JPS63299992A - Optical data recording medium - Google Patents

Abstract

PURPOSE:To enhance C/N and stability, by supporting a specified compound on a substrate to produce a recording medium for recording, reproduction and erasure by a laser beam. CONSTITUTION:A coloring matter of formula (I) is supported on a substrate. In formula (I), (Z) is an atomic, group necessary for forming a hydrocarbon ring or hetrocyclic ring, Q is an atomic group for completing a conjugated double bond chain, m is 0 or 1, M is hydrogen, a metal or the like, L is substd. or unsubstd. methine or the like, E is O, S or the like, each of R<1> and R<4> is a substd. or unsubstd. alkyl, alkenyl or the like, R<2> is a substd. or unsubstd. alkyl, aryl or the like, and R<3> is hydrogen, a halogen or the like. The compound can be synthesized by bringing a dioxopyrazolopyridine compound into reaction with an appropriate methine source, trimethine source or pentamethine source compound in a solvent such as methanol.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat mode optical information recording medium that has an organic dye thin film and performs recording and reproduction by causing a state change with a high-density energy beam. .

[Conventional technology]

2. Description of the Related Art Conventionally, information recording media have been known in which information is recorded and reproduced by irradiating a rotating disc-shaped information recording medium with a laser beam. As the recording layer of such a recording medium, one using a low melting point metal or a low melting point metal and a dielectric material has been proposed.

However, these have drawbacks such as poor storage stability, low separation ability, low recording density, and high manufacturing cost. recent years,
Although it has been proposed and implemented to use a dye thin film whose physical properties can be changed by relatively long wavelength light in the recording layer, dyes that have absorption bands at long wavelengths generally have low stability against heat and light. Due to these problems, the current situation is that a recording layer that has stable and satisfactory recording characteristics over a long period of time has not been developed.

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 have a major practical drawback in that it is generally difficult to obtain highly pure dyes in high yields. Furthermore, among the dyes described in JP-A No. 60-71295, there is only one example of a compound that is estimated to have an absorption maximum in the wavelength range of a semiconductor laser (specifically, the absorption maximum wavelength and the example (has not been disclosed), as can be inferred from the fact that
In particular, it is difficult to synthesize dyes that have absorption maximum wavelengths in the near-infrared wavelength range of semiconductor lasers, and it is difficult to synthesize and isolate the amount of dyes necessary to actually evaluate the performance of optical information recording media. It was an extremely difficult task.

[Problem that the invention seeks to solve]

A first object of the present invention is to provide an optical information recording medium that provides a high C/N ratio.

A second object of the present invention is to provide an optical information recording medium with 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 problems]

An object of the present invention is to provide an optical information recording medium for recording, reproducing, and erasing information using a laser beam, the optical information recording medium being characterized in that a dye represented by the following general formula ([) is supported on a substrate. This was achieved using digital information recording media.

Z In the formula, Z represents an atomic group necessary to form a carbocycle or a heterocycle, Q represents an atomic group that completes a conjugated double bond chain, m represents O or 1, M is a hydrogen atom, Represents a metal atom, metal complex ion, optionally substituted ammonium ion, or quaternary phosphonium ion; L is an optionally substituted methine group, or trimethine formed by connecting these with a conjugated double bond chain or pentamethine chain; E represents 0, S or NR'; R1 and R4 are optionally substituted alkyl groups;
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 represents an optionally substituted diazenyl group; R1
is an optionally substituted alkyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group,
represents an optionally substituted alkynyl group or an optionally substituted heterocyclic group; R3 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 alkenyl group,
an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted heterocyclic group, an optionally substituted alkoxycarbonyl group, an optionally substituted aryloxy group carbonyl group, optionally substituted amino group, optionally substituted acyloxy group, optionally substituted carbamoyl group, optionally substituted sulfamoyl group, optionally substituted alkylthio group, substituted represents an optionally substituted arylthio group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, or an optionally substituted alkynyl group, and R1 and R4 are linked to each other to form a ring. You may.

Among the groups represented by M, preferred are a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, a nickel ion, a copper ion, an iron ion, a cobalt ion, a chromium ion, or a cationic complex containing NxCusPesC0%Cr, Ammonium ion optionally substituted with an alkyl or aryl group having up to 30 carbon atoms, an aralkyl group, or a quaternary phosphonium salt substituted with an alkyl, aryl, or aralkyl group having up to 40 carbon atoms, particularly preferred. is a hydrogen atom.

The ring completed by Q and Z is preferably a 4-, 5-, 6-, and 7-membered ring, and even if it forms a condensed ring with another 4, 5, 6, or 7-membered ring, it is preferable that it has a substituent. You may do so.

Preferred heteroatoms forming the heterocycle completed by Q and Z are B, N, and 0.5XSesTe.

Among the atomic groups represented by Z, examples of those forming a carbon ring include the following.

(CHzh (CHgh, -CFl=CI!-, -C
Examples of the atomic group represented by I.Cl-Cl.C1-2Z that form a heterocycle include the following.

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

Among the atomic groups represented by Z, particularly preferred are those that can complete a 5-shell or 6-membered heterocycle, and include B, N,
○, S% Contains at least one type of heteroatom selected from Se and Te.

As the linking group represented by , those represented by the general formula (al or hl) are particularly preferred.

General formula (a) area C) l-00 piece Cl1-C=CH-(CH=CHhi
-General formula (bl=CH-CHI=C-CII=CH-General formula (
C) General formula (e) General formula (f) General formula (g) General formula (h) In general formulas (a) to fh), Y represents a hydrogen atom or a monovalent group, and p and q are independently 0 or 1
represents. In this case, monovalent groups include lower alkyl groups such as methyl groups, aralkyl groups such as benzyl groups and p-methoxybenzyl groups, aryl groups such as phenyl groups, m-chlorophenyl groups, and naphthyl groups, and methoxy groups. Lower alkoxy groups, dimethylamino groups, diphenylamino groups, methylphenylamino groups, morpholino groups, imidazolidino groups, disubstituted amino groups such as ethoxycarbonylpiperazino groups, alkylcarbonyloxy groups such as acetoxy groups, alkylthio groups such as methylthio groups Preferred are halogen atoms such as a group, a cyano group, a nitro group, F, and CplBr.

Of the linking groups represented above, particularly preferred are those represented by general formula (a) or (b), particularly those in which Y represents a hydrogen atom and at least one of p or q represents O. .

Preferred substituents on R, Y, or Z in general formula (I) have 30 or less carbon atoms and are selected from the groups listed below, and these groups may further have a substituent. may have.

That is, an alkyl group, an aralkyl group, an aryl group, a hydroxy group, F, CIl, Br, ■, a cyano group, a nitro group, an alkoxy group, an aralkyloxy group, an aryoloxy group, an acyl group, an acyloxy group, an acylamino group. group, sulfonamide group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, carboxy group or carboxylad group, sulfonic acid group or sulfonato group, carbamoylamino group, sulfamoylamino group, They are an alkylsulfonyl group, an aralkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an aralkylsulfinyl group, an arylsulfinyl group, an alkylthio group, an aralkylthio group, or an arylsulfonyl group.

Among the groups represented by F, preferred are O or N-R'
and preferred as R4 are an optionally substituted alkyl group, an optionally substituted hydrazino group,
is an optionally substituted diazenyl group, and E is N-R
In the case of ', it is particularly preferable that R4 is linked to R1 to form a ring. Preferred rings formed by connecting R1 and R4 are imidazole, pyrazole, triazole, and tetrazole rings, and these rings may have a substituent or form a fused ring with another ring. You may do so.

Among the groups represented by R1 or R4, 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 a group having 5 or 6 ring members. 1 to 3 carbon atoms
0 optionally substituted heterocyclic group (the petro atom includes, for example, B, N, 0.5SSe, Te). The substituents that may be substituted on these bases may be neutral or ionic, and preferred are halogen atoms (e.g. F, C1, Br,
), cyano group, nitro group, carboxyl group, sulfonic acid group, hydroxyl group, alkoxy group (e.g. methoxy group, impropoxy group, hexadecyloxy group, etc.), aryloxy group (e.g. phenoxy group, 2,4-di-t) -Pentylphenoxy group, m-pentadecylphenoxy group, p-
Methoxyphenyl group, 3,5-dichlorophenyl group, 3
-sulfophenyl group, 3,5-disulfophenyl group, etc.) Alkyl group (methyl group, 4-sulfobutyl group, 2-methoxyethyl group, trifluoromethyl group, etc.) Aryl group (e.g. phenyl group, 4-sulfonato group) I4.3-
chlorophenyl group, 4-hexylphenyl group, 2-naphthyl group), substituted or unsubstituted amino group (e.g. amino group, methylamino group, phenylamino group, acetylamino group, methanesulfonylamino group, methylcarbamoylamino group) , trimethylammonio group, phenylthiocarbamoylamino group, benzenesulfonylamino group, etc.), carbamoyl group (e.g. carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, octadecylcarbamoyl group, diethylcarbamoyl group, pyrrolidinocarbonyl group, etc.), sulfamoyl group (For example, sulfamoyl group, dimethylsulfamoyl group, t-butylsulfamoyl group, phenylsulfamoyl group, pyrrolidinosulfonyl group, 3-(2,4-di-t-pentylphenoxy)butylsulfamoyl group) ), alkyl or ruthio groups (e.g. methylthio, phenylthio, benzylthio, off, tadecylthio),
Alkylsulfonyl group (e.g. methanesulfonyl group, 2
-ethoxyethylsulfonyl group, etc.), irisulfonyl group (e.g. benzenesulfonyl group, dodecylbenzenesulfonyl group, 2-(2-methoxyethoxy)-5
= (4-hydroxyphenylazo)-benzenesulfonyl group, etc.).

Among the groups represented by R1 or R4, particularly preferred are an optionally substituted alkyl group having 1 to 20 carbon atoms (which may be substituted with the above-mentioned preferred substituents); an optionally substituted phenyl group (which may be substituted with the above-mentioned preferred substituents), a 5- or 6-membered heterocyclic group having 1 to 20 carbon atoms (e.g. 2-pyridyl, 4-pyridyl, 2- Benzthiazolyl, 2-(I-methylimidazolyl), 4.6
-diethylamino-2-triazinyl, etc.).

Among the groups represented by R2, 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 an optionally substituted phenyl group having 1 to 30 carbon atoms. A heterocyclic group that may be substituted (the number of ring members is 5 or 6, the heterobivalent atom is B,
N, OlS, Se.

(selected from Te). Preferred groups for substituting these bases include the groups mentioned above as preferred substituents on R1.

Among the groups represented by R2, particularly preferred are optionally substituted alkyl groups having 1 to 20 carbon atoms, such as methyl group, 4-sulfobutyl group, 2-methoxyethyl group, trifluoromethyl group, benzoyloxymethyl group. ), optionally substituted phenyl having 6 to 20 carbon atoms! (Example, tL; I' phenyl group, 4-sulfophenyl group, 3-chlorophenyl i, 3-1-lifluoromethylphenyl group, 2-methanesulfonyJ ray 4
-nitrophenyl group, 2-nitro-4-dimethylsulfamoylphenyl group, 4-methanesulfonylphenyl group, etc.), having 1 to 20 carbon atoms and 5 or 6 ring members
heterocyclic groups (e.g. 2-pyridyl, 4-pyridyl, 3-
Pyridyl, 2-benzthiazolyl, 2-(I-methyl-
imidazolyl), 4,6-dibutylamino-2-triazinyl, etc.).

Among the groups represented by R3, preferred 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.1. An optionally substituted alkoxycarbonyl group having 2 to 30 carbon atoms, an optionally substituted phenoxycarbonyl group having 7 to 30 carbon atoms, a carboxyl group, or a hydroxyl group.

Preferred groups for substituting these bases are R1
Preferred substituents on the above include the groups mentioned above.

Among the groups represented by R3, particularly preferred are optionally substituted alkyl groups having 1 to 20 carbon atoms (
(e.g., methyl group, t-butyl group, trifluoromethyl group, etc.), optionally substituted phenyl group having 6 to 20 carbon atoms (e.g., phenyl group, 4-methoxyphenyl group, 3.5-dichlorophenyl group, etc.) , carboxyl groups and salts thereof, optionally substituted carbamoyl groups having 1 to 20 carbon atoms (e.g. carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, pyrrolidimecarbonyl group, 2-ethylhexylcarbamoyl group, etc.) , an alkoxycarbonyl group having 2 to 20 carbon atoms (for example, an ethoxycarbonyl group, a hexadecyloxycarbonyl group, a 1-butoxycarbonyl group, a cholesteryloxycarbonyl group), a carboxyl group or a salt thereof, or a hydroxyl group.

Specific examples of oxonol dyes used in the present invention are shown below, but the present invention is not limited to these. Table 1 shows that among the compounds represented by general formula (I), E
represents O, and Compounds 1 to 50 are shown as specific examples of compounds in which the ring completed by Q and Z is represented by the following general formula (A).

[In formula 2. , R', R'', R3 have the same meaning as in the general formula (+)] B QCO ■ ■ ■
Roth
Compounds of the present invention include a dioxopyrazolopyridine compound represented by the following general formula (n) in a suitable solvent such as methanol, and a suitable methine source, trimethine source, or pentamethine source compound (for example, ethyl orthoformate, 1.5 -diphenyl-1,5-diaza-1°3-pentadiene, 1,5.5-1-dialkoxy-1,3-pentadiene, 1,7-diphenyl-
1,7-diaza-1,3,5-hebutatriene, etc.). On this occasion,
The reaction may be accelerated by adding a basic substance such as triethylamine or an acid anhydride such as acetic anhydride. More specifically, Special Publication No. 39-22069, No. 43-3504
No. 52-38056, No. 54-38129, No. 55-10059, JP-A-49-99620, No. 5
No. 9-16834 or U.S. Patent No. 4.181,2
It can be synthesized using the method described in, for example, No. 25.

General formula (n) [In the formula, R1, R1, and R3 represent the same groups as defined in the general formula (I). ] -i The compound represented by formula (II) is represented by the following general formula (II
It can be synthesized by heating the compound represented by I) and the compound represented by general formula (IV) under acidic conditions.

General formula (III) ■ ll [In the formula, R'SR'' represents a group having the same meaning as R' and R2 in the general formula (I)] General formula (IV) [In the formula, R3 represents R3 in the general formula (I) and R4 represents an alkyl group or an aryl group.] The compound represented by the general formula (II) is also disclosed in JP-A No. 52
-112626, the dioxopyrazolopyridine compound (general formula (■)) is alkylated, arylated,
Alternatively, it can also be synthesized by acylation.

General formula (■): In the formula, RISR3 represents a group having the same meaning as R1 and R3 in general formula (I). It goes without saying that the functional group of the compound represented by general formula (I) or general formula (n) can be converted into another functional group by a known method.

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

Synthesis example 1. Synthesis of Compound 2 1-phenyl-3-anilino-2-pyrazolin-5-one (25 g), ethyl acetoacetate (I8 g), and acetic acid (I50 mj) were heated under reflux for 6 hours. The reaction solution was diluted with water, 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.

Melting point: 145-147°C This 2,7-diphenyl-4-methylpyrazolo(3,4
-b) Pyridine-3,6-dione (3,17 g) with methanol (50 ml) and triethylamine (2,8 mJ)
1.7-diphenyl-1,7-
Diaza-1,3,5-heptatriene hydrochloride (2,85
g) was added and dissolved, and then acetic anhydride (I, 88 mA'
) and 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-pentagenylidene)-2,
7=diphenyl-4-methylpyrazolo(3,4-b)
Pyridine-3,6-dione (I, 9 g) was obtained. This crystal (I, 5 g) was added to N,N-dimethylformamide (60 g).
m12), 2,7-diphenyl-4-methylpyrazolo(3,4-b)pyridine-3,6-dione (0,95g
), and triethylamine (0.42g) were added, and 5
Stirred at 0°C for 2 hours. After filtering off a trace amount of insoluble matter, 10 times the volume of ethyl acetate was added to the mixture while stirring to cause crystallization. After dissolving the obtained crystals in a small amount of N,N-dimethylformamide again, 10 times the volume of ethyl acetate was added to crystallize.
The residue was collected by filtration and dried to obtain Compound 2 (I, 3 g). Golden crystals, melting point 300°C or higher, Awamx 7 9 2 nm Synthesis Example 2 Synthesis of Compound 1 3-Methylamino-1-phenyl-2-pyrazoline-5
-one (I, 9g), ethyl acetoacetate (I, 4g),
and acetic acid (8 mA) were heated under reflux for 6 hours. The reaction solution was diluted with water, the resulting crystals were collected by filtration, washed with isopropyl alcohol, and 1.8 g of 4.7-dimethyl-2-phenylpyrazolo[3,4-b)pyridine-3,6-dione (melting point 179-181"C) was obtained. Methanol (20+++j') and triethylamine (0,
7m! 1,7-diphenyl-1,7-diaza-1,3,5-hebutatriene hydrochloride (0.7 g) was added and dissolved in the solution prepared by adding the
n+1) was added and 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)
-4,7-dimethyl-2-phenylpyrazolo[3,4-
b) BiIJ syn-3,6-dione (0.2 g) was obtained. This crystal (0.15 g) was mixed with N,N-dimethylformamide (5 mff) and 4,7-dimethyl-2-phenylpyrazolo(3,4-b)pyridine-3,6-dione (0,
08g) was added thereto, and the mixture was stirred at 50°C for 2 hours.

The reaction solution was filtered, diluted with water, crystallized, collected by filtration, washed with water, and dried to obtain Compound 1 (0.2 g).

Melting point 300℃ or higher λlI-X760nm Synthesis Example 3
Synthesis of compound 4 3-(3-chlorophenylamino)-1-phenyl-2
Ethyl acetoacetate (2.8 g) and acetic acid (40 mf) were added to -pyrazolin-5-one (5.7 g) and heated under reflux for 6 hours. The formed crystals were collected by filtration, washed with isopropyl alcohol, and 2 g of 7. -(3-chlorophenyl)
-4-Methyl-2-phenylpyrazolo(3,4-b)pyridine-3,6-dione was obtained (melting point 27B-282℃
). 1,7-diphenyl-1,7-diaza-1,3
,55-hebutatriene hydrochloride (I, 13 g) was added and dissolved, and then acetic anhydride (0.75 ml) was added and 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]-7-(3-chlorophenyl)-4-methyl-2-phenylpyrazolo(3,4
-b) Pyridine-3,6-dione was obtained. This crystal (0
, 5g) to N,N-dimethylformamide (30m6)
, 7 (3-chlorophenyl)-4-methyl-2
-phenylpyrazolo(3,4-b)pyridine-3,6
-dione (0,32 g), and triethylamine (0
, 13-1) and stirred at 50°C for 2 hours.

After filtering the reaction solution, 10 times the volume of ethyl acetate was added to the solution while stirring for crystallization. The obtained crystals are again treated with a small amount of N, N
- After dissolving in dimethylformamide, add 10 times the amount of ethyl acetate to crystallize, collect by filtration, wash with ethyl acetate,
After drying, compound 4 (0.4 g) was obtained.

Melting point 300℃ or higher Amax 762nm Synthesis Example 4
Synthesis of compound 3 3-(4-methoxyphenylamino)-1-phenyl-
Ethyl acetoacetate (8.5 g) and acetic acid (75 mA) were added to 2-pyrazolin-5-one (I4 g), and the mixture was heated under reflux for 6 hours. Pour the reaction solution into water 1501Tlj2,
The resulting solid was mixed with methanol (500mj2) and acetone (
8.4 by heating and dissolving in a mixture of I50mj and then cooling.
g of 7-(4-methoxyphenyl)-4-methyl-2
-phenylpyrazolo(3,4-b)pyridine-3,6
-dione (melting point 189-190°C) was obtained. This crystal (
3.47 g), methanol (40 mA') and triethylamine (2.8 mj).
-Diphenyl-1,7-diaza-1,3°5-hepcutriene hydrochloride (2.85 g) was added and dissolved, and then acetic anhydride (I, 88 ml) was added and stirred at room temperature for 1 hour.

The resulting precipitate was collected by filtration, washed with methanol, and dried.
-(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. This crystal (3,8
g) to N,N-dimethylformamide (40 mj, 7
-(4-Methoxyphenyl)-4-methyl-1-phenyl-2-pyrazolin-5-one (2.4 g) and 0.98 m6 of triethylamine were added and stirred at 50°C for 2 hours. After filtering the reaction solution, 10 times the volume of ethyl acetate was added while stirring to cause crystallization.

The obtained crystals were recrystallized from acetonitrile to obtain compound 3.
(I, 0g) was obtained. Melting point 260℃ (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-4
Compound 5 was prepared in the same manner except that -methoxyphenylamino)-1-phenyl-2-pyrazolin-5-one was used.
I got it.

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

(Melting point 220-223°C) Synthesis Example 7 Compounds 12-16.27.30.33-
35.44-60 were synthesized. The melting points of these compounds were all 300°C or higher.

The oxonol dyes used in the optical recording medium of the invention may be used alone, in combination of two or more, or in combination with dyes other than the oxonol dye of the invention. It is also effective to use various antioxidants and singlet oxygen quenchers in combination to improve reading durability. Moreover, various resins may be used in combination.

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

Various quenchers can be used in the optical recording medium of the present invention. As such an encher, a transition metal complex that reduces regeneration deterioration and has good compatibility with the dye is preferable. In this case, preferable central metals are Nis CoCu, Pd.
s Pt etc.

Examples of novel enchers include those represented by the following general formula (n) or (III).

(In the formula, (Cat, ) and (CaLz) represent cations necessary to neutralize the complex, and Ml and M
, indicates nickel, copper, cobalt, palladium or platinum. In the compound represented by the general formula Cm) or (III), in which n represents 1 or 2, (Cat+
Among the cations represented by 3 or (Cat, ), inorganic ions include alkali metals (for example, Li,
(Na, K, etc.), alkaline earth metals (Mg, Ca,
(Ba, etc.) or NH.

Examples of the organic cation include quaternary ammonium ions and quaternary phosphonium ions.

Among the above cations (Cat, ) and (Catz), the following general formulas (IV-a) and (rV-b) are preferred.
, (rV-c), (IV-d) or (IV-e).

In the formula, R eyes, R eyes, R13, RI 4, R''% R1b
sR1? , R"% R", R26, R1+ and R22
each represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 6 to 14 carbon atoms, and Zl and Zl are bonded to the nitrogen or phosphorus atom in each formula. represents a group of nonmetallic atoms that form a 5- or 6-membered ring.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-butyl group, 1so-amyl group, n-dodecyl group, and n-octadecyl group. Carbon number 6 to 14
Examples of the aryl group include phenyl group, tolyl group, and α-naphthyl group.

These alkyl groups 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.),
Aryl groups having 6 to 14 carbon atoms (for example, phenyl group, tolyl group, α-naphthyl group, etc.), acyloxy groups having 2 to 20 carbon atoms (for example, acetoxy group, benzoyloxy group, p-methoxybenzoyloxy group, etc.), Alkoxy group having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.)
, an aralkyl group (such as a benzyl group, a phenethyl group or anisyl group), an alkoxycarbonyl group (such as a methoxycarbonyl group, an ethoxycarbonyl group, a n-butoxy group) carbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, triloxycarbonyl group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), acylamino group (e.g., acetylamino group, benzoylamino group, etc.) , carbamoyl group (e.g., N-ethylcarbamoyl group, N-phenylcarbamoyl group, etc.), alkylsulfonylamino group (e.g., methylsulfonylamine group, phenylsulfonylamino group, etc.), sulfamoyl group (e.g., N-ethylsulfamoyl group, etc.) group, N-
phenylsulfamoyl group, etc.), sulfonyl group (eg, mesyl group, tosyl group, etc.).

Further, Zl and Zl represent a group of nonmetallic atoms necessary to form a 5-membered ring or a 6-membered ring as described above. These 5@ rings or 6-membered rings include pyridine ring, imidazole ring, pyrrole ring, 2-pyrroline ring, pyrrolidine ring,
Examples include a piperidine ring, a pyrazole ring, a pyrazoline ring, and an imidacilline ring. General formula (IV-b)
Examples of the cation represented by the formula include dodecylpyridinium group, hexadecylpyridinium group, and dodecylimidazolium group.

Examples of the cation represented by general formula (IV-c) include N-ethyl-N-hexadecylpiperidinium group and N-ethyl-N-dodecylpyrazolidinium group.

The above general formulas (TV-a), (TV-b), (IV-C
), (rV-d) and (IV-e), those particularly preferably used in the present invention are:
In terms of availability of manufacturing raw materials and manufacturing costs, (IV-a
), (IV-b), NY-d) and (rV-e).

The types of the cations (Cat+) and (Catz) affect the solubility of the compound represented by the general formula (n) or (III) in an organic solvent.

Generally, when the R substituent bonded to a quaternary heteroatom is an alkyl group, the longer the chain length, the higher the solubility;
This tendency is particularly remarkable in the case of tetraalkyl-substituted ammonium or phosphonium; in the case of ammonium cations, cations with a total number of carbon atoms of 17 or more, and in the case of phosphonium cations, cations with a total number of carbon atoms of 4 or more have high solubility. give.

In the compound represented by the general formula (n) or (I[I), the preferable order of Ml or M2 is nickel, cobalt, copper, palladium, and platinum.

The metal complex of general formula (n) or (I[I) has a three-dimensional structure with four planar coordinations. In the compound of general formula (III), it is not unambiguously determined whether the thioketone group is symmetrical or asymmetrical with respect to the central metal, but it is expressed as general formula [■] for convenience in this specification.

The compound represented by the general formula (II) or Cl11) can be synthesized as follows.

The compound of general formula (n) (n-2) is prepared by first converting disodium 1,3-dithiol-2-thione-4,5-dithiolate obtained by reacting carbon disulfide and sodium into a zinc complex, and then converting it into a zinc complex. React benzoyl to form bisbenzoylthio compound. After decomposing this with alkali,
Obtained by reacting metal salts.

Further, the compound of general formula (II) (n=1) can be obtained by oxidizing the complex (n=2) obtained above with a suitable oxidizing agent.

The compound of general formula (I[I) (n=2) is prepared by first reacting dindiram-1,3-dithiol-2-thione-4°5-dithiolate, which is obtained by reacting carbon disulfide with sodium, at about 130% Heating to ℃ disodium 1.2
-dithiol-3-thione-4°5-dithiolate is isomerized. This is made into a zinc complex, and this is reacted with benzoyl chloride to form a bisbenzoylthio compound. It is obtained by decomposing this with an alkali and then reacting it with a metal salt.

Further, general formula (III) (n=1) can be obtained by oxidizing the complex (n,=2) obtained above with a suitable oxidizing agent.

1,3-dithiol-2-thione-4,5, which is an intermediate for obtaining the compound of general formula (II) or (II[]
The -dithiolate anion can be obtained not only by the reduction method using Na as described above but also by electrochemical reduction.

Preferred examples of the compounds represented by the general formula (II) are as follows.

Country …
#… general formula (
A synthesis example of the compound represented by II) is shown below.

Synthesis Example n-1 <Synthesis of Exemplary Compound 1fi (II-4)> (
I-1) Bis(tetraethylammonium)-'bis(
Synthesis of I,3-dithiol-2-thione-4゜5-dithiolato)zinc complex.

All reaction operations were performed under an argon atmosphere.

Cut 23g of sodium into small pieces and add 180ml of carbon disulfide.
After being dispersed in the solution, 200 mJ of dimethylformamide was slowly added dropwise to the solution while stirring. Be careful not to generate too much heat at this time. After dropping dimethylformamide, the mixture was carefully heated and refluxed for 24 hours. After the reaction was completed, unreacted sodium was filtered off. Next, 50+111 ethanol was added to the filtrate, and the mixture was stirred at room temperature for 2 hours. Carbon disulfide was distilled off from this solution under reduced pressure at room temperature. Then, 300 ml of water was slowly added dropwise, and the resulting solution was filtered.

Next, add 20 g of zinc chloride to 500 g of methanol in advance.
Prepare a solution by dissolving 53 g of tetraethylammonium bromide in 250 mJ of water and adding 500 m6 of concentrated ammonium water to it. Add this to the above reaction solution and stir for 5 minutes (at room temperature). When added, a red precipitate immediately separates out. This was filtered and air-dried to obtain a zinc complex.

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

22g of the zinc complex obtained in (I-1) was added to 500mf of acetone.
Dissolve and filter. While stirring the filtrate, add 150 ml of benzoyl chloride. A yellow precipitate immediately separates out. After filtration, washing with water, and air drying, 16 g of the title compound was obtained.

(I-3) Synthesis of Exemplified Compound (II-4) 9.2 g of the bis(benzoylthio) compound obtained in (I-2) was added to 5 g of methanol
Dissolve in 01I11. To this was added 6.3 g of a 28% methanol solution of sodium methoxide, and the mixture was stirred for 10 minutes. A solution of 2.4 g of nickel chloride (hexahydrate) dissolved in 50+t' of methanol was added to this solution, and the mixture was heated to room temperature for 30 minutes.
Stir for 0 minutes. Add 8.5 g of tetrabutylphosphonium bromide to this solution and add 10011 I of methanol! When a solution dissolved in is added, a black precipitate immediately precipitates out.

Stir for an additional 20 minutes, filter, wash with acetone, air dry, and recrystallize from acetone-isopropyl alcohol to yield the title compound. Yield: 3.8 g Synthesis Example ■-2 Synthesis of Exemplified Compound (II-2) 1 g of the nickel complex obtained in (I-3) was dissolved in 60 ml of acetone, 30 ml of acetic acid was added thereto, and the mixture was stirred for 3 hours to dissolve the solvent. When it was distilled off, black crystals were precipitated. This was recrystallized from acetone-methanol to obtain the target exemplary compound (II-2).

Yield 110.4 g, m, p, 185°C λ-,:
1125 nm, εlI□: 2.51 x 10'
(in CH□C12) Also, a known quencher is described in Japanese Patent Application Laid-open No. 178295/1983. The following compounds may be mentioned.

(i) Bisdithio-α-diketone system R1 and R4 represent an alkyl group or an alkyl group, and M
represents a divalent transition metal atom.

(ii) Bisphenyldithiol system R5, R6 represent an alkyl group or a halogen atom, and M represents a divalent transition metal atom.

(iii) Acetylacetonate chelate system (iv)
Dithiocarbamate chelate system (v) Bisphenylthiol system (vi) Thiocatechol chelate system (vi) Salicylaldehyde oxime system (vii) Thiobisferrate chelate system (ix) Phosphonous acid chelate system (x) Benzoate system (xi) Hindered amine type (xii) transition metal salts In addition, aminium type or diimonium type compounds represented by the following formula can be mentioned, and specific examples include IRQ-002, IRG-003, and IRG-0 manufactured by Nippon Kayaku Co., Ltd.
22 and IRG-033.

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

The quencher is generally 0.05% per mole of the dye.
~12 mol, preferably 0.1-1.2 mol is used.

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

Any known substrate can be used as the substrate. Typical examples include glass or plastic; plastics include acrylic, polycarbonate,
Polysulfone, polyimide, amorphous polyolefin, epoxy resin, polyester, etc. are used. Its shape can be various, such as a disk, card, sheet, or roll film.

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

The formation of the recording layer in the present invention can be carried out, for example, by formula (I)
The dye and quencher represented by
2.2,3.3-Tetrafluoropropanol, etc., dichloromethane, dichloroethane, acetone, etc.), and optionally a suitable binder (e.g. PVA, PVP, polyvinyl butyral, etc.).
This can be done by adding (polycarbonate, nitrocellulose, polyvinyl formal, methyl vinyl ether, chlorinated paraffin, maleic anhydride copolymer, styrene-butadiene copolymer, xylene resin) and applying this solution (for example, by spin cord). Alternatively, the dye and the quencher can be co-deposited, or the dye represented by the general formula (I) can be vacuum-deposited and then a quencher can be applied. When a binder is used, the weight of the binder is preferably 0.01 to 2 times the weight of the dye. The dye of general formula (I) can also be used in the form of a thin film by the so-called Langmuir-Prodgett method.

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

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

The thickness of the recording layer is usually in the range of 0.01 μm to 2 μm, preferably 0.02 to 0.8 μm. In the case of reflective readout, the wavelength is particularly preferably an odd multiple of 2 of the laser wavelength used for readout.

When a reflective layer is provided for a semiconductor laser or a He-Ne laser, the reflective layer is provided on the substrate and then a recording layer is provided on the reflective layer using the method described above, or the recording layer is placed on the substrate. There is a method of providing a reflective layer and then providing a reflective layer thereon.

The reflective layer can be made by the following methods, in addition to vapor deposition, sputtering, and ion blating.

For example, a solution containing a metal salt or a metal complex salt dissolved in a water-soluble resin (PVP, PVA, etc.) and a reducing agent added thereto is applied to the substrate at 50°C to 150°C, preferably at 60°C.
It is formed by heating and drying at ~100°C.

The weight ratio of the metal salt or metal complex salt to the resin is 0.
1 to 10, preferably 0.5 to 1.5. In this case, the appropriate thickness of the recording layer is 0.01 to 0.1 μm for the metal particle anti-fouling layer and 0.01 to 111 m for the light absorption 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. As a reducing agent, formalin, tartaric acid, tartrate, reducing agent,
Hypophosphite, sodium borohydride, dimethylamine borane, etc. can be used. The reducing agent can be used in an amount of 0.2 to 10 mol, preferably 0.5 to 4 mol, per mol of metal salt or metal complex salt.

In the optical recording medium of the present invention, information is recorded by irradiating the recording layer with a spot-like high-energy beam of a laser (e.g., semiconductor laser, He-Ne laser, etc.) through the substrate or from the opposite side of the substrate. The light absorbed by the recording layer is converted into heat and focused on the recording layer (
hole) is formed.

Information is read out by irradiating a laser beam with a low output power below the recording darkness value and detecting changes in the amount of reflected light or transmitted light in the pit portion and the portion where no pits are formed.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 The dye shown in Table 1, Quencher 1, and binder if present are dissolved in a mixed solvent of methanol-methyl ethyl ketone-dichloroethane in an appropriate ratio, and a surface-hardened grouped (I, 6tt pitch, depth 750 It was applied to a polycarbonate 1-5 plate using a spinner to a thickness of 0.1 μm 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 175% of the weight of the dye.

The evaluation conditions were as follows.

(Recording and reproduction) Laser: Semiconductor laser (GaAlAs) Laser wavelength near 80 nm Laser beam diameter = 1.6 μm Linear velocity: 5 m, /s Recording power 28 m- Recording frequency: 2.5 MHz Recording duty = 50% Reproduction Power: 0.4mW (Evaluation of playback deterioration) Playback power: 1. OmW Number of plays: 105 times (evaluation of deterioration during storage) Storage temperature and humidity: 60℃ 90%RH storage time
: The results for 30 days are shown in Table 1.

Comparative Compound A [Effect of the Invention] From the results in Table 1, the optical information recording medium of the present invention has a C/N
It is clear that the material has sufficient recording properties with a high degree of stability, and has high stability for long-term storage or long-term reading.

Procedural Amendment 62, 7.24 Director General of the Patent Office Kunio Ogawa 1, Indication of Case Patent Application No. 135750 of 1985
No. 2, Title of the invention Optical information recording medium 3, Relationship with the case of the person making the amendment Applicant name (520) Fuji Photo Film Co., Ltd. 4, Agent 5, Date of amendment order Author: 00 Ibid., same page No. 9 Line, 3rd line from the bottom and the subsidiary company (
I) Correct "(n)" on lines 7, 8, and 14 of No. 46 due east of the specification to r (Vl) J, respectively.

(2) "[■]" in lines 7, 9, and 13 of the same book are corrected to "[■]" respectively.

(3) " in the same book, page 55, lines 10, 11, 13, and 14.
Correct “■” to “■”.

(4) "■" in lines 1, 2, and 3 of page 55 of the same book are corrected to "■" respectively.

(5) Ibid., page 55, 3.7.11.12.15.
The “■” on the 16th line is corrected to “■”.

(6) Correct “■” in the third line from the bottom of the same page of the same book to rVIJ.

(7) “■” in the third line from the bottom of the same page of the same book has been corrected to “■”.

(8) "■" in lines 8, 12, 13, 16, and 17 of page 55 of the same book are corrected to "■" respectively.

(9) “■” in line 8, 12, 17, 19 of the same book
” are respectively corrected as rVIJ.

00 The "■" in page 53, line 6 of the same book and in Suesha are corrected to rVIJ.

and r　Vl　−(4)　j.

Q21 Correct “■” on page 54, line 5 of the same book to rVTJ.

α■ “II-(I)”, “II-(I)” on page 55 of the same book
(2)", "II - (3)", and "II - (4)" respectively r VI - (I) J, r VI - (2)
J, r VI - (3) j, r VI - (4)
Correct with J.

04) Correct "■" in the 1st and 3rd lines of page 55 of the same book with rVIJ.

0ω Correct "■" in the 7th line from the bottom of page 57 of the same book to rVIJ.

00 "■" on page 55, line 7.12 of the same book is corrected to rVIJ.

α″D “Table 1” in the second line of page 66 of the same book is amended to “Table 2”.

00 “Table 1” in the same book, page 67, line 7, line 4 from the bottom
are respectively corrected as "Table 2".

α mark “■-2” in the quencher column of Table 2 on page 68 of the circular
” and “n-4” respectively
No. 2, Title of the invention Optical information recording medium 3, Relationship with the case of the person making the amendment Applicant name (520) Fuji Photo Film Co., Ltd. 4, Agent 5, Date of amendment order Initiator (I) Specification No. Column for R2 in Compound 42 on page 27 (2) Column for R2 in Compound 48 on page 27 of the same book (3) "Dichloroethane" on page 66, line 4 of the same book
Insert "r-2,2,3,3-tetrafluoropropatool" after.

(4) Set "Q, 3 m W continuous playback" in Table 2 on page 68 of the same book to r 1. "Om W continuous playback" is corrected.

Claims (1)

[Claims] An optical information recording medium for recording, reproducing, or erasing using a laser beam, which has the following general formula (
An optical information recording medium characterized in that a compound represented by I) is supported on a substrate. General Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. , m represents 0 or 1; M is a hydrogen atom,
Represents a metal atom, metal complex ion, optionally substituted ammonium ion, or quaternary phosphonium ion; L is an optionally substituted methine group, or is formed by connecting these with a conjugated double bond Represents trimethine chain or pentamethine chain, E is O, S or NR^
4; R^1 and R^4 are an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, or a substituted represents an optionally substituted heterocyclic group, an optionally substituted amino group, an optionally substituted hydrazino group, or an optionally substituted diazenyl group; R^2 is an optionally substituted alkyl group; represents an optionally substituted aryl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted 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, optionally substituted aryloxy group, substituted optionally substituted heterocyclic group, optionally substituted alkoxycarbonyl group, optionally substituted aryloxycarbonyl group, optionally substituted amino group, optionally substituted acyloxy group, optionally substituted carbamoyl group, optionally substituted sulfamoyl group, optionally substituted alkylthio group, optionally substituted arylthio group, optionally substituted alkylsulfonyl group, optionally substituted represents an arylsulfonyl group or an optionally substituted alkynyl group;
R^1 and R^4 may be connected to each other to form a ring. ]