JP2587635B2 - Optical information recording medium - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a heat mode optical information recording medium having an organic dye thin film and performing recording and reproduction by causing a state change by a high-density energy beam. About.

[Conventional technology]

2. Description of the Related Art Conventionally, there has been known an information recording medium that records and reproduces information by irradiating a rotating disk-shaped information recording medium with a laser beam. As a recording layer of such a recording medium, one using a low-melting metal or a low-melting metal and a dielectric has been proposed. But these are poor storage,
There are drawbacks such as low separation power, low recording density, and high braking cost. In recent years, it has been proposed and practiced to use a dye thin film whose physical properties can be changed by light having a relatively long wavelength for the recording layer, but dyes having an absorption band at a long wavelength generally have stability to heat and light. There is a problem that the recording layer is low and the recording layer having satisfactory recording characteristics is not necessarily developed over a long period of time.

On the other hand, an optical information recording medium containing an oxonol dye, particularly an oxonol dye having a dioxopyrazolopyridine ring, is described in JP-A-60-71295. However, the dyes used in these recording media are difficult to synthesize, and it is generally difficult to obtain high-purity dyes in high yield, which has a serious practical disadvantage. In addition, JP 60
Among the dyes described in JP-A-71295, only one compound is presumed to have an absorption maximum in the wavelength region of a semiconductor laser (specifically, the absorption maximum wavelength and Examples are not disclosed). As can be inferred from the above, it is difficult to synthesize a dye having an absorption maximum wavelength particularly in the wavelength region of a semiconductor laser, that is, in the near infrared region, and the amount of the dye necessary for actually evaluating the performance as an optical information recording medium is difficult. Is synthesized,
Isolation was a difficult task.

[Problems to be solved by the invention]

An object of the present invention is, firstly, to provide an optical information recording medium giving a high C / N ratio.

A second object of the present invention is to provide an optical information recording medium having excellent stability.

A third object of the present invention is to provide an optical information recording medium in which a novel oxonol dye which is easy to synthesize is supported on a substrate.

[Means for solving the problem]

The object of the present invention is to record, reproduce,
The object has been attained by an optical information recording medium for erasing, wherein a dye represented by the following general formula (I) is carried on a substrate.

General formula (I) In the formula, Z represents an atomic group necessary to form a carbocyclic or heterocyclic ring, Q represents an atomic group that completes a conjugated double bond chain, m represents 0 or 1, M represents a hydrogen atom, a metal atom, L represents an atom, a metal salt ion, an optionally substituted ammonium ion, or a quaternary phosphonium ion; L represents an optionally substituted methine group, or a trimethine chain formed by linking these with a conjugated double bond Or represents a pentamethine chain; E represents O, S or NR ⁴ and R ¹ and R ⁴ represent an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, An optionally substituted aryl group, or an optionally substituted heterocyclic group, an optionally substituted amino group, an optionally substituted hydrazino group, or an optionally substituted dia It represents a sulfonyl group; R ² is an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, an alkynyl group which may be substituted, or substituted Represents a good heterocyclic group; R ³ is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted Good alkenyl group, optionally substituted alkoxy group, optionally substituted aryloxy group, optionally substituted heterocyclic group, optionally substituted alkoxycarbonyl group, optionally substituted aryl An oxycarbonyl group, an optionally substituted amino group, an optionally substituted acyloxy group,
Carbamoyl group which may be substituted, sulfamoyl group which may be substituted, alkylthio group which may be substituted, arylthio group which may be substituted, alkylsulfonyl group which may be substituted, Represents an arylsulfonyl group or an alkynyl group which may be substituted; R ¹ and R ⁴ may be linked to each other to form a ring;

Preferred among the groups represented by M are a hydrogen atom,
Alkali metal ion, alkaline earth metal ion, nickel ion, copper ion, iron ion, cobalt ion, chromium ion or cation complex containing Ni, Cu, Fe, Co, Cr, alkyl or aryl having 30 or less carbon atoms Group, an ammonium ion optionally substituted with an aralkyl group, or an alkyl or aryl having 40 or less carbon atoms,
Alternatively, it is a quaternary phosphonium salt substituted with an aralkyl group, particularly preferably a hydrogen atom.

The ring completed by Q and Z is preferably a 4, 5, 6, or 7-membered ring, and may further form a condensed ring with another 4, 5, 6, or 7-membered ring. It may be.

Preferred as hetero atoms forming the heterocycle completed by Q and Z are B, N, O, S, Se and Te.

Among the atomic groups represented by Z, those that form a carbon ring include, for example, the following.

_{CH 2 3 CH 2 4, -CH} = CH -, - CH = CH-CH = CH
−, Examples of the atomic group represented by Z which form a heterocyclic ring include the following.

R represents an optionally substituted alkyl group (including a benzyl group) or an optionally substituted aryl group.

Particularly preferred among the atomic groups represented by Z are those capable of completing a 5- or 6-membered heterocyclic ring.
It contains at least one heteroatom selected from N, O, S, Se, and Te.

As the linking group represented by L, those represented by formulas (a) to (h) are particularly preferable.

General formula (a) General formula (b) General formula (c) General formula (d) General formula (e) General formula (f) General formula (g) General formula (h) In the general formulas (a) to (h), Y represents a hydrogen atom or a monovalent group, and p and q independently represent 0 or 1. In this case, examples of the monovalent group include a lower alkyl group such as a methyl group, an aralkyl group such as a benzyl group and a p-methoxybenzyl group, an aryl group such as a phenyl group, an m-chlorophenyl group and a naphthyl group, and a methoxy group. Lower alkoxy group, dimethylamino group, diphenylamino group, methylphenylamino group, morpholino group, imidazolidino group, disubstituted amino group such as ethoxycarbonylpiperazino group, alkylcarbonyloxy group such as acetoxy group, alkylthio group such as methylthio group Groups, cyano groups, nitro groups, halogen atoms such as F, Cl, Br and the like are preferable.

Particularly preferred among the linking groups represented by L are those represented by the general formula (a) or (b),
In particular, Y represents a hydrogen atom, and at least one of p and q represents 0.

Preferred as substituents on L, Y or Z in the general formula (I) are those having 30 or less carbon atoms and are selected from the following groups, and these groups further have a substituent. You may have. That is, an alkyl group,
Aralkyl, aryl, hydroxy, F, Cl, B
r, I, cyano group, nitro group, alkoxy group, aralkyloxy group, aryloxy group, acyl group, acyloxy group, acylamino group, sulfonamide group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkoxycarbonyl group, carbamoyl group , Sulfamoyl, carboxy or carboxylato, sulfonic or sulfonato, carbamoylamino, sulfamoylamino, alkylsulfonyl, aralkylsulfonyl, arylsulfonyl, alkylsulfinyl, aralkylsulfanyl, arylsulfinyl Group, alkylthio group, aralkylthio group, or arylthio group.

Of the groups represented by F, preferred are O or NR ⁴
Preferred as R ⁴ are an optionally substituted alkyl group, an optionally substituted hydrazino group, and an optionally substituted diazenyl group, particularly when E is NR ^4. Those in which R ⁴ is linked to R ¹ to form a ring are preferred. Preferred as a ring formed by linking R ¹ and R ⁴ are imidazole, pyrazole, triazole, and tetrazole rings, and these rings may have a substituent, and may be a fused ring with another ring. May be formed.

Of the groups represented by R ¹ or R ⁴ , preferred are an optionally substituted alkyl group having 1 to 30 carbon atoms,
An optionally substituted phenyl group having 6 to 30 carbon atoms, an optionally substituted heterocyclic group having 5 or 6 ring members and 1 to 30 carbon atoms (hetero atoms include, for example, B, N, O, S, Se, Te). The substituents which may be substituted on these groups may be neutral or other ionic ones. Preferred are halogen atoms (eg, F, Cl, Br, I), cyano groups, nitro groups, Carboxyl group, sulfonic acid group, hydroxyl group, alkoxy group (for example, methoxy group, isopropoxy group, hexadecyloxy group, etc.), aryloxy group (for example, phenoxy group, 2,4-di-t-pentylphenoxy group, m-pentane Decylphenoxy group, p-methoxyphenyl group, 3,
5-dichlorophenyl group, 3-sulfophenyl group, 3,5-
Alkyl group (methyl group, 4-
Sulfobutyl group, 2-methoxyethyl group, trifluoromethyl group, etc.), aryl group (for example, phenyl group, 4-
A sulfophenyl group, a 3-chlorophenyl group, a 4-hexylphenyl group, a 2-naphthyl group, etc., a substituted or unsubstituted amino group (for example, an amino group, a methylamino group, a phenylamino group, an acetylamino group, a methanesulfonylamino group) , Methylcarbamoylamino group, trimethylammonio group, phenylthiocarbamoylamino group, benzenesulfonylamino group, etc.), carbamoyl group (for example, carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, octadecylcarbamoyl group, diethylcarbamoyl group, pyrrolidinocarbonyl) A sulfamoyl group (for example, a sulfamoyl group, a dimethylsulfamoyl group, a t-butylsulfamoyl group, a phenylsulfamoyl group, a pyrrolidinosulfonyl group, a 3- (2,
4-di-t-pentylphenoxy) butylsulfamoyl group, etc., alkyl or arylthio group (eg, methylthio group, phenylthio group, benzylthio group, octadecylthio group), alkylsulfonyl group (eg, methanesulfonyl group, 2-ethoxyethyl) Sulfonyl group), arylsulfonyl group (for example, benzenesulfonyl group, dodecylbenzenesulfonyl group, 2- (2-methoxyethoxy) -5- (4-hydroxyphenylazo)
-Benzenesulfonyl group).

Particularly preferred among the groups represented by R ¹ or R ⁴ are an optionally substituted alkyl group having 1 to 20 carbon atoms (optionally substituted with the above-mentioned preferred substituents),
An optionally substituted phenyl group having 6 to 20 carbon atoms (optionally substituted with the aforementioned preferred substituents),
A 5- or 6-membered heterocyclic group having 1 to 20 carbon atoms (for example, 2-pyridyl, 4-pyridyl, 2-benzthiazolyl, 2- (1-methylimidazolyl), 4,6-diethylamino-2-triazinyl and the like); is there.

Of the groups represented by R ² , preferred are an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted phenyl group having 6 to 30 carbon atoms, and 1 to 30 carbon atoms. An optionally substituted heterocyclic group (having 5 or 6 ring members and heteroatoms represented by B, N,
O, S, Se, and Te). Preferred as the group substituting on these groups include the groups described above as preferred substituents on R ^1.

Among the groups represented by R ² , particularly preferred are an optionally substituted alkyl group having 1 to 20 carbon atoms (eg, a methyl group, a 4-sulfobutyl group, a 2-methoxyethyl group, a trifluoromethyl group, a benzoyl group). An oxymethyl group, etc., an optionally substituted phenyl group having 6 to 20 carbon atoms (for example, phenyl group, 4-sulfophenyl group, 3-chlorophenyl group, 3-trifluoromethylphenyl group, 2-methanesulfonyl- A 4-nitrophenyl group, a 2-nitro-4-dimethylsulfamoylphenyl group, a 4-methanesulfonylphenyl group, etc., a heterocyclic group having 1 to 20 carbon atoms and 5 or 6 ring members (for example, 2-pyridyl, 4-pyridyl, 3-pyridyl, 2-benzthiazolyl, 2- (1-methyl-imidazolyl), 4,
6-dibutylamino-2-triazinyl).

Preferred among the groups represented by R ³ are a hydrogen atom,
An optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted phenyl group having 6 to 30 carbon atoms, an optionally substituted carbamoyl group having 1 to 30 carbon atoms, carbon atom An optionally substituted alkoxycarbonyl group having 2 to 30 carbon atoms, having 7 to 7 carbon atoms
30 optionally substituted phenoxycarbonyl groups, carboxyl groups, or hydroxyl groups. Preferred as the group substituting on these groups are those groups described above as preferred substituents on R ^1.

Among the groups represented by R ³ , particularly preferred are an optionally substituted alkyl group having 1 to 20 carbon atoms (eg, a methyl group, a t-butyl group, a trifluoromethyl group, etc.), a C ⁶ to C 20 group. 20 optionally substituted phenyl groups (for example, phenyl group, 4-methoxyphenyl group, 3,5-dichlorophenyl group and the like), carboxyl group and salts thereof, optionally substituted carbamoyl having 1 to 20 carbon atoms Groups (for example, carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, pyrrolidimecarbonyl group, 2-ethylhexylcarbamoyl group, etc.), and alkoxycarbonyl groups having 2 to 20 carbon atoms (for example, ethoxycarbonyl group, hexadecyloxycarbonyl group, t -Butoxycarbonyl group, cholesteryloxycarbonyl group, etc.) Bokishi group or a salt thereof,
Or a hydroxyl group.

Hereinafter, specific examples of the oxonol dye used in the present invention are shown, but the present invention is not limited to these. Table 1 shows that, among the compounds represented by the general formula (I), E represents O, and a ring completed by Q and Z represents a compound represented by the following general formula (A).
Or 50 was indicated.

General formula (A) [Wherein E, R ¹ , R ² and R ³ have the same meanings as in the general formula (I)] The compound of the present invention is prepared by converting a dioxopyrazolopyridine compound represented by the following general formula (II) into a suitable methine source, trimethine source or pentamethine source compound (for example, ethyl orthoformate, 1,5- Diphenyl-
Reaction with 1,5-diaza-1,3-pentadiene, 1,5,5-trialkoxy-1,3-pentadiene, 1,7-diphenyl-1,7-diaza-1,3,5-heptatriene) Can be synthesized. At this time, if a basic substance such as triethylamine and an acid anhydride such as acetic anhydride are added, the reaction may be accelerated. More specifically, Akira Tokuno
39-22069, 43-3504, 52-38056, 54-38
Nos. 129, 55-10059, JP-A-49-99620, 59-168
No. 34, or a method described in US Pat. No. 4,181,225, for example.

General formula (II) [Wherein R ¹ , R ² and R ³ represent the same groups as defined in the general formula (I). The compound represented by the general formula (II) has the following general formula (II)
It can be synthesized by heating the compound represented by I) and the compound represented by the general formula (IV) under acidic conditions.

General formula (III) [Wherein R ¹ and R ² represent the same groups as R ¹ and R ² in formula (I). General formula (IV) [In the formula, R ³ represents a group having the same meaning as R ³ in formula (I), and R ⁴ represents an alkyl group or an aryl group. The compound represented by the general formula (II) is disclosed in
It can also be synthesized by alkylating, aryl grouping or acylating the dioxopyrazolopyridine compound (general formula (V)) described in 112626.

General formula (V): Table of R ^1, R ³ as defined for group wherein R ^1, R ³ is the general formula (I). It should be noted that the general formula (I) or the general formula (I
The functional group of the compound represented by I) can be converted to another functional group by a known method.

Examples of the synthesis of the compound represented by formula (I) are described below.

Synthesis Example 1. Synthesis of compound 2 1-phenyl-3-anilino-2-pyrazolin-5-
On (25 g), ethyl acetoacetate (18 g), and acetic acid (150 ml) were heated at reflux for 6 hours. The reaction solution was diluted with water, and the resulting solid was crystallized from acetonitrile to obtain 10.9 g of 2,7-diphenyl-4-methylpyrazolo [3,4-b] pyridine-3,6-dione. 145-1 melting point
47 ° C The 2,7-diphenyl-4-methylpyrazolo [3.4-
b] Pyridine-3,6-dione (3.17 g) in methanol (50
1,7-diphenyl-1,7-diaza-1,3,5-heptatriene hydrochloride (2.85 g) was added to a solution prepared by adding triethylamine (2.8 ml) and triethylamine (2.8 ml) and dissolved. (1.88 ml) was added and the mixture was stirred at room temperature for 1 hour. The resulting precipitate was collected by filtration, washed with methanol, and dried to give 5- [5-
(N-acetylanilino) -2,3-pentadienylidene] -2,7-diphenyl-4-methylpyrazolo [3,4-
b] Pyridine-3,6-dione (1.9 g) was obtained. N, N-dimethylformamide (60 ml), 2,7-
Diphenyl-4-methylpyrazolo [3,4-b] pyridine-3,6-dione (095 g) and triethylamido (0.42 g)
g) was added and the mixture was stirred at 50 ° C for 2 hours. After filtering off a trace amount of insoluble matter, 10 times volume of ethyl acetate was added with stirring to crystallize. The obtained crystals were redissolved in a small amount of N, N-dimethylformamide, crystallized by adding 10 volumes of ethyl acetate, collected by filtration and dried to obtain Compound 2 (1.3 g). Golden crystal, melting point 300 ° C or higher, Synthesis Example 2 Synthesis of Compound 1 3-Methylamino-1-phenyl-2-pyrazolin-
5-One (1.9 g), ethyl acetoacetate (1.4 g), and acetic acid (8 ml) were heated under reflux for 6 hours. The reaction solution was diluted with water, and the resulting crystals were collected by filtration, washed with isopropyl alcohol, and 1.8 g of 4,7-dimethyl-2-phenylprizolo [3.4-
b] Pyridine-3,6-dione (melting point 179-181 ° C.) was obtained. To a solution prepared by adding methanol (20 ml) and triethylamine (0.7 ml) to the crystals (1 g), 1,7-diphenyl-1,7-diaza-1,3,5-heptatriene hydrochloride (0.7 g) was added.
Was added and dissolved, then acetic anhydride (0.6 ml) was added, and the mixture was stirred at room temperature for 1 hour. The resulting precipitate is collected by filtration, washed with methanol, dried and dried to give 5- [5- (N-acetylanilino).
-2,3-pentadienylidene] -4,7 dimethyl-2-phenylpyrazolo [3,4-b] pyridine-3,6-dione (0.2
g) was obtained. N, N-dimethylformamide (5 ml) and 4,7-dimethyl-2-phenylpyrazolo [3,4-b] pyridine-3,6-dione (0.08 g) were added to the crystals (0.15 g), and
Stirred at 0 ° C. for 2 hours. The reaction solution was filtered and diluted with water to obtain Compound 1 (0.2 g).

Synthesis Example 3 Synthesis of Compound 4 3- (3-chlorophenylamino) -1-phenyl-
Ethyl acetoacetate (2.8 g) and acetic acid (40 ml) were added to 2-pyrazolin-5-one (5.7 g), and the mixture was heated under reflux for 6 hours. The resulting crystals were collected by filtration, washed with isopropyl alcohol, and washed with 2 g of 7- (3-chlorophenyl) -4-methyl-
There was obtained 2-phenylpyrazolo [3,4-b] pyridine-3,6-dione (melting point 278-282 ° C). To a solution prepared by adding methanol (24 ml) and triethylamine (1.12 ml) to the crystals (1.4 g) was added 1,7-diphenyl-1,7-diaza-1,
3,55-Heptatriene hydrochloride (1.13 g) was added to dissolve, then acetic anhydride (0.75 ml) was added, and the mixture was stirred at room temperature for 1 hour. The resulting precipitate was collected by filtration, washed with methanol, dried and dried to give 5- [5- (N-acetylanilino) -2,3-pentadienylidene] -7- (3-chlorophenyl) -4-.
Methyl-2-phenylpyrazolo [3,4-b] pyridine-
3,6-dione was obtained. N, N-dimethylformamide (30 ml), 7- (3-chlorophenyl)-
4-Methyl-2-phenylpyrazolo [3,4-b] pyridine-3,6-dione (0.32 g) and triethylamine (0.13 ml) were added, and the mixture was stirred at 50 ° C. for 2 hours.

After filtering the reaction solution, 10-fold volume of ethyl acetate was added with stirring to crystallize. The obtained crystals were again added to a small amount of N, N-
After dissolving in dimethylformamide, a 10-fold amount of ethyl acetate was added for crystallization, which was collected by filtration, washed with ethyl acetate, and dried to obtain Compound 4 (0.4 g).

Synthesis Example 4 Synthesis of Compound 3 Ethyl acetoacetate (8.5 g) and acetic acid (75 ml) were added to 3- (4-methoxyphenylamino) -1-phenyl-2-pyrazolin-5-one (14 g), and the mixture was heated for 6 hours. Refluxed. The reaction solution was poured into 150 ml of water, and the resulting solid was dissolved by heating in a mixture of methanol (500 ml) and acetone (150 ml), and then cooled to 8.4 g of 7- (4-methoxyphenyl)-.
4-Methyl-2-phenylpyrazolo [3,4-b] pyridine-3,6-dione (melting point 189-190 ° C.) was obtained. To a solution prepared by adding methanol (40 ml) and triethylamine (2.8 ml) to the crystals (3.47 g), 1,7-diphenyl-
1,7-diaza-1,3,5-heptatriene hydrochloride (2.85 g)
Then, acetic anhydride (1.88 ml) was added, and the mixture was stirred at room temperature for 1 hour. The resulting precipitate was collected by filtration, washed with methanol, dried and dried to give 5- [5-N-acetylanilino)-.
2,3-pentadienylidene] -7- (4-methoxyphenyl) -4-methyl-2-phenylpyrazolo [3,4-
b] Pyridine-3,6-dione (4.1 g) was obtained. N, N-dimethylformamide (40 ml), 7-
(4-Methoxyphenyl) -4-methyl-1-phenyl-2-pyrazolin-5-one (2.4 g) and 0.98 ml of triethylamine were added, and the mixture was stirred at 50 ° C. for 2 hours. After filtering the reaction solution, 10-fold volume of ethyl acetate was added with stirring to crystallize. The obtained crystals were recrystallized from acetonitrile to obtain Compound 3 (1.0 g). 260 ° C. (decomposition) Synthesis Example 5 Synthesis of Compound 5 In Synthesis Example 1, 1-phenyl-3-anilino-2
-Instead of pyrazolin-5-one, 3- (3-methyl-
Compound 5 was obtained in the same manner except that 4-methoxyphenylamino) -1-phenyl-2-pyrazolin-5-one was used.

(Melting point: 300 ° C. or higher) Synthesis Example 6 Synthesis of Compound 6 In Synthesis Example 1, 1-phenyl-3-anilino-2
Compound 6 was obtained in the same manner except that 3- (4-n-hexylphenylamino) -1-phenyl-2-pyrazolin-5-one was used instead of -pyrazolin-5-one.

(Melting point: 220-223 ° C) Synthesis Example 7 Compounds 12-16, 27, 30, 33-35, 44-
60 was synthesized. The melting point of each of these compounds is 300 ° C
That was all.

The oxonol dye used in the optical recording medium of the present invention may be used alone, in combination of two or more kinds, or may be used in combination with a dye other than the oxonol dye of the present invention. It is also effective to use various antioxidants and singlet oxygen quencher in combination for improving the reading durability. Further, various resins may be used in combination.

Alternatively, the durability can be increased by adding a transition metal ion to form a chelate.

As the quencher used for the optical recording medium of the present invention, various quenchers can be used. As such a quencher, a transition metal complex that reduces regeneration deterioration and has good compatibility with a dye is preferable. In this case, preferred as the central metal are Ni, Co, Cu, Pd, Pt and the like.

Examples of the new quencher include those represented by the following general formula [VI] or [VII].

(Wherein [Cat ₁ ] and [Cat ₂ ] represent cations necessary for neutralizing the complex, and M ₁ and M ₂ represent nickel, copper, cobalt, palladium or platinum. N is 1 Or 2). In the compound represented by the general formula [VI] or [VII], the inorganic cation among the cations represented by [Cat ₁ ] or [Cat ₂ ] is an alkali metal (for example, Li) , Na, K, etc.), alkaline earth metals (Mg, Ca, Ba
Etc.) or NH ₄ ⁺ .

Examples of the organic cation include a quaternary ammonium ion and a quaternary phosphonium ion.

Among the above-mentioned cations [Cat ₁ ] and [Cat ₂ ], the following general formulas (VIII-a), (VIII-b) and (VI
II-c), (VIII-d) or (VIII-e).

Where R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R
¹⁹ , R ²⁰ , R ²¹ and R ²² each represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, and Z ¹ and Z ² each represent Represents a nonmetallic atomic group which forms a 5- or 6-membered ring by bonding to a nitrogen or phosphorus atom in the formula.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-butyl group, an iso-amyl group, an n-dodecyl group and an n-octadecyl group. The aryl group having 6 to 14 carbon atoms includes, for example, phenyl group, tolyl group, α
-Naphthyl group and the like.

These alkyl or aryl groups include a cyano group, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, an n-butyl group, an n-octyl group, etc.),
An aryl group having 6 to 14 carbon atoms (for example, a phenyl group, a tolyl group, an α-naphthyl group, etc.);
20 acyloxy groups (eg, acetoxy group, benzoyloxy group, p-methoxybenzoyloxy group, etc.), alkoxy groups having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), aryloxy group (eg, , Phenoxy group, toloxy group, etc.), aralkyl group (for example, benzyl group, phenethyl group or anisyl group, etc.), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, etc.),
Aryloxycarbonyl group (eg, phenoxycarbonyl group, toloxycarbonyl group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, etc.), carbamoyl group (For example, N-ethylcarbamoyl group, N-phenylcarbamoyl group, etc.),
Alkylsulfonylamino group (eg, methylsulfonylamino group, phenylsulfonylamino group, etc.), sulfamoyl group (eg, N-ethylsulfamoyl group, N-phenylsulfamoyl group, etc.), sulfonyl group (eg, mesyl Group, a tosyl group, etc.).

Z ¹ and Z ² each represent a nonmetallic atom group necessary for forming a 5- or 6-membered ring as described above. These 5
Examples of the six-membered or six-membered ring include a pyridine ring, an imidazole ring, a pyrrole ring, a 2-pyrroline ring, a pyrrolidine ring, a piperidine ring, a pyrazole ring, a pyrazoline ring, and an imidazoline ring. Examples of the cation represented by the general formula (VIII-b) include a dodecylpyridinium group, a hexadecylpyridinium group, a dodecylimidazolium group, and the like. General formula (VIII
Examples of the cation represented by -c) include N-
Examples thereof include an ethyl-N-hexadecylpiperidinium group and an N-ethyl-N-dodecylpyrazolidinium group.

The above general formulas (VIII-a), (VIII-b) and (VIII-
Among the cations represented by c), (VIII-d) and (VIII-e), those which are particularly preferably used in the present invention are (VIII) in view of the availability of production raw materials and production costs.
-A), (VIII-b), (VIII-d) and (VIII-
e).

The types of the cations [Cat ₁ ] and [Cat ₂ ] affect the solubility of the compound represented by the general formula [VI] or [VII] in an organic solvent.

In general, when the substituent bonded to the quaternary heteroatom is an alkyl group, the solubility increases as the chain length increases, especially in the case of tetraalkyl-substituted ammonium or phosphonium, and this tendency is remarkable. A cation having a total of 17 or more carbon atoms, and a cation having a total of 4 or more carbon atoms in the case of a phosphonium cation gives high solubility.

Nickel when M ₁ or M ₂ is mentioned in a preferred order in the compound represented by the general formula (VI) or (VII).
The order is cobalt, copper, palladium, and platinum.

The metal complex represented by the general formula [VI] or [VII] has a planar four-coordinate configuration. In the compound of the general formula [VII], whether the thioketone group is symmetric or asymmetric with respect to the central metal is not uniquely determined, but in this specification, it is represented as the general formula [VII] for convenience.

The compound represented by the general formula [VI] or [VII] can be synthesized as follows.

The compound of the general formula [VI] (N = 2) is obtained by converting disodium-1,3-dithiol-2-thione-4,5-dithiolate obtained by reacting carbon disulfide and sodium into a zinc complex first. The benzoyl chloride is reacted to form a bisbenzoylthio form. It is obtained by decomposing it with an alkali and then reacting with a metal salt.

The compound of the general formula [VI] (n = 1) can be obtained by oxidizing the complex (n = 2) obtained above with an appropriate oxidizing agent.

The compound of the general formula [VII] (n = 2) is obtained by reacting carbon disulfide with sodium to obtain disodium-
1,3-dithiol-2-thione-4,5-dithiolate is
Heat to about 130 ° C and disodium-1,2-dithiol-3
-Isomerize to thione-4,5-dithiolate. This is made into a zinc complex, which is reacted with benzoyl chloride to form a bisbenzoylthio form. This is obtained by decomposing it with calcali and reacting with a metal salt.

Further, the general formula [VII] (n = 1) can be obtained by oxidizing the complex (n = 2) obtained above with an appropriate oxidizing agent.

The 1,3-dithiol-2-thione-4,5-dithiolate anion, which is an intermediate for obtaining the compound of the general formula [VI] or [VII], can be used as described above in other electrochemical reduction methods using Na. It can also be obtained by effective reduction.

Preferred examples of the compound represented by the general formula [VI] are as follows.

The synthesis example of the compound represented by the general formula (VI) is shown below.

Synthesis Example VI-1 <Synthesis of Exemplified Compound (VI-4)> (1-1) Synthesis of bis (tetraethylammonium) -bis (1,3-dithiol-2-thione-4,5-dithiolato) zinc complex.

All reaction operations were performed under an argon atmosphere. After 23 g of sodium was cut into small pieces and dispersed in 180 ml of carbon disulfide, 200 ml of dithimerformamide was slowly added dropwise thereto with stirring. At this time, take care not to violently generate heat. After the completion of the dropwise addition of dimethylformamide, the mixture was carefully heated and refluxed for 24 hours. After completion of the reaction, unreacted sodium was filtered off. Then add ethanol to the filtrate
50 ml was added and the mixture was stirred at room temperature for 2 hours. From this solution, carbon disulfide is distilled off under reduced pressure at room temperature. Then, 300 ml of water was slowly added dropwise, and the resulting solution was filtered.

Then, a solution prepared by dissolving 20 g of zinc chloride in 500 ml of methanol in advance and adding 500 ml of concentrated ammonium water thereto was prepared, and added to the above reaction solution (room temperature).
After stirring for 5 minutes, tetraethylammonium bromide 53
When an aqueous solution of g in 250 ml of water is added, a red precipitate immediately precipitates. This was filtered and air-dried to obtain a zinc complex.

(1-2) Synthesis of 4,5-bis (benzoylthio) -1,3-dithiol-2-thione.

22 g of the zinc complex obtained in (1-1) is dissolved in 500 ml of acetone and filtered. While stirring the filtrate, add benzoyl chloride
Add 150 ml. A yellow precipitate precipitates immediately. Filtration,
After washing with water and air drying, 16 g of the title compound was obtained.

(1-3) Synthesis of Exemplified Compound (VI-4) 9.2 g of the bis (benzoylthio) derivative obtained in (1-2) is dissolved in 50 ml of methanol. To this, 6.3 g of a 28% methanol solution of sodium methoxide is added and stirred for 10 minutes.
2.4 g of nickel chloride (hexahydrate) in methanol
Add the solution dissolved in 50 ml and stir at room temperature for 30 minutes. When a solution of 8.5 g of tetrabutylphosphonium bromide dissolved in 100 ml of methanol is added to this solution, a black precipitate immediately precipitates. The mixture was further stirred for 20 minutes, filtered, washed with acetone, air-dried, and recrystallized from acetone-isopropyl alcohol to obtain the title compound. Yield 3.8 g Synthesis Example VI
-2 <Synthesis of Exemplified Compound (VI-2)> 1 g of the nickel complex obtained in (1-3) is mixed with 60 ml of acetone.
And 30 ml of acetic acid was added thereto, and the mixture was stirred for 3 hours and the solvent was distilled off. As a result, black crystals were precipitated. This was recrystallized from acetone-methanol to give the target compound (VI
-2) was obtained. The yield _{0.4g, mp185 ℃ λ max: 1125nm} ,
ε _max : 2.51 × 10 ⁴ (in CH ₂ Cl ₂ ) Also, as a known quencher, JP-A-59-178295
No. The following compounds may be mentioned.

(I) Bisdithio-α-diketone type R ^{1 to} R ⁴ represent an alkyl group or an aryl group, and M represents a divalent transition metal atom.

(Ii) bisphenyldithiol R ⁵ and R ⁶ represent an alkyl group or a halogen atom;
Represents a divalent transition metallite.

(Iii) acetylacetonate chelate (iv) dithiocarbamic acid chelate (v) bisphenylthiol (vi) thiocatechol chelate (vii) salicylaldehyde oxime (viii) thiobisphenolate chelate (ix) phosphonous acid Acid chelate type (x) benzoate type (xi) hindered amine type (xii) transition metal salt In addition, aminium type or diimmonium type compounds represented by the following formulas may be mentioned, and specific examples are IRG-002 manufactured by Nippon Kayaku Co., Ltd. IRG-003, IRG-002 and IRG-023.

(In the formula, R represents an alkyl group or an aryl group.) In the present invention, a conjugate of the cation of the dye and the anion of the quencher can also be used.

The quencher is generally 0.05 to 1 mol per the dye.
12 mol, preferably 0.1 to 1.2 mol, is used.

The quencher is preferably contained in the dye thin film recording layer, but may be contained in a layer different from the recording layer. In the optical recording medium of the present invention, if necessary, an undercoat layer may be provided on the substrate, a protective layer may be provided on the recording layer, and a reflective layer may be provided on the substrate or the recording layer.

Any known substrate can be used. Typical examples are glass or plastic, and acrylic, polycarbonate, polysulfone, polyimide, amorphous polyolefin, epoxy resin, polyester, etc. are used as plastic. Various shapes such as a disk shape, a card shape, a sheet shape, and a roll film shape are possible.

A guide groove may be formed on the glass or plastic substrate to facilitate tracking during recording. A glass or plastic substrate may be provided with a subbing layer such as a plastic binder or an inorganic oxide or inorganic sulfide. An undercoat layer having lower thermal conductivity than the substrate is preferred. It is also possible to use a so-called air sandwich structure in which two recording media face each other with the recording layers inside.

In the formation of the recording layer in the present invention, for example, a dye and a quencher represented by the general formula (I) may be fluorinated with an organic solvent (eg, methanol, ethanol, isopropyl alcohol, 2,2,3,3-tetrafluoropropanol, etc.). Dissolve in alcohols, dichloromethane, dichloroethane, acetone, etc., and if necessary, appropriate binders (for example, PVA, PVP, polyvinyl butyral, polycarbonate, nitrocellulose, polyvinyl formal, methyl vinyl ether, chlorinated paraffin, maleic anhydride copolymer) A styrene-butadiene copolymer, a xylene-based resin) and applying the solution (for example, spin coating), or by co-evaporating a dye and a quencher, or represented by the general formula (I). After vacuum-depositing the dye to be This can be done by applying an enture. When a binder is used, the weight of the binder is preferably 0.01 to 2 times the weight of the dye. Further, the dye of the general formula (I) can be used as a thin film by a so-called Random Muir projection method.

 In the invention, one or more recording layers are provided.

An antioxidant or an anti-fading agent may be present in the recording layer or in a layer adjacent thereto in order to prevent deterioration of the dye.

The thickness of the recording layer is usually 0.01 μm to 2 μm, preferably
It is in the range of 0.02 to 0.8 μm.

When a reflective layer such as a semiconductor laser or a He-Ne laser is provided, a reflective layer is provided on the substrate and then a recording layer is provided on the reflective layer by the method described above, or the recording layer is provided on the substrate. And then a reflective layer on top of this.

The reflection layer can be formed by the following method in addition to a vapor deposition method, a sputtering method, an ion plating method, and the like.

For example, a metal salt or a water-soluble resin (PVP, PVA, etc.)
It is formed by dissolving a metal complex salt, further applying a solution containing a reducing agent to a substrate, and drying by heating at 50 ° C to 150 ° C, preferably 60 ° C to 100 ° C.

The amount of the metal salt or metal complex relative to the resin is 0.
It is 1 to 10, preferably 0.5 to 1.5. At this time, the thickness of the recording layer is suitably from 0.01 to 0.1 μm for the metal particle reflection layer and from 0.01 to 1 μm for the light absorbing layer.

As the metal salt or metal complex salt, silver nitrate, potassium silver cyanide, potassium gold cyanide, silver ammine complex, silver cyanide complex, gold salt or gold cyanide complex can be used.
Examples of the reducing agent include formalin, oxalic acid, oxalate, a reducing agent, hypophosphite, sodium borohydride, dimethylamine borane, and the like. The reducing agent can be used in the range of 0.2 to 10 mol, preferably 0.5 to 4 mol, per 1 mol of the metal salt or metal complex.

In the optical recording medium of the present invention, information is recorded by irradiating the recording layer with a spot-like high energy beam such as a laser (for example, a semiconductor laser, a He-Ne laser, etc.) through the substrate or from the side opposite to the substrate. Then, the light absorbed by the recording layer is converted into heat, and pits (holes) are formed in the recording layer.

Reading of information is performed by irradiating a laser beam with a low output equal to or lower than the recording threshold energy, and detecting a change in the amount of reflected light or the amount of transmitted light in a pit portion and a portion where no pit is formed.

 Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 The dyes, quencher and, in some cases, the binder shown in Table 2 were dissolved in a mixed solvent of methanol-methylethylketone-dichloroethane-2,2,3,3, -tetrafluoropropanol in a suitable ratio, A 0.1 μm thick spinner was applied to a surface-hardened polycarbonate substrate with grooves (1.6 μ pitch, depth 750 mm) and dried. The weight ratio of the dye to the quencher was 3: 1, and when a binder was used, the weight of the binder was 1/5 of the dye.

 The evaluation conditions were as follows.

(Recording and reproduction) Laser: Semiconductor laser (GaAlAs) Laser wavelength: 780 nm Laser beam diameter: 1.6 μm Linear velocity: 5 m / s Recording power: 8 mW Recording frequency: 2.5 MHz Recording duty: 50% Reproduction power: 0.4 mW Play evaluation of degradation) reproduction power: 1.0 mW Views: 10 ⁵ times (during storage degradation assessment) storage temperature and humidity: 60 ° C. 90% RH storage time: shown in Table 2 for 30 days results.

Comparative compound A [Effects of the Invention] From the results shown in Table 2, the optical information recording medium of the present invention has C / N
It is apparent that the recording medium has high recording characteristics and high stability for long-term storage or long-term reading.

Claims (1)

(57) [Claims] 1. An optical information recording medium for recording, reproducing or erasing by a laser beam, wherein a compound represented by the following general formula (I) is carried on a substrate. Information recording medium. General formula (I) [Wherein, Z represents an atomic group necessary to form a carbocyclic or heterocyclic ring, Q represents an atomic group that completes a conjugated double bond chain, m represents 0 or 1, and M represents a hydrogen atom. L represents a metal atom, a metal complex ion, or an optionally substituted ammonium ion, or a quaternary phosphonium ion; L is an optionally substituted methine group, or a methine group formed by linking these with a conjugated double bond. Represents a trimethine chain or a pentamethine chain, E represents O, S or NR ⁴ ; R ¹ and R ⁴ represent an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl Group, optionally substituted aryl group, or optionally substituted heterocyclic group, optionally substituted amino group, optionally substituted hydrazino group, or optionally substituted di R ² represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted Represents a good heterocyclic group; R ³ is a hydrogen atom, a halogen atom,
Cyano group, nitro group, hydroxyl group, carboxyl group, optionally substituted alkyl group, optionally substituted aryl group, optionally substituted alkenyl group, optionally substituted alkoxy group, substituted An optionally substituted aryloxy group, an optionally substituted heterocyclic group, an optionally substituted alkoxycarbonyl group, an optionally substituted aryloxycarbonyl group, an optionally substituted amino group, An optionally substituted acyloxy group, an optionally substituted carbamoyl group, an optionally substituted sulfamoyl group, an optionally substituted alkylthio group, an optionally substituted arylthio group,
Represents an alkylsulfonyl group which may be substituted, an arylsulfonyl group which may be substituted or an alkynyl group which may be substituted; R ¹ and R ⁴ may be linked to each other to form a ring; ]