JP2858071B2 - Method for producing metal complex, metal complex, metal complex quencher, and optical recording medium - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a metal complex,
The present invention relates to an optical recording medium such as an optical recording disk having a recording layer of a metal complex, a metal complex quencher and a dye film.

[0002]

2. Description of the Related Art In recent years, various types of optical recording disks of the write-once type and the rewritable type have been receiving attention as large-capacity information carrying media. Some of such optical recording disks use a dye film containing a dye as a main component as a recording layer.
Conventionally, a so-called air sandwich structure in which an air layer is provided on a recording layer composed of a dye film, which has been widely used, or a dye film that can be reproduced in compliance with the Compact Disc (CD) standard A structure having a structure in which a reflective layer is provided in close contact with a recording layer made of Nitrogen has been proposed (Nikkei Electronics, January 23, 1989, No. 4).
65, P107, Kinki Chemical Association Functional Dye Subcommittee, March 3, 1989, Osaka Science and Technology Center, PROC
EEDINGS SPIE-THE INTERNATIONAL SOCIETY FOR OPTICAL
ENGINEERINGVOL.1078 PP80-87, "OPTICAL DATA STORAGE
TOPICAL MEETING "17-19, JANUARY 1989 LOS ANGELES
etc).

[0003] Dyes used in such a recording layer include:
In view of heat resistance, water resistance and the like, indolenine-based cyanine dyes are preferably used (JP-A-59-24692).
No.).

However, such indolenine-based cyanine dyes have a drawback that reproduction deterioration due to repeated irradiation of reproduction light and light deterioration under storage in a bright room are apt to occur. For this reason, it has been proposed to use a mixture of a dye and a metal complex quencher, which has been put into practical use (Japanese Patent Application Laid-Open No. 59-5799).
No. 5, etc.). Among such metal complexes, particularly, bis (phenylenedithiol) -based Ni complexes and the like exhibit extremely excellent effects in terms of preventing reproduction deterioration and light deterioration of cyanine dyes.

However, the solubility is insufficient, and the alcohol system such as methanol has a solubility of 1% or less, and it is impossible to coat the recording layer using these solvents. Further, the absorption wavelength is 700 to 1000 nm, which affects the absorption of the dye, and as a result, the reflectance is reduced and the reproduction output is low.

It is also conceivable to newly design a quencher with improved solubility, but it is difficult to obtain a raw material by a usual synthesis method, or it is disadvantageous in terms of cost because it is expensive. At present, it is difficult to obtain the desired product.

[0007]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a metal complex which exhibits good solubility and facilitates preparation of a dye coating solution when used as a quencher. An object of the present invention is to provide a method for producing a metal complex, a metal complex obtained by the method, and a metal complex quencher. Another object of the present invention is to provide an optical recording medium in which the recording layer can be easily formed, the reflectance of the recording layer does not decrease, and the reproduction deterioration and the light deterioration are small.

[0008]

This and other objects are achieved by the present invention which is defined below as (1) to (11). (1) A method for producing a metal complex obtained by reacting a compound represented by the following formula 5 with a compound represented by the following formula 6 in a non-aqueous solvent to obtain a metal complex represented by the following formula 7.

[0009]

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[0010]

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[0011]

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Wherein R ₁ and R ₂ each represent a hydrogen atom or a monovalent substituent, which may be the same or different. R ₁ and R ₂ may combine with each other to form a ring. R ₃ represents a monovalent substituent. t represents an integer of 0 to 4. When t is 2 or more, R ₃
It may be the same or different, adjacent R ₃ each other may form a ring. X and Y are each S
Or, it represents Se, and X and Y may be the same or different. M represents a metal atom. In Chemical Formula 6, R ₄ and R ₅ each represent a hydrocarbon group or a carbamoyl group, and R ₄ and R ₅ may be the same or different. In the chemical formula 7, R ₁ , R ₂ ,
R ₃ , t, X, Y and M have the same meanings as in Chemical formula 5, respectively. R ₄ and R ₅ have the same meanings as in Chemical Formula 6, respectively. v and w each represent an integer of 0 to 5, but are not both 0, and t + v + w is 5 or less. (2) The method for producing a metal complex according to the above (1), wherein R ₄ and R ₅ of the compound represented by the above formula (6) are cyanoalkyl groups. (3) The method for producing a metal complex according to the above (1) or (2), wherein the metal complex represented by the above formula (7) has higher solubility than the compound represented by the above formula (5). (4) The method for producing a metal complex according to any one of (1) to (3), wherein the reaction is performed at a temperature of 10 to 200 ° C. (5) The method for producing a metal complex according to any one of the above (1) to (4), wherein the metal complex represented by the above formula (7) is used as a quencher. (6) A metal complex represented by the following formula (8):

[0013]

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[In the formula, R ₁ and R ₂ each represent a hydrogen atom or a monovalent substituent, and these may be the same or different. R ₁ and R ₂ may combine with each other to form a ring. R ₆ represents a cyanoalkyl group. X and Y each represent S or Se;
X and Y may be the same or different. M
Represents a metal atom. (7) A metal complex quencher which is the metal complex of the above (6). (8) An optical recording medium having a recording layer containing the metal complex quencher of (7) and a dye on a substrate. (9) The optical recording medium according to the above (8), wherein the dye is a cyanine dye. (10) The optical recording medium according to the above (9), wherein the cyanine dye has an indolenine ring. (11) The optical recording medium according to any one of (8) to (10), wherein the dye has an absorption maximum of 600 to 900 nm.

[0015]

[Specific Configuration] Hereinafter, a specific configuration of the present invention will be described in detail.

In the present invention, the metal complex represented by Chemical Formula 7 (also referred to as “Compound of Chemical Formula 7”) is represented by the compound represented by Chemical Formula 5 (also referred to as “Compound of Chemical Formula 5”) and Chemical Formula 6. It is obtained by reacting a compound (also referred to as “compound of formula 6”) in a non-aqueous solvent. The compound of Chemical formula 7 is a metal complex quencher used as a quencher.

The compound of formula 5 is disclosed in Japanese Patent Application No.
As described in JP-A-269449 and Japanese Patent Application No. 5-60890, it functions as a singlet oxygen quencher for the dye. In the present invention, as described above, a compound of formula (7) is obtained by substituting a hydrogen atom of the cyclopentadiene ring of the compound of formula (5) with the compound of formula (5) as a starting material. In the compound of Chemical Formula 7, the quencher function of the compound of Chemical Formula 5 is maintained, and the solubility is improved as compared with the compound of Chemical Formula 5. Also, synthesis is easy. In other words, compared to the case of newly designing and synthesizing a compound having a quencher function and high solubility, the target compound can be synthesized without being affected by the availability of raw materials or the cost. This is extremely advantageous.

The metal complex or metal complex quench of the present invention
The compound of Chemical Formula 5, which is used as a starting material for the catalyst, will be described.
In the chemical formula 5, R₁ And R_Two Are hydrogen atoms or
Or monovalent substituents, which are the same or different
May be. In this, R ₁ And R_Two Represented by
Examples of the monovalent substituent include an alkyl group, an aryl group,
Group, ether group, ester group, acyl group, alkyl group
O, sulfamoyl, alkylsulfonyl, hetero
Examples include a ring group, a halogen atom or a nitro group. this
R₁ And R_Two Is a halogen atom such as fluorine and chlorine,
A nitro group, preferably an alkyl group having 1 to 4 carbon atoms,
An aryl group, preferably an alkyl group having 1 to 4 carbon atoms
Having an alkoxy group, a substituted or unsubstituted amino group, etc.
May be further substituted.

Preferred examples of R ₁ and R ₂ include:
Hydrogen atom; an alkyl group having 1 to 4 carbon atoms (—CH ₃ ,
_{-C 2 H 5, -C 3 H} 7, -C 4 H 9, -CF 3 , etc.);
An ether group having an alkyl group having 1 to 4 carbon atoms (-
OCH _3, -OCF _3, etc.); an ester group having an alkyl group of 1 to 4 carbon atoms (-COOCH _3, -COOC
₂ H ₅ and the like); an acyl group having an alkyl group of 1 to 4 carbon atoms (-COCH _3, etc.); an alkylthio group (-SCH ₃ having an alkyl group of 1 to 4 carbon atoms, -SCF ₃
Etc.); a sulfamoyl group (-SO ₂ NH _2, etc.); an alkylsulfonyl group having an alkyl group of 1 to 4 carbon _{atoms, (- SO 2 CH 3,} -SO 2 CF 3 , etc.); NO _2;
CN; an aryl group having 6 to 12 carbon atoms (phenyl group,
p-nitrophenyl group, p-aminophenyl group, etc.); 5
Or a heterocyclic group which may have a 6-membered condensed ring (such as a 2-pyridyl group, a 3-pyridyl group, or a 4-pyridyl group); and a halogen atom (such as F, Cl, or Br).

R ₁ and R ₂ are usually the same, but may be different from each other. R ₁ and R ₂ may combine with each other to form a ring, for example, an aromatic ring such as a benzene ring and a naphthalene ring. In addition, a substituent such as an alkyl group, an aryl group, a halogen, a substituted or unsubstituted amino group, or an alkoxy group may be further bonded to the ring. Of these, an unsubstituted benzene ring is preferred.

Of these, a hydrogen atom or a monovalent substituent having a Hammett sigma (σ) value of 0 or more is preferable. Specific examples of the monovalent substituent having a Hammett sigma (σ) value of 0 or more include —CF ₃ , —CN, and —OCF.
_{3, -COOCH 3, -COOC 2 H} 5, -SCF 3,
—NO ₂ , —SO ₂ NH ₂ , —SO ₂ CH ₃ , a halogen atom and the like are preferable. When R ₁ and R ₂ are bonded to each other to form a ring, an unsubstituted benzene ring is preferable.

In the formula 5, R ₃ represents a monovalent substituent, and t represents an integer of 0-4. However, the group other than R ₃ bonded to the cyclopentadiene ring is a hydrogen atom. Therefore, at least one hydrogen atom is bonded to the cyclopentadiene ring of Chemical formula 5, and 1 to 5 hydrogen atoms can be bonded. In the present invention, the hydrogen atom is replaced to obtain the target product.

As the monovalent substituent represented by R ₃ ,
A substituted or unsubstituted alkyl group having 1 to 4 carbon atoms _{(-CH 3, -C 2 H 5} , -CF 3, -C 2 F 5 , etc.),
A substituted or unsubstituted aryl group (such as a phenyl group), a cyano group, or a substituted or unsubstituted ether group (—OCH
_3, -OCF _3, etc.), substituted or unsubstituted ester group (-COOCH _3, -COOC ₂ H _5, etc.), a substituted or unsubstituted acyl group (-COCH _3), a substituted or unsubstituted alkylthio group ( -SCH _3, -SCF
₃ ), a substituted or unsubstituted sulfamoyl group (-S
O ₂ NH _2, etc.), a substituted or unsubstituted alkylsulfonyl group _{(-SO 2 CH 3, -SO 2} CF 3 , etc.), a halogen atom (F, Cl, Br, I, etc.), nitro group and the like.

When t is 2 or more, R ₃ may be the same or different. Also by bonding adjacent R ₃ each other to form a ring cycloalkanes (cyclopentane, etc.), may be fused to the cyclopentadiene ring. However, even when such a condensed ring is formed, there is at least one hydrogen atom.

It is particularly preferable that t = 0.

In the chemical formula 5, X and Y coordinated to the metal atom M represent S or Se, respectively, and may be the same or different. Among them, a combination of S members is preferable.

Further, M is a metal atom such as Co, N
i, Pt, Zn, Cu, Rh, etc.
o, Ni or Rh is preferred, and Co is particularly preferred.

Compounds of formula 5 are represented by M, X, Y, C, C
The ring formed by has aromaticity. The aromatic character of the ring formed by these means that ¹³ CNM
It is confirmed from the chemical shift (δ) value of ¹³ C of cyclopentadiene due to R, the reduced half-wave potential (E ^r _1/2 ) value of the polarogram, and the like.

For example, in a dithiol ring in which both X and Y are S, the E ^r _1/2 value is -1.8 to OV and the δ value of ¹³ C is 75 to 90 ppm. When the δ value is plotted against the E ^r _1/2 value, a linear relationship is shown, and the slope △ (δ /
E ^r _1/2 ) is in the range of 2.0 to 15.0 (ppm / V).
In addition, E ^r _1/2 is tetraethylammonium perchlorate (TEAP) as a supporting electrolyte in acetonitrile.
Using a reference electrode (Ag | 0.1 mol dm ^-3 AgClO)
_The potential with respect to ₄ ) was determined by measuring at 25 ° C.

The compound of formula (5) may be a dimer as shown in formula (9).

[0031]

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In Chemical Formula 9, R ₁ , R ₃ , t, X, Y and M have the same meanings as in Chemical Formula 5, respectively.

The compound of formula 5 is described by Akira Sugimori, Yoka, 48,
788 (1990), Akira Sugimori, Organometallics News,
1990, No. 1, P2, H. Boennemann, B. Bogdanovic, W. Brij
oux, R. Brinkmann, M. Kajitani, R. Mynott, GS Nataraj
an and MGSanson "Transition-Metal-Catalyzed Synt
hesis of Heterocyclic Compounds "in" Catalysisin
Organic Reactions "ed. By JRKosak, Marcel Dekke
r, 1984, P31-62, Japanese Patent Application No. 4-269449, Japanese Patent Application No. 5-60890, etc., and specific examples and synthesis methods are also described in these documents.

Among these, preferred compounds used in the present invention are exemplified below.

[0035]

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On the other hand, the compound of the formula 6, which reacts with the compound of the formula 5, decomposes by releasing N ₂ by heating or the like, so that R ₄ .
It is an azo compound that generates a radical of ₅ . Explaining Chemical formula 6, R ₄ and R ₅ each represent a hydrocarbon group or a carbamoyl group. The hydrocarbon group represented by R ₄ or R ₅ may be any of aliphatic, alicyclic and aromatic, and may have a substituent. Specific examples include an aryl group such as an alkyl group and a phenyl group. Among them, an alkyl group is preferable, and this may be linear or branched. Further, it has a substituent such as a cyano group, an ester group such as a methoxycarbonyl group, an ether group, an acyl group such as an acetyl group, a carboxy group, an amino group, a hydroxy group, and a heterocyclic group such as a 2-imidazolinyl group. Is also good. The total number of carbon atoms in the alkyl group is preferably 1 to 10.
Particularly, a cyanoalkyl group is preferable, and specifically, a 1-cyano-1-methylethyl group, a 1-cyano-1-methylpropyl group, a 1-cyano-1,3-dimethylbutyl group, and the like are preferable.

The carbyl groups represented by R ₄ and R ₅ are preferably unsubstituted, but may have a substituent. R ₄ and R ₅ are preferably the same, but may be different in some cases.

Specific examples of the compound of the formula (6) are shown below. Particularly preferred are the α and α 'of the exemplified compound R-1.
- As such azobisisobutyronitrile azobisisobutyronitrile (AIBN), it is one having a cyanoalkyl group, R ₄ and R
_{And 5} is the same.

[0039]

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When reacting the compound of the formula (5) and the compound of the formula (6), the amount ratio of the two compounds is such that the compound of the formula (6) is about 0.1 to 10 mol per mol of the compound of the formula (5). do it.

The non-aqueous solvent used in the reaction is not particularly limited. Examples thereof include aromatic solvents such as benzene, toluene, nitrobenzene and xylene, cellosolves such as methyl cellosolve and ethyl cellosolve, alcohols such as methanol and ethanol, and methylene chloride. And the like. Above all, aromatic compounds such as benzene, toluene, nitrobenzene, and xylene are preferable.

The reaction is preferably carried out at a temperature of 10 to 200 ° C., more preferably at a temperature of 30 to 150 ° C. The reaction time may be about 0.5 to 50 hours. Such a reaction may be performed by raising or lowering the temperature from about room temperature (20 ° C.) to the above temperature, and maintaining the above temperature for the above time. The reaction is preferably performed in an inert atmosphere such as Ar. Reflux may be carried out during the reaction if necessary.

The reaction product thus obtained is concentrated by distilling off the solvent with a rotary evaporator or the like, and the product is separated and purified by column chromatography or the like.
A compound of formula 7 is obtained.

Describing the compound of Chemical formula 7, R _{1 to} R ₃ , t, X, Y and M in Chemical formula 7 have the same meanings as those of Chemical formula 5, and preferred compounds are also the same. R ₄ and R ₅ have the same meanings as in Chemical Formula ₅ , respectively, and preferred ones are also the same.

V and w each represent an integer of 0 to 5, but they are not both 0, and v + w is 1 to 5, more preferably 1 to 3. Further, t + v + w is 5 or less, that is, 1 to 5, and particularly preferably 1 to 3. The compound of Chemical formula 7 may be a dimer as shown in Chemical formula 12.

[0046]

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In the formula 12, R ₁ , R ₃ , R ₄ , R
₅ , t, v, W, X, Y and M have the same meanings as in Chemical formula 7, respectively.

As described above, the hydrogen of the cyclopentadiene ring of the compound of the formula ( ₅₎ is appropriately substituted with at least one or both of R ₄ and R ₅ to obtain the compound of the formula (7).

As described above, the compound represented by the general formula (6) is usually represented by a compound represented by the general formula:
_{Since the} same compound is used for ₄ and R ₅ , and considering the reactivity, a compound of v + w = 1 is particularly likely to be formed in Chemical formula 7.

Specific examples of the compound of formula 7 are shown below.

[0051]

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[0052]

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Note that Von GE Herberich, J. Schwarzer,
Angrew.Chem., 82, Johrg., 1970, Nr. 21 reports a radical addition reaction of dicyclopentadienylcobalt, and specifically, a reaction with α, α'-azobisisobutyronitrile. The reaction is described. The reaction is α, α '
-Is similar to the reaction of the present invention in that azobisbutyronitrile is used, but is an addition reaction unlike the reaction of the present invention. Therefore, in the reaction product, the resonance structure of the cyclopentadiene ring is broken, and the position of the double bond is fixed. In contrast, the reaction of the present invention is a substitution reaction, and the resonance structure of the cyclopentadiene ring is maintained. The maintenance of the resonance structure can be confirmed by ¹ HNMR (signal of cyclopentadiene ring hydrogen) and the like. Therefore, the reaction described in the above-mentioned literature is completely different from the reaction of the present invention. The details of the reason why the addition reaction occurs with dicyclopentadienyl cobalt and the substitution reaction occurs with the monocyclopentadienyl metallocene compound of Chemical Formula 5 are currently unknown.
Further, the compound obtained by the addition reaction according to the above literature does not exhibit a quencher function unlike the compound of the present invention.

The compound of formula 7 has a mass spectrum of ¹ HN
It can be confirmed by MR ( ¹ H nuclear magnetic resonance spectrum), ¹³ C NMR and the like.

The compound of the formula (7) is similar to the compound of the formula (5) in that the ring formed by M, X, Y, C and C has an aromatic character. This can be confirmed in the same manner as described above.

Further, the compound of the formula (7) is 2 to 2 times more soluble in solvents such as aliphatic alcohols, cellosolves, ketone alcohols and halogenated alcohols than the compound of the formula (5).
The solubility is improved about 0 times.

The absorption maximum of the metal complex quencher represented by Chemical Formula 7 is preferably 600 nm or less, particularly preferably 550 to 595 nm, and has no influence on the absorption characteristics of the dye preferably used in the present invention. Accordingly, there is no decrease in reflectance when used as an optical recording medium, and there is no decrease in reproduction output.

The optical recording medium of the present invention has a recording layer containing a dye and a quencher. In this case, a metal complex quencher represented by Chemical Formula 7 is used. Such a quencher has sufficient solubility in preparing a coating solution for forming a dye film, and facilitates film formation. For this reason, light resistance becomes sufficient and reflectance can be sufficiently ensured. Therefore, the present invention can be applied to an optical recording disk corresponding to the compact disk (CD) standard.

The optical recording medium of the present invention includes, in addition to the metal complex quencher represented by Chemical Formula 7 obtained as described above, a compound represented by Chemical Formula 7,
The novel metal complex represented by Chemical formula 8 can be used as a quencher.

In formula 8, R ₁ , R ₂ , X, Y and M have the same meanings as in formulas 5 and 7, and R ₆ represents a cyanoalkyl group, especially 1-cyano-1-methylethyl. Group, 1-cyano-1-methylpropyl group, 1-cyano-
A 1,3-dimethylbutyl group is preferred.

Specific examples of the metal complex quencher represented by Chemical Formula 8 include those shown in Chemical Formulas 13 and 14 described above. However, the production method is not limited to the method of the present invention, and is the same as or similar to the compound of Chemical Formula 5 as a starting material for obtaining the metal complex quencher represented by Chemical Formula 7, or a method similar to Friedel- A synthesis method such as a ligand reaction based on the Crafts reaction may be used.

The light-absorbing dye used in the recording layer together with the metal complex quencher of Chemical formula 7 or 8 has an absorption maximum of 600 to 900 nm, more preferably 600 to 80 nm.
It is preferably 0 nm, more preferably 650-750 nm. For example, cyanine, phthalocyanine, naphthalocyanine, anthraquinone, azo, triphenylmethane, pyrylium or thiapyrylium salt,
One or more of squarylium, croconium, metal complex dyes and the like may be appropriately selected according to the purpose. As the cyanine dye, a cyanine dye having an indolenine ring which may have an aromatic condensed ring, particularly a benzoindolenine ring is preferable. At this time, the two indolenine rings may have different condensed states.

With respect to preferred dyes used for the recording layer,
For example, JP-A-59-24692 and JP-A-59-5579.
No. 4, No. 59-55795, No. 59-81194,
No. 59-83695, No. 60-18387, No. 60
-19586, 60-19587, 60-35
No. 054, No. 60-36190, No. 60-36191
No. 60-44554, No. 60-44555, No. 60-44389, No. 60-44390, No. 60-
No. 47069, No. 60-20991, No. 60-712
No. 94, No. 60-54892, No. 60-71295
No. 60-71296, No. 60-73891, No. 60-73892, No. 60-73893, No. 60-
No. 83892, No. 60-85449, No. 60-928
No. 93, No. 60-159087, No. 60-16269
No. 1, No. 60-203488, No. 60-201988
Nos. 60-234886 and 60-234892
No. 61-16894, No. 61-11292, No. 61-11294, No. 61-16891, No. 61-
No. 8384, No. 61-14988, No. 61-1632.
No. 43, No. 61-210538, Japanese Patent Application No. 60-540
No. 13, JP-A Nos. 62-30088 and 62-3213
Nos. 2, 62-31792, and "Chemistry of Functional Dyes" published by CMC, pp. 74-76.

The metal complex quencher represented by the formulas (7) to (8) is usually used in an amount of 0.1 to 1 with respect to 1 mol of the dye.
0 mol is used. If necessary, in addition to the metal complex quencher of Chemical formula 7 or 8, other known quencher may be used in combination.

The recording layer is formed by a spin coating method in which a coating solution containing a metal complex quencher of Chemical formula 7 or 8, a dye and an organic solvent is used, and the coating solution is spread and applied on a rotating substrate. Is preferred. The organic solvent used for the coating liquid for forming the recording may be appropriately selected from alcohols, ketones, esters, ethers, aromatics, alkyl halides and the like according to the dye used. After spin coating, the coating film is dried if necessary. The thickness of the recording layer thus formed is
Although it is appropriately set according to the target reflectance and the like, it is usually about 1000 to 3000 A.

The content of the dye in the coating solution is 2
The content of the quencher is 0.5 to 10% by weight, preferably 1 to 8% by weight. Note that the coating liquid may appropriately contain a binder, a dispersant, a stabilizer and the like.

Preferred examples of the optical recording medium having a dye film containing the metal complex quencher of Chemical formula 7 or 8 as a recording layer include an optical recording disk such as a write-once compact disk (CD). FIG. 1 shows a configuration example of an optical recording disk. FIG. 1 is a partial sectional view. The optical recording disk 1 shown in FIG. 1 is a contact-type optical recording disk having a reflective layer adhered on a recording layer and capable of reproducing data in compliance with the CD standard. As shown in the figure, the optical recording disk 1 has a recording layer 3 containing the above-described dye as a main component on the surface of a substrate 2, and has a reflective layer 4 and a protective film 5 in close contact with the recording layer 3.

The substrate 2 is in the form of a disk. To enable recording and reproduction from the back side of the substrate 2,
Recording light and reproduction light (semiconductor laser light having a wavelength of about 600 to 900 nm, particularly about 770 to 900 nm,
80 nm), which is substantially transparent (preferably a transmittance of 88
% Or more) using a resin or glass. The size is about 64 to 200 mm in diameter and about 1.2 mm in thickness.

A tracking groove 23 is formed on the surface of the substrate 2 on which the recording layer 3 is formed, as shown in FIG.
The groove 23 is preferably a spiral continuous groove, having a depth of 0.1 to 0.25 μm, a width of 0.35 to 0.50 μm, and a groove pitch of 1.5 to 0.5 μm.
It is preferably 1.7 μm. With such a configuration of the groove, a good tracking signal can be obtained without lowering the reflection level of the groove portion. In particular, it is important to limit the groove width to 0.35 to 0.50 μm. If the groove width is less than 0.35 μm, it is difficult to obtain a tracking signal of a sufficient size, and a slight offset of the tracking during recording. As a result, jitter tends to increase. 0.50μm
Exceeding the limit causes waveform distortion of the reproduced signal to occur easily, which causes an increase in cross stroke.

The material of the substrate 2 is preferably a resin, and various thermoplastic resins such as polycarbonate resin, acrylic resin, amorphous polyolefin, TPX, and polystyrene resin are suitable. And it can manufacture according to well-known methods, such as injection molding, using such a resin. The groove 23 is preferably formed when the substrate 2 is formed. After the manufacture of the substrate 2, a resin layer having the groove 23 may be formed by a 2P method or the like. In some cases, a glass substrate may be used.

As shown in FIG. 1, the recording layer 3 provided on the substrate 2 is formed by using the above-mentioned dye-containing coating solution and preferably by the spin coating method as described above. The spin coating may be performed under normal conditions, for example, by adjusting the number of revolutions from 500 to 5000 rpm from the inner circumference to the outer circumference.

The thickness of the recording layer 3 formed as described above is 500 to 3000 A (50 to 300 n
m) is preferable. Outside of this range, the reflectivity decreases, making it difficult to perform reproduction conforming to the CD standard. At this time, the thickness of the recording layer 3 in the recording track in the groove 23 is set to 1000 A (100 nm) or more, especially 1500
When it is ３3000 A (150-300 nm), the modulation degree becomes extremely large.

The recording layer 3 formed in this manner has C
When recording a D signal, the extinction coefficient (imaginary part of the complex refractive index) k of the recording light and the reproduction light wavelength is 0.02 to 0.02.
It is preferably 0.05. When k is less than 0.02, the absorptivity of the recording layer decreases, and it is difficult to perform recording with normal recording power. On the other hand, if k exceeds 0.05, the reflectivity falls below 70%, making it difficult to perform reproduction according to the CD standard. Further, the refractive index (real part of the complex refractive index) n of the recording layer 3 is 2.0 to 2.6. n
If it is less than 2.0, the reflectivity tends to be low, and the reproduction signal tends to be small, so that reproduction according to the CD standard tends to be difficult.

As shown in FIG. 1, on the recording layer 3,
The reflection layer 4 is provided in close contact with the substrate. The reflective layer 4 is preferably made of a high-reflectance metal or alloy such as Au or Cu. The thickness of the reflective layer 4 is preferably 500 A or more, and may be provided by vapor deposition, sputtering, or the like. The upper limit of the thickness is not particularly limited, but is preferably about 1200 A or less in consideration of cost, production operation time and the like. Thereby, the reflectance of the reflection layer 4 alone becomes 9
0% or more, the reflectance of the unrecorded portion of the medium through the substrate is:
60% or more, especially 70% or more, is obtained.

As shown in FIG. 1, on the reflection layer 4,
A protective film 5 is provided. The protective film 5 is made of, for example, various resin materials such as an ultraviolet curable resin, and is usually 0.5 to 100 μm.
It may be formed to a thickness of about m. The protective film 5 may be in the form of a layer or a sheet. The protective film 5 may be formed by an ordinary method such as spin coating, gravure coating, spray coating, dipping, or the like.

The optical recording disk of the present invention is not limited to a contact type optical recording disk as shown in the figure, but may be any optical disk having a recording layer containing a dye. Examples of such a disk include a pit-formed optical recording disk having an air sandwich structure, and similar effects can be obtained by applying the present invention.

[0077]

EXAMPLES Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention.

Example 1 136 mg of Exemplified Compound P-1 [Chemical Formula 10] and 136 mg of Exemplified Compound R-
169 mg of 1 [Chemical Formula 11] was reacted in 100 ml of benzene under reflux for 40 hours under an argon atmosphere. The temperature was raised from room temperature and maintained at the reflux temperature (about 80 ° C.). The reaction product thus obtained was concentrated by a rotary evaporator, and the concentrate was separated and purified by column chromatography to obtain Exemplified Compound Q-1 [Chemical Formula 13].

The yield was 9.2 mg (5.6%).

The mass spectrum and ¹
When the H-NMR spectrum was measured, the following results were obtained.

Mass spectrum (electron impact ionization method: EI) m / E (mass / charge number) 397 Metal complex 255 1-cyano-1-methylethylpentadienyl cobalt S ₂

¹ H-NMR spectrum 1-cyano-1-methylethyl group (methyl hydrogen):
1.6 ppm cyclopentadiene ring hydrogen: 5.3 ppm,
5.8 ppm methoxycarbonyl group (methyl hydrogen):
3.9 ppm

Example 2 Exemplified Compound P-2 [Chemical Formula 10] 126 mg and Exemplified Compound R-
Exemplified compound Q-2 [Chemical Formula 13] was obtained in the same manner as in Example 1 except that 190 mg of 1 [Chemical Formula 11] was used. Yield 55mg
(Yield 34.8%).

Mass spectrum (EI) m / E 331 Metal complex (however, it is unknown whether the 1-cyano-1-methylethyl group is bonded to the cyclopentadiene ring or the benzene ring. Confirmed by ¹ HNMR ).

¹ H-NMR spectrum 1-cyano-1-methylethyl group (methyl hydrogen):
1.6 ppm cyclopentadiene ring hydrogen: 5.4 ppm,
5.8 ppm benzene ring hydrogen:
8.1 ppm

Further, other exemplified compounds represented by Chemical Formulas 13 and 14 were synthesized in the same manner. These also have mass spectra,
^It was identified by ¹ H-NMR spectrum.

Example 3 The solubility of the exemplified compounds Q-1 and Q-2 synthesized in Examples 1 and 2 in ethyl cellosolve at 25 ° C. was examined. Further, the solubility of the exemplified compounds P-1 and P-2, which are the starting materials, was similarly examined. Table 1 shows the results.

[0088]

[Table 1]

As is clear from Table 1, the compounds of the present invention have remarkably improved solubility as compared with the compounds of the starting materials. In addition, the solubility of each of the other exemplary compounds represented by Chemical Formulas 13 and 14 and each of the starting materials were similarly examined and compared, and in each case, the compound of the present invention was the same as the above in comparison with the starting material. It was found that the solubility was improved.

Example 4 Using the compounds shown in Table 2 as quenchers, an ethyl cellosolve solution containing a total of 2.5 wt% of an indolenine-based cyanine dye represented by Chemical Formula 15 and a quencher was prepared. In this case, the ratio between the dye and the quencher was 85/15 by weight. Using each of these solutions,
A dye film was formed by spin coating on a glass substrate having a diameter of 50 mm and a thickness of 1.2 mm.
o. 1-4 were obtained. The thickness of the dye film was 70 nm. Each of these sample Nos. 1 to 4 has an initial transmittance T _0.
Was measured. Further, the sample was irradiated with a xenon lamp of 80,000 lux, the transmittance T after the irradiation was measured, and (100-T) × 1
The dye remaining rate was calculated as 00 / (100-T ₀ ). The time required for the dye remaining rate to reach 80% was examined, and the light resistance of each sample was compared. Table 2 shows the results.

[0091]

Embedded image

[0092]

[Table 2]

As is clear from Table 2, the compounds of the present invention are excellent in light resistance. In addition to the above compounds,
The light resistance of the other compounds shown in No. 14 was also examined, and good results equivalent to the above were obtained.

Example 5 An optical recording disk sample having the structure shown in FIG. 1 was prepared by using the solutions used in Sample Nos. 1 and 3 of Example 4 as a coating solution for forming a recording layer. Sample N of Example 4
o. Optical recording disk sample No. according to No. 1 and No. 3
1, No. 3. However, the total content of the dye and the quencher in the coating solution was 5 wt%, and the ratio of the dye and the quencher was the same as in Example 4.

First, a recording layer containing a dye was formed on a polycarbonate resin substrate having a diameter of 120 mm and a thickness of 1.2 mm by spin coating. The thickness of the recording layer is 200 nm
And A reflective layer was formed on this recording layer. The reflective layer was made of Au, and was formed to a thickness of 85 nm by a sputtering method. Then, a UV-curable acrylic resin protective film (5 μm thick) was formed thereon.

With respect to the disk samples No. 1 and No. 3, the reflectance at 780 nm was measured. The reflectivities were 70% and 71%, respectively, and were found to sufficiently correspond to the CD standard. In addition, the exemplary compounds Q-1, Q
The absorption maximum at -2 is 575 nm and 590 nm, respectively.
nm.

In addition, disk samples were prepared using the above compounds and other compounds shown in Chemical formulas 13 and 14, and the reflectance was measured for these. As a result, good results equivalent to the above were obtained.

[0098]

According to the present invention, a metal complex quencher exhibiting good solubility and facilitating preparation of a dye coating solution can be easily obtained. Further, since such a metal complex quencher is used for the optical recording medium, it is easy to form the recording layer and there is no decrease in the reflectance of the recording layer. In addition, there is little reproduction deterioration and light deterioration, and the light resistance is excellent.

[Brief description of the drawings]

FIG. 1 is a partial sectional view showing an example of an optical recording disk of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Optical recording disk 2 Substrate 23 Groove 3 Recording layer 4 Reflective layer 5 Protective film

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03C 1/735 G03C 1/735 G11B 7/24 516 G11B 7/24 516 (72) Inventor Noriyoshi Nanba 1-1-13 Nihonbashi, Chuo-ku, Tokyo (56) Reference JP-A-6-309969 (JP, A) JP-A-63-74689 (JP, A) JP-A-1-163189 (JP, A) JP-A-1-210389 (JP, A) Journal of Organometallic Chemistry, 388 (1990) p89-94 Journal of Organometallic Chemistry, 441 (1992) p143-154 Polyhedron (1988), p10-34 (10-34). an Chemical Society (1986), 108 (11) p3114-3115 (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 15/06 C07F 15/00 C07F 15/04 C09B 57/00 G03C 1/735 G11B 7/24 516 CA (STN) REGISTRY (STN) WPIDS (STN)

Claims (11)

(57) [Claims] A compound represented by the following formula (1) and a compound represented by the following formula (2)
A method for producing a metal complex, which comprises reacting a compound represented by the following formula with a non-aqueous solvent to obtain a metal complex represented by the following formula: Embedded image [Image Omitted] R ₄ -N = NR ₅ [In formula ₁ , R ₁ and R ₂ each represent a hydrogen atom or a monovalent substituent, and these may be the same or different. R ₁ and R ₂ may combine with each other to form a ring. R ₃ represents a monovalent substituent. t is 0 to 4
Represents an integer. When t is 2 or more, R ₃ may be the same or different, and adjacent R ₃ may combine to form a ring. X and Y each represent S or Se, and X and Y may be the same or different. M represents a metal atom. In Chemical Formula 2, R ₄ and R ₅ each represent a hydrocarbon group or a carbamoyl group, and R ₄ and R ₅ may be the same or different. In Formula 3, R ₁ , R ₂ , R ₃ , t, X,
Y and M have the same meanings as in Chemical Formula 1, respectively. R ₄
And R ₅ have the same meanings as in Chemical Formula 2, respectively. v and w each represent an integer of 0 to 5, but are not both 0, and t + v + w is 5 or less. ] 2. The method for producing a metal complex according to claim 1, wherein R ₄ and R ₅ of the compound represented by Formula 2 are cyanoalkyl groups. 3. The method for producing a metal complex according to claim 1, wherein the metal complex represented by the chemical formula (3) has higher solubility than the compound represented by the chemical formula (1). 4. The method for producing a metal complex according to claim 1, wherein the reaction is performed at a temperature of 10 to 200 ° C. 5. The method for producing a metal complex according to claim 1, wherein the metal complex represented by the above formula (3) is used as a quencher. 6. A metal complex represented by the following chemical formula 4. Embedded image [In formula 4, R ₁ and R ₂ each represent a hydrogen atom or a monovalent substituent, and these may be the same or different. R ₁ and R ₂ may combine with each other to form a ring. R ₆ represents a cyanoalkyl group. X and Y each represent S or Se, and X and Y may be the same or different. M represents a metal atom. ] 7. A metal complex quencher, which is the metal complex according to claim 6. 8. An optical recording medium having a recording layer containing the metal complex quencher according to claim 7 and a dye on a substrate. 9. The dye according to claim 8, wherein the dye is a cyanine dye.
Optical recording medium. 10. The optical recording medium according to claim 9, wherein said cyanine dye has an indolenine ring. 11. A dye having an absorption maximum of 600 to 900.
The optical recording medium according to any one of claims 8 to 10, wherein the diameter is in nm.