4) is
It is particularly preferably represented by the following general formula (II-4-1) or (II-4-2).

[0173]

Embedded image In the formula, R ₁₇ and R ₁₈ have the same meanings as the substituents represented by R ₅ and R ₆ described above, respectively, and their preferred ranges are also the same. R _{1 9} and R ₂₀ are the same as the substituents represented by R ₇ and R ₈ which are mentioned above, also for each of their preferred scopes are identical. r and s are each independently 0 to
And when r and s are 2 or more, a plurality of r and s may be the same or different from each other.

[0174]

Embedded image In the formula, R ₂₁ and R ₂₂ have the same meanings as the substituents represented by R ₅ and R ₆ described above, respectively, and their preferred ranges are also the same. R _{2 1} and R
₂₂ are also preferably linked to each other to form a carbocyclic or heterocyclic ring, and particularly preferably, R ₂₁
And R ₂₂ are each a condensed aromatic ring with a pyridine ring bonded thereto. r and s each independently represent an integer of 0 to 4, and when r and s are 2 or more, a plurality of r and s
May be the same or different from each other.

Examples of the moiety represented by the general formula (II-4) in the compound represented by the general formula (II) used in the present invention are specifically described below.

[0176]

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Embedded image Further, as another preferable combination of the chemical species represented by the general formula (II), [FL] is the following general formula (II-5) or
And an anion represented by (II-6), wherein [Q] is a cation represented by the general formula (II-4).

[0177]

Embedded image In the formula, A ¹ , A ² , B ¹ and B ² represent a substituent,
L ¹ , L ² , L ³ , L ⁴ and L ⁵ represent a methine group;
¹ represents ＝ O, ＮＲNR, ＣC (CN) ₂ (where R represents a substituent), and X ² represents —O, —NR, —C (CN) _2.
(Where R represents a substituent), and m and n each represent an integer of 0 to 2. Y ¹ and E each represent an atom or a group of atoms necessary to form a carbocyclic or heterocyclic ring, and Z ¹ and G each represent an atom or a group of atoms necessary to form a carbocyclic or heterocyclic ring. x and y each independently represent 0 or 1. M
^{k +} represents an onium ion. k represents the number of charges.

The above-mentioned anion portion (color component) used in the present invention will be described below.

In the above formula, examples of the substituent represented by A ¹ , A ² , B ¹ and B ² include the following.

C1-18 (preferably C1-18)
8) a substituted or unsubstituted linear, 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.); substituted or unsubstituted one having 7 to 18 carbon atoms (preferably 7 to 12 carbon atoms). A substituted aralkyl group (eg, benzyl, carboxybenzyl, etc.); an alkenyl group having 2 to 18 carbon atoms (preferably, 2 to 8 carbon atoms) (eg, vinyl, etc.); 8) an alkynyl group (eg, ethynyl, etc.);
To 18 (preferably 6 to 10 carbon atoms) substituted or unsubstituted aryl group (eg, phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-carboxyphenyl,
3,5-dicarboxyphenyl, etc.);
(Preferably 2 to 8 carbon atoms) substituted or unsubstituted acyl group (eg, acetyl, propionyl, butanoyl, chloroacetyl, etc.); substituted or unsubstituted 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) An alkyl or aryl sulfonyl group (e.g., methanesulfonyl, p-toluenesulfonyl, etc.); having 1 to 18 carbon atoms (preferably 1 carbon atom)
To 8) alkylsulfinyl groups (eg, methanesulfinyl, ethanesulfinyl, octanesulfinyl, etc.); alkoxycarbonyl groups 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.);
(Preferably 1 to 8 carbon atoms) substituted or unsubstituted alkoxy group (for example, methoxy, ethoxy, n-butoxy, methoxyethoxy, etc.); substituted or substituted with 6 to 18 carbon atoms (preferably 6 to 10 carbon atoms) An unsubstituted aryloxy group (eg, phenoxy, 4-methoxyphenoxy, etc.); an alkylthio group having 1 to 18 (preferably 1 to 8) carbon atoms (eg, methylthio, ethylthio, etc.); Arylthio (eg, phenylthio etc.); a substituted or unsubstituted acyloxy group having 2 to 18 (preferably 2 to 8 carbons) (eg, acetoxy, ethylcarbonyloxy, cyclohexylcarbonyloxy, benzoyloxy, chloroacetyloxy, etc.) );
18 (preferably 1 to 8 carbon atoms) substituted or unsubstituted sulfonyloxy group (eg, methanesulfonyloxy etc.); 2 to 18 (preferably 2 to 8 carbon atoms) substituted or unsubstituted carbamoyloxy Groups (eg, methylcarbamoyloxy, diethylcarbamoyloxy, etc.); substituted or unsubstituted amino groups having 0 to 18 (preferably 0 to 8) carbon atoms (eg, unsubstituted amino, methylamino, dimethylamino, Diethylamino, anilino, methoxyphenylamino, chlorophenylamino,
Morpholino, piperidino, pyrrolidino, pyridylamino, methoxycarbonylamino, n-butoxycarbonylamino, phenoxycarbonylamino, methylcarbamoylamino, phenylcarbamoylamino, ethylthiocarbamoylamino, methylsulfamoylamino,
Phenylsulfamoylamino, acetylamino, ethylcarbonylamino, ethylthiocarbonylamino, cyclohexylcarbonylamino, benzoylamino, chloroacetylamino, methanesulfonylamino, benzenesulfonylamino, and the like; C1-18 (preferably C1) To 8) substituted or unsubstituted carbamoyl groups (eg, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, dimethylcarbamoyl, morpholinocarbamoyl, pyrrolidinocarbamoyl, etc.); ~
18 (preferably 0 to 8 carbon atoms) substituted or unsubstituted sulfamoyl group (eg, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, etc.); halogen atom (eg, fluorine, chlorine, bromine, etc.) A hydroxyl group; a nitro group; a cyano group; a carboxyl group; a heterocyclic group (eg,
Oxazole, benzoxazole, thiazole, benzothiazole, imidazole, benzimidazole, indolenine, pyridine, sulfolane, furan, thiophene, pyrazole, pyrrole, chroman, coumarin, etc.).

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, Ch
em. 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 )-which binds to Y ^{1
(E) x -C (= X} 1) - ] (hereinafter, for convenience, W1
Called. ) And Z ¹ [-C (-L ⁵ ) =
(G) y = C (-X 2 -) - ] (hereinafter, for convenience, W
2) are in a conjugate state, and therefore Y ¹
And a carbocyclic or heterocyclic ring formed by W1 and Z ¹
And the carbocycle or heterocycle formed by W2 are each considered as one of the resonance structures.

[0184] carbocyclic or heterocyclic ring formed by the ^{Y 1} and W1, and ^{Z 1} and W2 is 4-7 membered ring is preferred, particularly preferably a 5-membered ring 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 those described as the substituents represented by A ¹ , A ² , B ¹ and B ² . Preferred as hetero atoms 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 is represented. X ² represents —O, —NR or —C (C
N) represents ₂ . 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.

[0189]

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

[0190] ^{Y 1} and W1, and the heterocyclic ring formed by ^{Z 1} and W2 is, for example, include the following.
In the examples, Ra, Rb and Rc each independently represent a hydrogen atom or a substituent.

[0191]

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Embedded image Preferred heterocycles are the heterocycles represented by A-5, A-6, and A-7.

The substituents represented by Ra, Rb and Rc are
It has the same meaning as the substituents represented by A ¹ , A ² , B ¹ and B ² .

Ra, Rb and Rc may be mutually linked to form a carbocyclic or heterocyclic ring.

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,
Aryloxy group, alkylthio group, 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, cyclopentene ring, 1-dimethylaminocyclopentene ring, 1-diphenylaminocyclopentene ring, cyclohexene ring, 1-chlorocyclohexene ring, isophorone ring, 1-morpholinocyclopentene ring) , A cycloheptene ring).

K represents a number necessary to neutralize the charge of the counter cation.

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.

Specific examples of the anions represented by the general formulas (II-5) and (II-6) are shown below, but the present invention is not limited to these.

[0198]

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Embedded image On the other hand, an information recording method according to the present invention is a method for recording information on each recording medium according to the present invention described above, wherein the recording layer is irradiated with a recording light having a predetermined wavelength λ1 carrying the recording information. The present invention is characterized in that the substance in the irradiated part is changed to a fluorescent substance.

As the recording light, evanescent light emitted from a range of a diameter shorter than the wavelength can be preferably used.

An information recording apparatus according to the present invention is an apparatus for recording information on each recording medium according to the present invention as described above, and irradiates a recording light having a predetermined wavelength λ1 carrying recorded information to the recording layer. Recording means for changing the substance in the recording light irradiation part to a fluorescent substance.

The recording means includes a micro-aperture probe having at one end a light-passing aperture having a diameter smaller than the wavelength of the recording light, and irradiates the recording layer with evanescent light radiated from the aperture of the micro-aperture probe. Are preferably used.

As the recording means, a means for irradiating the recording layer with evanescent light radiated from the solid immersion lens can be suitably used.

On the other hand, the information reproducing method according to the present invention irradiates each recording medium according to the present invention with the recording light having a predetermined wavelength λ1 carrying the recording information to the recording layer, and the recording light irradiated portion is In the method of reproducing recorded information from a recorded recording medium in which the substance is changed to a fluorescent substance, the recording layer is irradiated with excitation light having a wavelength λ2 in an excitation wavelength range of the fluorescent substance to generate fluorescence. And detecting the fluorescence.

In the information reproducing method according to the present invention, light having a wavelength λ2 equal to the wavelength λ1 of the recording light is used as the excitation light, and the excitation light having the wavelength λ2 has a lower intensity than the recording light. May be applied to the recording layer. Alternatively, light having a wavelength λ2 different from the wavelength λ1 of the recording light may be used as the excitation light.

In the information reproducing method according to the present invention, light for irradiating a minute area is used as the excitation light, and the recording layer is scanned with the excitation light, and fluorescence generated at that time is detected for each scanning position. It is desirable. In such a case, evanescent light emitted from a range of a diameter shorter than the wavelength can be suitably used as the excitation light.

Further, in the information reproducing method according to the present invention, the excitation light is incident on the support so as to propagate while repeating total reflection between both surfaces of the support. The recording layer may be irradiated with evanescent light that has leached to the side, and the fluorescence generated by the evanescent light irradiation may be spatially resolved and detected.

In the information reproducing method according to the present invention,
As described above, in the case where a recording medium is used in which the support is made of a dielectric material, a metal film is formed on one surface thereof, and the recording layer is formed thereon, It is desirable that excitation light be incident on the metal film from the support side at a specific incident angle.

On the other hand, the information reproducing apparatus according to the present invention irradiates the recording layer of the above-mentioned recording medium according to the present invention with recording light having a predetermined wavelength λ1 carrying recording information to the above-mentioned recording layer, so that the recording light irradiated portion is In an apparatus for reproducing recorded information from a recorded recording medium obtained by changing the substance into a fluorescent substance, the recording layer is irradiated with excitation light having a wavelength λ2 in an excitation wavelength range of the fluorescent substance to generate fluorescence. And a reading means for detecting the fluorescence.

[0209] In the information reproducing apparatus according to the present invention,
As the excitation means, a means for irradiating the recording layer with excitation light having a wavelength λ2 equal to the wavelength λ1 of the recording light with a lower intensity than the recording light can be suitably used. Alternatively, as the excitation means, a means for irradiating the recording layer with excitation light having a wavelength λ2 different from the wavelength λ1 of the recording light can be suitably used.

[0210] In the information reproducing apparatus according to the present invention, the excitation means preferably scans the recording layer with a focused beam-like excitation light. Is configured to detect the fluorescence at each scanning position.

The information reproducing apparatus according to the present invention employs a recording medium in which a support is made of a dielectric material, a metal film is formed on one surface thereof, and a recording layer is formed thereon, as described above. When used, the excitation means is desirably configured to irradiate the recording medium with excitation light from the support side to the metal film.

In the information reproducing apparatus according to the present invention,
As the excitation unit, a unit that scans the recording layer with evanescent light emitted from a solid immersion lens is also preferably used, and in that case, the reading unit detects fluorescence at each scanning position of the excitation light. Be composed.

Further, in the information reproducing apparatus according to the present invention,
Preferably, the excitation means includes a micro-aperture probe having at one end a light-passing aperture having a diameter shorter than the wavelength of the excitation light, and a means for scanning the recording layer with evanescent light emitted from the aperture of the micro-aperture probe. Used for
At this time, the reading means is configured to detect the fluorescence at each scanning position of the excitation light.

Further, in the information reproducing apparatus according to the present invention,
As the excitation means, the excitation light is incident on the support so as to propagate while repeating total reflection between both surfaces of the support, and at this time, evanescent light leaching from the support to the recording layer side is emitted. A device that irradiates the recording layer is also preferably used, and in that case, a device that spatially resolves and detects fluorescence emitted from the recording layer by irradiation with excitation light is used as the reading unit.

On the other hand, in the information reproducing apparatus according to the present invention, in the optical system through which the excitation light passes, an optical member which emits fluorescence having the same wavelength as the fluorescence emitted by the fluorescent substance when the excitation light having the wavelength λ2 is irradiated is provided. Is preferably not included.

[0216]

The recording medium according to the present invention has a predetermined wavelength λ1.
The recording layer is formed from a substance that emits fluorescence when irradiated with excitation light having a wavelength of λ2 after the recording layer is irradiated with the recording light, so that the recording layer is formed by the information recording method of the present invention. By irradiating the recording light with the wavelength λ1 and changing this substance into a fluorescent substance, for example, as one pit, information such as image information and computer data can be recorded.

Since the recording medium according to the present invention has the recording layer formed from the substance having the above-described characteristics, when the recording layer is irradiated with the excitation light for reproducing the recorded information, the fundamental effect is obtained. Then, no fluorescence is emitted from the portion of the recording layer to which the recording light was not irradiated, and the fluorescence is emitted only from the portion of the recording layer to which the recording light was irradiated. That is, when recording information is reproduced from this recording medium, there is no occurrence of fluorescence that acts as a background from the non-irradiated portion of the recording medium, so that a reproduction signal with a high S / N can be obtained. Become.

In the recording medium according to the present invention, a support that does not emit fluorescence having the same wavelength as that of the fluorescent substance when irradiated with excitation light having the wavelength λ2 is used as a support for supporting the recording layer. When the recording layer is irradiated with the excitation light for reproducing the recorded information, the support does not generate uniform fluorescent light as a background, and a reproduced signal with a higher S / N can be obtained. Become like

Then, the recording medium of the present invention is provided on a support.
Since it has a simple configuration in which a substance that changes into a fluorescent substance by light irradiation is simply supported, it can be produced without using a special method, and thus the productivity is sufficiently high.

On the other hand, in the information recording method according to the present invention, if the evanescent light radiated from the range of the diameter shorter than the wavelength λ1 is used as the recording light of the wavelength λ1, it is not limited to the diffraction limit, but is smaller than the light wavelength. A pit having a size can be formed, and extremely high-density recording can be achieved.

In order to use such evanescent light, a minute aperture probe having a light passage opening at one end having a diameter smaller than the wavelength λ1 of the recording light is provided, and the evanescent light radiated from the opening of the minute aperture probe is used. Recording means configured to irradiate the recording layer or recording means configured to irradiate the recording layer with evanescent light emitted from the solid immersion lens may be used.

The recording layer on which the information has been recorded as described above is subjected to the information reproducing method of the present invention so that the wavelength λ2 different from the recording light wavelength λ1 in the excitation wavelength range of the fluorescent substance is applied.
When the excitation light is irradiated, fluorescence is generated from a portion where the substance constituting the recording layer is changed to a fluorescent material, and this fluorescence is not generated from a portion where the material is not changed. Therefore, for example, if the recording medium is scanned by the excitation light and the fluorescence generated at that time is detected for each scanning position, the recorded information can be read based on the presence or absence of the fluorescence.

Further, even when the recording layer is irradiated with excitation light having a wavelength λ2 equal to the recording light wavelength λ1, the excitation light intensity is lower than the recording light intensity, and the material constituting the recording layer is markedly converted to a fluorescent material. If the intensity is set to a level that does not cause a problem, the recorded information can be read without any problem in the same manner as described above.

Further, even if the excitation light is not scanned as described above, the excitation light is made to enter the support so that the excitation light propagates while repeating total reflection between both surfaces of the support of the recording medium. The recording information can be read by irradiating the recording layer with evanescent light leached from the support to the recording layer side, and detecting the fluorescence generated at that time by spatially resolving it.

If the evanescent light emitted from the above-described micro-aperture probe or the like from the diameter shorter than the wavelength is used as the excitation light, the excitation light is not limited to the diffraction limit, but is smaller than the light wavelength. Since only the excitation light can be irradiated to only the pits having the same size, information recorded at high density can be accurately reproduced.

As described above, when the recorded information is reproduced from a recording medium having a support formed of a dielectric material, a metal film formed on one surface thereof, and a recording layer formed thereon, When excitation light is incident on the metal film from the body side at a specific incident angle, surface plasmon resonance is excited in the metal film. As a result, a plasma wave (light wave) appears on the recording layer side
Oozes out and the recording layer can be excited by this plasma wave.

Further, the excitation light is made to enter the support so as to propagate while repeating total reflection between both surfaces of the support of the recording medium. At this time, the evanescent light seeping from the support toward the recording layer side Is applied to the recording layer, the excitation light seeps out over a wide area of the recording layer. That is, in this case, it is not possible to irradiate the excitation light only in a range smaller than the light wavelength. However, also in this case, if the fluorescence generated by the excitation light irradiation is spatially resolved and detected, the fluorescence generated from each of the small pits described above can be detected separately for each pit.

When the excitation light is made to enter the support as described above, the excitation light only seeps into the recording layer side as evanescent light, so that strong excitation light is applied to the means for detecting fluorescence. There is no incidence. Therefore, in this case, the fluorescence detecting means does not detect the excitation light which becomes a large noise component, and a reproduced signal having a higher S / N can be obtained.

[0229]

Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 shows a recording medium according to an embodiment of the present invention. As shown in the figure, the recording medium 10 has a recording layer 12 supported on a transparent substrate (support) 11.

The recording layer 12 is formed of a substance which is not a fluorescent substance but has a property of changing to a fluorescent substance when irradiated with light having a predetermined wavelength λ1. In the present embodiment, as such a substance, for example, a compound represented by the chemical formula (Formula 29) among the compounds represented by the aforementioned general formula (II-1):
The recording layer 12 is formed using a combination of the compound represented by the general formula (II-2) with the compound represented by the formula A-1.

The compound constituting the recording layer 12 has a wavelength λ1
Is converted into a fluorescent substance by irradiating a predetermined wavelength λ2
Emits fluorescent light of wavelength λ3. FIGS. 1 (1), (2) and (3) show this property.
That is, as shown in FIG. 1A, even if this compound is irradiated with light 2 having a wavelength λ2 in its original state, no fluorescence is emitted. However, as shown in FIG.
When this compound is irradiated with light 1 having a wavelength λ1, an irradiated portion P
Is changed to a fluorescent substance, and then, when the light P having the wavelength λ2 is irradiated on the portion P as shown in FIG.
Fluorescence 3 is emitted.

As described above, the recording layer of the present embodiment comprising a combination of the compound represented by the chemical formula (Formula 29) and the compound represented by the general formula (II-2) A-1 In the case of 12, λ1 = λ2 ≠ λ3.

Next, an embodiment of an information recording / reproducing apparatus using the recording medium 10 will be described. FIG. 2 shows an information recording / reproducing apparatus according to one embodiment of the present invention. This information recording / reproducing apparatus includes a recording light source 13 that emits recording light 1 having a wavelength of λ1 = 532 nm, a lens 14 that diverges the recording light 1, and a recording light 1 that is emitted from the lens 14 in a divergent light state. A collimator lens 15 for focusing, and a condenser lens 16 for converging the recording light 1 parallelized by the collimator lens 15 on the recording layer 12 of the recording medium 10.
As will be described later, an objective lens 17 for condensing the fluorescent light 3 emitted from the recording layer 12, a filter 18 for transmitting only light in the wavelength region of the fluorescent light 3, and a fluorescent light 3 for passing through the filter 18.
And a photodetector 20 such as a photodiode for detecting the fluorescent light 3 condensed by the condensing lens 19.

Recording Layer Formed Using Each of the Above Compounds
12 is that when irradiated with light having a wavelength of λ1 = 532 nm, the irradiated portion becomes a fluorescent material, and then this portion is also irradiated with a wavelength of 532 nm.
nm light, the wavelength λ3 = 650 nm
Which emits fluorescent light.

The recording light source 13 is composed of, for example, a combination of a semiconductor laser and a light wavelength conversion element, and is driven by a modulation driving circuit 21 receiving the digital data S. On the other hand, the photodetector 20 is composed of, for example, a photodiode or the like having sensitivity in the wavelength region of the fluorescence 3.

Hereinafter, the operation of the information recording / reproducing apparatus having the above configuration will be described. First, information recording will be described.
The modulation drive circuit 21 receives digital data S such as image data and computer data. Modulation drive circuit
The reference numeral 21 drives the recording light source 13 based on the digital data S, and ON-OFF modulates the recording light 1.

When the recording light 1 narrowed to a minute light spot by the condenser lens 16 irradiates the recording layer 12 of the recording medium 10, the recording light is applied to the recording layer 12 as described above with reference to FIG. Fine pits whose portions have been changed to fluorescent material are formed.

When forming pits in this way, the recording medium 10 is moved in the direction of arrow X by a known linear moving mechanism (not shown). Therefore, the pits are formed on the recording medium 10 in a line. Further, after forming such a pit row, if the recording medium 10 is moved in a direction substantially perpendicular to the arrow X direction, two pits are formed in the plane of the recording layer 12.
It is, of course, possible to form them three-dimensionally.

Next, reproduction of information recorded on the recording medium 10 in the form of the pits will be described. In the case of this information reproduction, the recording medium 10 is moved linearly as in the case of the information recording, and the recording light source 13 is driven at the same time. At this time, the recording light source 13 has a constant intensity unlike the case of information recording,
In addition, it is driven so as to emit light 2 having an intensity lower than that in the case of recording and which does not cause the recording layer 12 to remarkably become a fluorescent material. In the case of the present embodiment, the wavelength λ2 of the light 2 is 532 nm, which is the same as the recording light wavelength λ1, but this light 2 is hereinafter referred to as excitation light to distinguish it from the case of recording.

When the excitation light 2 is applied to the recording layer 12 of the recording medium 10, the portion where the pits are formed, that is, the portion that has been converted to a fluorescent material, emits the fluorescent
Is emitted, but the fluorescent light 3 is not emitted from a portion where no pit is formed.

The fluorescent light 3 passes through a filter 18 and is detected by a photodetector.
The photodetector 20 outputs a fluorescence detection signal SR corresponding to the fluorescence intensity. Therefore, the digital data S can be reproduced by sampling and quantizing the fluorescence detection signals SR output in time series in synchronization with the movement of the recording medium 10.

Note that the excitation light 2 having a wavelength of 532 nm is
Since it is cut by 8, it is not detected by the photodetector 20. Further, instead of such an optical filter 18, a prism, a grating, a hologram element or the like can be used as the wavelength selecting means.

As is clear from the above description, in this embodiment, the recording light source 13 also functions as an excitation light source for reproducing information.

Next, an information recording / reproducing apparatus according to another embodiment of the present invention will be described with reference to FIG. In FIG. 3, the same elements as those in FIG. 2 are denoted by the same reference numerals, and description thereof will be omitted unless otherwise required (the same applies hereinafter).

The information recording / reproducing apparatus of the present embodiment is basically different from the apparatus of FIG. 2 in that a disc-shaped recording medium 30 is used. This disk-shaped recording medium 30 has the same support and recording layer as the recording medium 10 in the apparatus shown in FIG. In this case, the recording light 1 or the excitation light 2 is guided to the lens 14 by bending the optical path by the mirror 31.

In recording and reproducing information, the recording medium is rotated in the direction of arrow R by driving means (not shown), and the entire optical system is relatively moved in the radial direction of the recording medium 30 so that the recording light 1 Alternatively, the excitation light 2 is
Is scanned two-dimensionally in a spiral or concentric manner. In order to track a spiral or concentric pit array, a conventionally known optical disk tracking technique may be applied. Otherwise, information recording and information reproduction on the recording medium 30 are performed in the same manner as in the apparatus of FIG.

Next, an information recording / reproducing apparatus according to still another embodiment of the present invention will be described with reference to FIG. The information recording / reproducing apparatus of the present embodiment is basically a near-field optical head instead of the lenses 15 and 16 as compared with the apparatus of FIG.
The difference is that 40 is used.

The near-field light head 40 has a small opening 41 having a diameter (for example, about several nm) shorter than the wavelength of the recording light 1 at the tip. Such a minute opening 41 is
For example, it is formed by sharpening the tip of the core of the optical fiber, depositing an opaque metal film 42 thereon, and then removing the metal film 42 only at the tip.

When the recording light 1 is introduced into the near-field light head 40, the evanescent light E
Is emitted. When this evanescent light E irradiates the recording layer 12 of the recording medium 10, the recording layer
Small pits are formed in which the compound composing 12 is converted to a fluorescent substance. Since the evanescent light E is emitted from a range of a diameter shorter than the recording light wavelength,
The pit diameter is smaller than the wavelength of the recording light, and from this point the recording density is greatly improved.

The information reproduction from the recording medium 10 is performed as shown in FIG.
In this case, the evanescent light E as the excitation light emitted from the near-field optical head 40 is emitted from a range of a diameter shorter than the wavelength. Each of the pits formed to have a diameter smaller than the light wavelength can be individually irradiated.

FIG. 5 shows an image of a pit formed on the recording medium 10 by this apparatus by a near-field optical microscope. As shown in the figure, it was confirmed that pits smaller in diameter than the recording light wavelength λ1 = 532 nm were formed.

Next, an information recording / reproducing apparatus according to still another embodiment of the present invention will be described with reference to FIG. The information recording / reproducing apparatus of the present embodiment is basically different from the apparatus of FIG. 2 in that a solid immersion lens 50 is arranged between the condenser lens 16 and the recording medium 10. When used in air, the solid immersion lens 50 emits evanescent light E from the other end (the lower end in the figure) when light is input from one end.

By using such a solid immersion lens 50, the near-field optical head can be used in the apparatus shown in FIG.
As in the case where 40 is used, the diameter of the pit becomes smaller than the wavelength of the recording light, and from this point the recording density is greatly improved.

Next, an information recording / reproducing apparatus according to still another embodiment of the present invention will be described with reference to FIG. The information recording / reproducing apparatus of the present embodiment is basically different from the apparatus of FIG. 2 in that an excitation light source 60 is provided separately from the recording light source 13 for information reproduction. The excitation light 2 emitted from the excitation light source 60 is made to travel on the same optical path as the recording light 1 thereafter by the beam splitter 61 inserted into the optical path of the recording light 1.

In this example, the recording light source 13 has a wavelength λ.
The one that emits recording light 1 of 1 = 350 nm is used. On the other hand, as the excitation light source 60, one that emits excitation light 2 having a wavelength λ2 = 532 nm is used. And recording media
As 10 ′, when the recording light 1 having the wavelength λ1 = 350 nm is irradiated, the material becomes a fluorescent material, and when the excitation light 2 having the wavelength λ2 = 532 nm is irradiated, the wavelength λ3 =
The one in which the recording layer 12 'is formed from a compound that emits fluorescence 3 of 600 nm is used. Specific examples of such a compound include those represented by formula (I-4) among the compounds represented by formula (I).

In this information recording / reproducing apparatus, information recording is performed in the same manner as in the apparatus shown in FIG. The information is reproduced by the excitation light 2 of a constant intensity emitted from the excitation light source 60.
To the recording layer 12 ′ of the recording medium 10 ′. In this case, the intensity of the excitation light 2 is required to be set particularly low when reproducing information, since the compound constituting the recording layer 12 'does not become a fluorescent substance even when the excitation light 2 having the wavelength λ2 = 532 nm is irradiated. There is no.

Next, an information recording / reproducing apparatus according to still another embodiment of the present invention will be described with reference to FIG. The information recording / reproducing apparatus of the present embodiment is basically different from the apparatus of FIG. 3 in that an excitation light source 60 is provided separately from the recording light source 13 for information reproduction. The excitation light 2 emitted from the excitation light source 60 is made to travel on the same optical path as the recording light 1 thereafter by the beam splitter 61 inserted into the optical path of the recording light 1.

In this example, the recording light source 13 and the excitation light source 60
The same as the recording light source 13 and the excitation light source 60 in the apparatus of FIG. 7 is used. As the recording medium 30 ', the recording layer of the recording medium 10' used in the apparatus of FIG.
A recording medium having the same recording layer as that of 12 ′ is used. Therefore, in this apparatus, information recording and information reproduction are performed by driving the recording light source 13 and the excitation light source 60, respectively, as in the apparatus of FIG.

Next, an information recording / reproducing apparatus according to still another embodiment of the present invention will be described with reference to FIG. The information recording / reproducing apparatus of the present embodiment is basically different from the apparatus of FIG. 4 in that an excitation light source 60 is provided separately from the recording light source 13 for information reproduction. The excitation light 2 emitted from the excitation light source 60 is made to travel on the same optical path as the recording light 1 thereafter by the beam splitter 61 inserted into the optical path of the recording light 1.

In this example, the recording light source 13 and the excitation light source 60
The same as the recording light source 13 and the excitation light source 60 in the apparatus of FIG. 7 is used. Also, the recording medium 10 '
As the recording medium, the same one as the recording medium 10 'used in the apparatus of FIG. 7 is used. Therefore, in this apparatus, information recording and information reproduction are performed by driving the recording light source 13 and the excitation light source 60, respectively, as in the apparatus of FIG.

Next, an information recording / reproducing apparatus according to still another embodiment of the present invention will be described with reference to FIG. The information recording / reproducing apparatus of this embodiment is basically different from the apparatus of FIG. 6 in that an excitation light source 60 is provided separately from the recording light source 13 for information reproduction. The excitation light 2 emitted from the excitation light source 60 is made to travel on the same optical path as the recording light 1 thereafter by the beam splitter 61 inserted into the optical path of the recording light 1.

In this example, the recording light source 13 and the excitation light source 60
The same as the recording light source 13 and the excitation light source 60 in the apparatus of FIG. 7 is used. Also, the recording medium 10 '
As the recording medium, the same one as the recording medium 10 'used in the apparatus of FIG. 7 is used. Therefore, in this apparatus, information recording and information reproduction are performed by driving the recording light source 13 and the excitation light source 60, respectively, as in the apparatus of FIG.

In the recording medium of the present invention, the substance used for forming the recording layer is the same as the recording medium 10 described above.
The present invention is not limited to the compounds used in the recording medium 10 ′.

For example, among the compounds represented by the general formula (II-1), the compound of the formula B-6 is designated as a fluorescent species, and the compound of the general formula (II-2) is designated as A-4. The recording layer can also be formed by combining these as chemical species that quench fluorescence. The recording layer formed thereby becomes a fluorescent material by the light having a wavelength of 532 nm, and also emits fluorescence when excited by the light having a wavelength of 532 nm.

Further, among the compounds represented by the above general formula (II-3), those of A-11 are designated as fluorescent chemical species, and B-40 of the compounds represented by the general formula (II-4)
Can be combined as a chemical species that quenches fluorescence to form a recording layer. The recording layer formed thereby becomes a fluorescent material by the light having a wavelength of 680 nm, and is also excited by the light having a wavelength of 680 nm to emit fluorescence having a wavelength of 750 nm.

Further, among the compounds represented by the above general formula (II-5), B-74 is a chemical species that emits fluorescence, and the compound represented by the general formula (II-4) is represented by B-5. The recording layer can also be formed by combining these as chemical species that quench fluorescence. The recording layer formed thereby becomes a fluorescent material by light having a wavelength of 680 nm, and also emits fluorescence when excited by the light having a wavelength of 680 nm.

Further, among the compounds represented by the above general formula (II-6), those of the compound represented by the formula B-136 are used as fluorescent chemical species, and the compounds represented by the general formula (II-4)
The recording layer can also be formed by combining 64 substances as chemical species that quench fluorescence. The recording layer formed thereby becomes a fluorescent material by the light having a wavelength of 532 nm, and also emits fluorescence when excited by the light having a wavelength of 532 nm.

[Brief description of the drawings]

FIG. 1 is a schematic side view showing an example of a recording medium of the present invention.

FIG. 2 is a side view showing an information recording / reproducing apparatus according to one embodiment of the present invention;

FIG. 3 is a side view showing an information recording / reproducing apparatus according to another embodiment of the present invention.

FIG. 4 is a side view showing an information recording / reproducing apparatus according to still another embodiment of the present invention.

5 is a photomicrograph of a pit formed on a recording medium by the apparatus of FIG.

FIG. 6 is a side view showing an information recording / reproducing apparatus according to still another embodiment of the present invention.

FIG. 7 is a side view showing an information recording / reproducing apparatus according to still another embodiment of the present invention.

FIG. 8 is a side view showing an information recording / reproducing apparatus according to still another embodiment of the present invention.

FIG. 9 is a side view showing an information recording / reproducing apparatus according to still another embodiment of the present invention.

FIG. 10 is a side view showing an information recording / reproducing apparatus according to still another embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Recording light 2 Excitation light 3 Fluorescence 10,10 ', 30,30' Recording medium 11 Transparent substrate 12,12 'Recording layer 15 Collimator lens 16 Condensing lens 17 Objective lens 18 Filter 19 Condensing lens 20 Photodetector 21 Modulation drive circuit 40 Near-field optical head 50 Solid immersion lens 60 Excitation light source 61 Beam splitter

Claims (33)

[Claims] 1. A recording layer comprising a substance which changes into a fluorescent substance when irradiated with recording light of a predetermined wavelength λ1 and emits fluorescence when irradiated with excitation light having a wavelength λ2, is carried on a support. recoding media. 2. The recording light wavelength λ1 and the excitation light wavelength λ
2. The recording medium according to claim 1, wherein 2 is equal to each other. 3. The recording light wavelength λ1 and the excitation light wavelength λ.
2. The recording medium according to claim 1, wherein 2 and 3 are different from each other. 4. The apparatus according to claim 1, wherein the support does not emit fluorescence having the same wavelength as the fluorescence emitted by the fluorescent substance when irradiated with the excitation light having the wavelength λ2. Recording medium according to the item. 5. The substrate according to claim 1, wherein the support is made of a dielectric, a metal film is formed on one surface thereof, and the recording layer is formed thereon. Recording medium. 6. The recording medium according to claim 5, wherein said metal film is made of gold or silver. 7. The recording medium according to claim 1, wherein the support is made of a material transparent to the excitation light having the wavelength λ2. 8. A substance which changes into a fluorescent substance when irradiated with the recording light having the predetermined wavelength λ1 protects a part of the functional groups of the compound [FL] with a protective group [PR]-to thereby emit fluorescence. The recording medium according to any one of claims 1 to 7, wherein the recording medium is a compound represented by the following general formula (I), the generation of which is suppressed. Formula (I) [FL]-[PR] In the formula, [FL] represents a compound residue that emits fluorescence;
[R] represents a group which can be separated from [FL] by light irradiation to [FL]. 9. A substance which changes into a fluorescent substance when irradiated with the recording light having the predetermined wavelength λ1 is a chemical species [F
The recording medium according to any one of claims 1 to 7, wherein the recording medium is represented by the following general formula (II), comprising a combination of [L] and a chemical species [Q] for quenching fluorescence. . General formula (II) [FL] + [Q] 10. The chemical species [FL] represented by the following general formula (II)
10. The recording medium according to claim 9, wherein the recording medium is a compound represented by the following general formula (II-2). Embedded image In the formula, Z ¹ and Z ² each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, and R ³⁰ and R ³¹
Each independently represents an alkyl group or an aryl group,
L ³ , L ⁴ , L ⁵ , L ⁶ and L ⁷ each independently represent a substituted or unsubstituted methine group (however, when a substituent is present on L ^{3 to} L ⁷ , they are linked to each other to form a ring; May be formed), p and q each independently represent 0 or 1, and n
1 and n2 each independently represent 0, 1 or 2;
Represents an anion, and m1 represents a number necessary to maintain charge balance. Embedded image In the formula, m and n each independently represent an integer of 0 to 2, and X ¹ ,
X ² represents ＮＲNR ¹ or ＣＲCR ² R ³ (R ¹ ,
R ² and R ³ represent a substituent), L ¹ and L ² each independently represent a divalent linking group. 11. The method according to claim 11, wherein the chemical species [FL] is represented by the following general formula (II)
The recording medium according to claim 9, wherein the recording medium is an anion represented by -3) and the chemical species [Q] is a cation represented by the following general formula (II-4). Embedded image In the formula, Za and Zb each independently represent a group of atoms necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring;
¹ and R ² each independently represent an alkyl group or an aryl group, and L ¹ , L ² , L ³ , L ⁴ and L ⁵
Each independently represents a substituted or unsubstituted methine group (however, when there is a substituent on L ^{1 to} L ⁵ , they may be linked to each other to form a ring), and n is an integer of 1 or more Represents
j represents 0, 1 or 2, and k represents 0 or 1. Embedded image In the formula, R ₅ and R ₆ each independently represent a substituent,
R ₇ and R ₈ each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group, and 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, r and s each independently represent an integer of 0 to 4, and when r and s are 2 or more, Multiple r and s
May be the same or different from each other. 12. The method according to claim 11, wherein the chemical species [FL] is represented by the following general formula (II)
-5) or (II-6), wherein the chemical species [Q] is a cation represented by the following general formula (II-4). recoding media. Embedded image In the formula, A ¹ , A ² , B ¹ and B ² represent a substituent,
L ¹ , L ² , L ³ , L ⁴ and L ⁵ represent a methine group;
¹ represents ＝ O, ＮＲNR, ＣC (CN) ₂ (where R represents a substituent), and X ² represents —O, —NR, —C (CN) _2.
(Where R represents a substituent), and m and n each represent an integer of 0 to 2. Y ¹ and E each represent an atom or a group of atoms necessary to form a carbocyclic or heterocyclic ring, and Z ¹ and G each represent an atom or a group of atoms necessary to form a carbocyclic or heterocyclic ring. x and y each independently represent 0 or 1. M
^{k +} represents an onium ion. k represents the number of charges. Embedded image In the formula, R ₅ and R ₆ each independently represent a substituent,
R ₇ and R ₈ each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group, and 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, r and s each independently represent an integer of 0 to 4, and when r and s are 2 or more, Multiple r and s
May be the same or different from each other. 13. A method for recording information on a recording medium according to claim 1, wherein the recording layer is irradiated with a recording light having a predetermined wavelength λ1 that carries the recording information. An information recording method, wherein the substance in the irradiated part is changed to a fluorescent substance. 14. The information recording method according to claim 13, wherein evanescent light emitted from a range of a diameter shorter than the wavelength is used as the recording light. 15. An apparatus for recording information on a recording medium according to claim 1, wherein the recording layer is irradiated with recording light having a predetermined wavelength λ1 carrying the recording information. An information recording apparatus, comprising: recording means for changing the substance in the irradiated portion to a fluorescent substance. 16. The recording means includes a micro-aperture probe having at one end a light-passing aperture having a diameter shorter than the wavelength of the recording light, and transmits evanescent light radiated from the aperture of the micro-aperture probe to the recording layer. The information recording apparatus according to claim 15, wherein the information recording apparatus performs irradiation. 17. The recording device according to claim 15, wherein the recording means irradiates the recording layer with evanescent light emitted from a solid immersion lens.
Information recording device according to the above. 18. The recording medium according to claim 1, wherein the recording layer is irradiated with recording light having a predetermined wavelength λ1 that carries recording information, and the substance in the recording light irradiated portion is irradiated with the recording light. A method for reproducing recorded information from a recorded recording medium which has been changed to a fluorescent substance, wherein the recording layer has a wavelength λ in an excitation wavelength range of the fluorescent substance.
2. An information reproducing method, comprising: irradiating excitation light of item 2 to generate fluorescence, and detecting the fluorescence. 19. A method of using a light having a wavelength λ2 equal to the wavelength λ1 of the recording light as the excitation light, and irradiating the recording layer with the excitation light having the wavelength λ2 at a lower intensity than the recording light. 19. The information reproducing method according to claim 18, wherein: 20. The information reproducing method according to claim 18, wherein light having a wavelength λ2 different from the wavelength λ1 of the recording light is used as the excitation light. 21. The recording medium according to claim 18, wherein light for irradiating a minute area is used as the excitation light, and the recording layer is scanned with the excitation light, and fluorescence generated at that time is detected for each scanning position. 21. The information reproducing method according to any one of claims 20 to 20. 22. The information reproducing method according to claim 21, wherein evanescent light emitted from a range of a diameter shorter than the wavelength is used as the excitation light. 23. An evanescent light which is made to enter the support so that the excitation light propagates while repeating total reflection between both surfaces of the support, and at this time, the evanescent light seeps out of the support toward the recording layer side. 21. The information reproducing method according to claim 18, wherein the recording layer is irradiated with a fluorescent light, and the fluorescence generated by the evanescent light irradiation is spatially resolved and detected. 24. The recording medium according to claim 5, wherein excitation light is incident on the metal film from the support at a specific incident angle. Information reproduction method described in section. 25. The recording medium according to claim 1, wherein the recording layer is irradiated with recording light having a predetermined wavelength λ1 that carries recording information, and the substance in the recording light irradiated portion is irradiated with the recording light. An apparatus for reproducing recorded information from a recorded recording medium that has been changed to a fluorescent substance, wherein the recording layer has a wavelength λ in an excitation wavelength range of the fluorescent substance.
An information reproducing apparatus, comprising: an excitation unit that emits fluorescence by irradiating the excitation light of claim 2; and a reading unit that detects the fluorescence. 26. The apparatus according to claim 26, wherein the excitation unit is configured to output the wavelength λ of the recording light.
26. The information reproducing apparatus according to claim 25, wherein the recording layer is irradiated with excitation light having a wavelength [lambda] 2 equal to 1 at a lower intensity than the recording light. 27. The apparatus according to claim 27, wherein the excitation unit is configured to output a wavelength λ of the recording light.
26. The information reproducing apparatus according to claim 25, wherein the recording layer is irradiated with excitation light having a wavelength λ2 different from 1. 28. The excitation means scans the recording layer with a focused beam of excitation light, and the reading means detects the fluorescence at each excitation light scanning position. The information reproducing apparatus according to any one of claims 25 to 27, characterized in that: 29. The recording medium according to claim 5, wherein the excitation unit is configured to irradiate the metal film with excitation light from the support side. The information reproducing apparatus according to the above. 30. The excitation means for scanning the recording layer with evanescent light emitted from a solid immersion lens, and the reading means for detecting the fluorescence at each excitation light scanning position. 29. The information reproducing apparatus according to claim 28, wherein: 31. The excitation means includes a micro-aperture probe having at one end a light-passing aperture having a diameter shorter than the wavelength of the excitation light, and the recording layer is irradiated with evanescent light emitted from the aperture of the micro-aperture probe. 29. The information reproducing apparatus according to claim 28, wherein the scanning is performed, and the reading unit detects the fluorescence at each scanning position of the excitation light. 32. The excitation means causes the excitation light to enter the support so as to propagate while repeating total reflection between both surfaces of the support. At this time, the excitation light impinges on the recording layer side from the support. 28. The recording layer is irradiated with evanescent light to be emitted, and the reading means spatially resolves and detects fluorescent light emitted from the recording layer by irradiation with excitation light. An information reproducing apparatus according to any one of the preceding claims. 33. An optical system through which the excitation light passes,
33. The information reproducing apparatus according to claim 25, wherein an optical member that emits fluorescence having the same wavelength as the fluorescence emitted by the fluorescent substance when irradiated with the excitation light having the wavelength [lambda] 2 is not included.