JP2001039032A - Optical information recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To optically record in a blue light region with high sensitivity by providing at least onto a base plate a record layer made of a cyclic compound having a structure for directly coupling four pyrrole rings which may each have a substituent, or coupling through a carbon atom which may have a substituent. SOLUTION: A record layer made of a compound having a substantially parallel opposing structure for coupling four pyrrole rings which may each have a substituent is provided directly or through a carbon atom which may have a substituent onto an at least base plate, in such a manner that two or more cyclic compounds which may be the same or different are coupled through a bonding site, and its recording and reproducing wavelengths are each 380 to 500 nm. As the above cyclic compound, a porphyrin derivative represented by the formula is preferably used, wherein R1 to R8 and X1 to X4 are each a hydrogen atom, halogen atom, nitro group, cyano group or the like and R9 to R15 are each a hydrogen atom, or a substituted or unsubstituted aliphatic or aromatic hydrocarbon group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recordable optical information recording medium on which information is recorded and reproduced optically, and more particularly to a recording material using an organic dye.

[0002]

2. Description of the Related Art As a laser beam for recording and reproducing information on and from an optical information recording medium, a laser beam in the red to infrared region is used, and recording media corresponding to the laser light are widely used. For example, a disc-shaped optical information recording medium (CD-Writable by a user, such as a write-once optical information recording medium).
R, DVD-R) are also examples. The write-once optical information recording medium has a configuration in which a recording layer made of, for example, an organic dye is formed on a substrate, and recording is usually performed in a heat mode. That is, when the recording layer is irradiated with laser light,
The energy of light is converted to heat by the light absorption of the organic dye, and the generated heat forms pits. The pit is detected by a difference in reflectance based on a phase change between a portion where the pit is formed and a portion where the pit is not formed when the laser light is irradiated.

In order to increase the recording density by recording / reproducing at the conventional laser wavelength, a device such as so-called super-resolution is required. However, in recent years, the practical use of a semiconductor laser in the blue light region has been becoming feasible, and it has become possible to increase the amount of recorded information without contrivance such as super-resolution. The oscillation wavelength of the semiconductor laser corresponding to the blue light region is about 380 to 500 (nm), particularly 400 to 450 (nm).
(Nm), and it is necessary to shorten the wavelength of the recording material accordingly. Usually, the maximum absorption wavelength is 35
Organic materials having a molecular weight of about 0 to 450 (nm) generally have a small molecular skeleton, and therefore have a low molecular extinction coefficient. In general, there are few compounds having sufficient solubility.

However, one of the materials that can solve this problem is
One example is a porphyrin derivative represented by [Chemical Formula 81]. A porphyrin derivative is a metal complex having a structure in which an atomic group is coordinated to a central metal, and contains at least 38 π electrons (the number of π electrons increases with a substituent). In this porphyrin derivative, in the molecular absorption spectrum,
It has an absorption band called a Soret band (S band) derived from the 16-membered ring (18 π-electron systems) on the short wavelength side.

This Soret band has a very large molecular extinction coefficient of 100,000 or more, and high sensitivity optical recording in the blue light region is possible by using this large absorption band. A porphyrin derivative is promising as a material which can be recorded / reproduced by a semiconductor laser in a blue light region. Most porphyrin derivatives have a porphyrin derivative of 380 to 500 (nm), especially 40 to 500 (nm).
It cannot respond to short wavelengths of 0 to 450 (nm).

As a short-wavelength recording medium using a porphyrin derivative, JP-A-7-304256 describes "an optical information recording medium comprising a porphyrin derivative and a polymer having a molecular structure having a coordinating ability in a side chain". And JP-A-7
No. 304304 describes "an optical information recording medium comprising a porphyrin derivative and a molecular compound having a coordination ability and a polymer". All aim at wavelength matching in the short wavelength region, but the recording wavelength is 480-49.
0 (nm), which is considered to be put to practical use in the future 38
0 to 500 (nm), especially 400 to 450 (nm)
Cannot be adapted to the recording / reproducing wavelength at all.

In these optical information recording media, a molecular compound having a coordinating ability or a polymer having a molecular structure having a coordinating ability in a side chain is coordinated with the central metal of the porphyrin derivative. The main focus is on increasing the coefficient and shifting the absorption wavelength in the Soret band to longer wavelengths.

In these optical information recording media, basically, tetraphenyltetrabenzporphyrin is used as a porphyrin derivative. However, since tetraphenyltetrabenzporphyrin has an absorption wavelength near 470 (nm), it is 380 to 500.
(Nm), especially a semiconductor laser having an oscillation wavelength in the range of 400 to 450 (nm) cannot be recorded and reproduced. Therefore, the recording described in the example of the above-mentioned document is performed using an AR laser (wavelength is 488).
(Nm)).

In the case of a porphyrin derivative, if a substituent is introduced at the meso-position carbon such as tetraphenylporphyrin, the wavelength becomes longer due to distortion of the porphyrin ring, and the wavelength becomes 380 to 500 (nm), especially 400 to 500 (nm). It cannot be applied to a recording / reproducing wavelength of 450 nm. Therefore, when trying to correspond to a recording / reproducing wavelength of 380 to 500 (nm), particularly 400 to 450 (nm), the position of introducing a substituent into porphyrin and the type of the introduced substituent are greatly restricted, The number of structures that satisfy all of the requirements of shorter wavelength, improved solubility, prevention of crystallization, and lowering of decomposition temperature is extremely reduced (the range of selection is narrowed).

[0010] Further, in order to improve the solubility and reduce the wavelength dependence, Japanese Patent No. 2741515 describes a phthalosinin dimer, and Japanese Patent No. 25455565 describes a porphyrazine dimer. However, these are related to phthalocyanine and naphthalosinine, and are different from the present invention in which the purpose is basically to shorten the wavelength. In addition, even if two molecules of phthalosinin described in Japanese Patent No. 2741515 may have any arrangement, there is no description of a structure necessary for shortening the wavelength.

[0011]

SUMMARY OF THE INVENTION The present invention has been proposed in view of such a conventional situation, and enables high-sensitivity optical recording in the blue light region and a recording / reproducing wavelength of 38.
The present invention provides a write-once optical information recording medium capable of coping with 0 to 500 (nm), especially 400 to 450 (nm), and light having excellent recording / reproducing characteristics by greatly increasing the introduction variation of substituents. It is an object to provide an information recording medium.

[0012]

Means for Solving the Problems As a result of intensive studies and investigations, the present inventors have found that a dimer or multimer of a parallel facing structure of a specific porphyrin derivative or isomer is 380 to 500 (n
m), in particular, it has been found that recording and reproduction are possible in a short wavelength region of 400 to 450 (nm) and that the compound has sufficient solubility in an organic solvent, and based on this, the present invention has been accomplished.

That is, according to the present invention, firstly, at least on the substrate, at least four pyrrole rings which may have a substituent are bonded via a carbon atom which may have a substituent or are directly bonded. In the cyclic compound having the above-mentioned structure, two or more cyclic compounds which may be the same or different from each other form a substantially parallel facing structure via a bonding site (so-called bridge structure)
And a recording / reproducing wavelength of 380 to 500 (nm) is provided.

An example of the structure of the dimer having a substantially parallel face-to-face structure is shown in [Formula 12] (however, the present invention is not limited to the dimer) and has the following features. .

Embedded image

(1) The upper and lower two rings may be the same or different from each other. (2) t, u, v, w, t ′, u ′, v ′, w ′ each represent an integer of 0 to 3, and (t + u + v + w) = (t ′)
+ U '+ v' + w ') = 3 or 4. (3) Y represents a bonding site connecting the central metals M and M ′, a bonding site connecting pyrrole rings of different skeletons, or a bonding site connecting substituents introduced at meso positions of different skeletons, A plurality may be introduced. (4) Note that R _{1 to} R ₈ , X _{1 to} X ₄ , and M are represented by the general formulas (2) to
Same as those of (6). R ₁ ′ to R ₈ ′ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group,
It represents a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group. M ′ is 2 or 3 hydrogen atoms, or a metal atom which may have oxygen or halogen, or (OR ₉ ) p, (OSiR ₁₀ R ₁₁
R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r, and a metal atom which may have (OCOR ₁₅ ) s. R _{9 to} R ₁₅ are each independently a hydrogen atom,
Represents a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and p, q, r, and s represent an integer of 0 to 1.

According to the first aspect of the invention, the wavelength can be shortened, and the number of substituents and substitution positions that can be used are dramatically increased, so that an excellent optical information recording medium can be obtained.

Second, in a cyclic compound having a structure in which at least four pyrrole rings which may have a substituent are bonded via at least a carbon atom which may have a substituent or directly on a substrate, Two or more cyclic compounds which may be the same or different from each other are provided with a recording layer made of a compound having a substantially parallel facing structure (a so-called bridge structure) via a bonding site introduced into the pyrrole ring, and An optical information recording medium having a recording / reproducing wavelength of 380 to 500 (nm) is provided.

An example of the structure of the dimer having a substantially parallel face-to-face structure is shown in [Formula 13] (however, the present invention is not limited to the dimer) and has the following features. .

Embedded image

(1) The upper and lower rings may be the same or different from each other. (2) t, u, v, w, t ′, u ′, v ′, w ′ each represent an integer of 0 to 3, and (t + u + v + w) = (t ′)
+ U '+ v' + w ') = 3 or 4. (3) Y represents a binding site that connects pyrrole rings having different skeletons in the upper and lower parts, and a plurality of Y's may be introduced. (4) R _{1 to} R ₈ , X _{1 to} X ₄ , M, R ′ _{1 to} R ′ ₈ and M ′ are the same as described above.

In the second aspect of the present invention, since a substituent for bonding to another skeleton is introduced into the pyrrole ring, the distortion of the basic skeleton is reduced, and it is possible to cope with a shorter wavelength. Also,
The number of substituents and substitution positions that can be used is dramatically increased, and an excellent optical information recording medium can be obtained.

Third, in a cyclic compound having a structure in which at least four pyrrole rings which may have a substituent are bonded via at least a carbon atom which may have a substituent or directly on a substrate, Two or more cyclic compounds which may be the same or different from each other are provided with a recording layer made of a compound having a substantially parallel facing structure (a so-called sandwich structure) via a metal atom, and have a recording / reproducing wavelength of 380 to 500.
(nm) is provided.

Here, an example of the structure of the substantially parallel facing dimer is shown in [Formula 14] (however, the present invention is not limited to the dimer) and has the following features. .

Embedded image

(1) The upper and lower two rings may be the same or different. (2) t, u, v, w, t ′, u ′, v ′, w ′ each represent an integer of 0 to 3, and (t + u + v + w) = (t ′)
+ U '+ v' + w ') = 3 or 4. (3) R _{1 to} R ₈ , X _{1 to} X ₄ , M and R ′ _{1 to} R ′ ₈ are the same as described above.

According to the third aspect of the present invention, the wavelength can be shortened, and the number of usable substituents and substitution positions is dramatically increased, so that an excellent optical information recording medium can be obtained.

Fourthly, in a cyclic compound having a structure in which at least four pyrrole rings which may have a substituent are bonded via a carbon atom which may have a substituent or at least directly on a substrate, Two or more cyclic compounds which may be the same or different from each other are provided with a recording layer made of a compound having a substantially parallel facing structure (a so-called bridge structure) via a bonding site and a metal atom.
An optical information recording medium characterized by having a thickness of 0 to 500 (nm) is provided.

An example of the structure of the dimer having a substantially parallel face-to-face structure is shown in [Formula 15] (however, the present invention is not limited to the dimer) and has the following features. .

Embedded image

(1) The upper and lower two rings may be the same or different from each other. (2) t, u, v, w, t ′, u ′, v ′, w ′ each represent an integer of 0 to 3, and (t + u + v + w) = (t ′)
+ U '+ v' + w ') = 3 or 4. (3) Y represents a binding site that connects pyrrole rings of different skeletons vertically or a binding site that connects substituents introduced at meso positions of different skeletons, and a plurality of Y may be introduced. (4) R _{1 to} R ₈ , X _{1 to} X ₄ , M, and R ′ _{1 to} R ′ ₈ are the same as described above.

According to the present invention, a shorter wavelength is achieved, and the number of substituents and substitution positions that can be used is drastically increased, so that an excellent optical information recording medium can be obtained.

Fifth, in a cyclic compound having a structure in which at least four pyrrole rings which may have a substituent are bonded via a carbon atom which may have a substituent or directly bonded on at least a substrate, Two or more cyclic compounds which may be the same or different from each other form a recording layer comprising a compound having a bonding site introduced into the pyrrole ring and a compound having a substantially parallel facing structure (a so-called bridge structure) via a metal atom. And an optical information recording medium characterized by having a recording / reproducing wavelength of 380 to 500 (nm).

An example of the structure of the dimer having a substantially parallel face-to-face structure is shown in [Formula 16] (however, the present invention is not limited to the dimer) and has the following features. .

Embedded image

(1) The upper and lower two rings may be the same or different from each other. (2) t, u, v, w, t ′, u ′, v ′, w ′ each represent an integer of 0 to 3, and (t + u + v + w) = (t ′)
+ U '+ v' + w ') = 3 or 4. (3) Y represents a binding site that connects pyrrole rings having different skeletons in the upper and lower parts, and a plurality of Y's may be introduced. (4) R _{1 to} R ₈ , X _{1 to} X ₄ , M, and R ′ _{1 to} R ′ ₈ are the same as described above.

In the fifth aspect of the present invention, since a substituent for bonding to another skeleton is introduced into the pyrrole ring, the distortion of the basic skeleton is reduced, and a shorter wavelength can be accommodated. Also,
The number of substituents and substitution positions that can be used is dramatically increased, and an excellent optical information recording medium can be obtained.

Sixth, in the optical information recording medium according to any one of the above first to fifth, four pyrrole rings which may have a substituent may be bonded via a carbon atom which may have a substituent, or An optical information recording medium is provided, wherein the cyclic compound having a directly bonded structure is a porphyrin derivative represented by the following general formula (1).

Embedded image X _{1 to} X ₈ and R _{1 to} R ₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Represents an unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group. M is two hydrogen atoms, or a metal atom which may have oxygen or halogen, or (OR ₉ )
p, (OSiR ₁₀ R ₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r,
Represents a metal atom which may have (OCOR ₁₅ ) s. R ₉ ~
R ₁₅ is independently a hydrogen atom, a substituted or unsubstituted aliphatic,
Represents an aromatic hydrocarbon group, and p, q, r, and s represent an integer of 0 to 1.

Seventh, in the optical information recording medium according to any one of the first to fifth aspects, the four pyrrole rings which may have a substituent may be bonded via a carbon atom which may have a substituent, or An optical information recording medium is provided, wherein the cyclic compound having a directly bonded structure is a corrole derivative represented by the following general formulas (2) to (6).

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image R _{1 to} R ₈ and X _{1 to} X ₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted Represents an unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group. M is three hydrogen atoms, or a metal atom which may have oxygen or halogen, or (OR ₉ )
p, (OSiR ₁₀ R ₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r,
Represents a metal atom which may have (OCOR ₁₅ ) s. R ₉
To R ₁₅ independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and p, q, r, and s are 0 to 1;
Represents an integer.

Eighth, in the optical information recording medium according to any one of the first to fifth aspects, the four pyrrole rings which may have a substituent are bonded via a carbon atom which may have a substituent, or An optical information recording medium is provided, wherein the cyclic compound having a directly bonded structure is a porphyrin isomer represented by the following general formulas (7) to (11).

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image R _{1 to} R ₈ and X _{1 to} X ₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted Represents an unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group. M is two hydrogen atoms, or a metal atom which may have oxygen or halogen, or (OR ₉ )
p, (OSiR ₁₀ R ₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r,
Represents a metal atom which may have (OCOR ₁₅ ) s. R ₉ ~
R ₁₅ is independently a hydrogen atom, a substituted or unsubstituted aliphatic,
Represents an aromatic hydrocarbon group, and p, q, r, and s represent an integer of 0 to 1.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The recording material of the present invention is capable of recording and reproducing in a short wavelength region of 380 to 500 (nm), particularly 400 to 450 (nm), and has excellent recording and reproducing characteristics. That is, the recording material of the present invention has an arrangement in which the wavelength is made shorter than the monomolecular state by exciton interaction between molecules in order to correspond to a short wavelength. 500 (nm), especially 40
Since it is possible to use a compound that cannot respond to the recording / reproducing wavelength of 0 to 450 (nm), the variation of the substituent can be greatly improved.

By utilizing the short wavelength due to the exciton interaction, a compound having a long wavelength in a single molecule (eg, tetraphenylporphyrin derivative: tetraphenylporphyrin has a wide variety of substituents) can be used. In addition, the types of the substituents and the substitution positions can be greatly varied, and excellent recording / reproducing characteristics can be realized. In addition, the compound of the present invention having at least two molecules having a substantially parallel facing structure can use molecules having different properties, such as shortening the wavelength, improving solubility, preventing crystallization, lowering the decomposition temperature, and improving weather resistance. It is also possible to individually have the function of.

First, a description will be given of an arrangement for shortening the wavelength from the monomolecular state by the exciton interaction between molecules. Now consider the exciton interaction between two molecules. In this regard, there is a kasha model for the exciton interaction of two chromophores (FIG. 2). The classic explanation of bimolecular exciton theory by Kasha is as follows. Note that the rod-shaped molecules shown in FIG. 2 indicate chromophores that can be excited only in one axial direction. When a molecule is excited, the excited state is delocalized, as if two molecules had an excited dipole.

When the molecules are arranged in parallel as shown in FIG. 2A (face-to-face molecular structure), the dipoles excited by the oscillating electric field of the excitation light are either parallel or antiparallel.
In the parallel configuration, the energy level rises because the Coulomb force between the dipoles acts as a repulsive force. In the antiparallel configuration, the energy level decreases because the interaction between the dipoles becomes attractive. However, since the oscillating electric field is uniformly applied to the whole system, an antiparallel state cannot appear. Therefore, only the shift to the high energy side is observed.

Similarly, in the arrangement of FIG. 2B, a transition to a low energy level is observed. In the arrangement shown in FIG. 2C, both the high energy level and the low energy level are generated by the electric field in the y direction, and the energy level splitting due to the exciton interaction is observed.

As described above, when at least two molecules have a substantially opposing planar structure, it is possible to make the wavelength shorter than that of a single molecule. Further, by using the compound of the present invention as a recording layer, an effect of improving the wavelength dependence can be expected.
This usually has a problem that, since a cyclic compound has a high absorption coefficient due to a large π-conjugated system, the wavelength dependency becomes large, and the recording / reproducing characteristics are largely different with respect to laser wavelength fluctuation due to individual difference and environmental temperature. This is because, by forming a three-dimensional structure as in the present invention, an appropriate broadening of the absorption band may occur due to the intermolecular interaction, and the wavelength dependence of the recording / reproducing characteristics can be improved. .

A single molecule generally has a larger absorption per unit film thickness than a multimer. Therefore, in the case of a single molecule, the change in the recording / reproducing characteristics with respect to the film thickness fluctuation at the inner and outer circumferences of the disc may be large. There are also benefits.

Further, recording is generally carried out by diffusion of a dye into a substrate in addition to substrate deformation and dye decomposition, and in order to obtain good recording / reproducing characteristics, the amount of dye decomposition and the amount of dye diffusion are well determined. It is necessary to control the amount of dye decomposition and the amount of dye diffusion, which can be controlled by the film thickness. That is, if the dye film thickness is small, the dye diffusion contribution to the phase change becomes relatively large, and if the dye film thickness is large, the dye decomposition contribution to the phase change becomes relatively large. Therefore, fine film thickness adjustment is required in order to obtain good recording / reproducing characteristics. In this case, too, the amount of absorption per unit film thickness is more appropriate than that of a single molecule having a larger absorption amount per unit film thickness. The multimers of the invention are more advantageous.

Next, the relationship between the recording / reproducing wavelength for the optical information recording medium using the organic material and the maximum absorption wavelength of the solution or thin film spectrum of the organic material will be described. In the case of optical information recording media using organic materials, the maximum absorption wavelength in the solution or thin film spectrum of the organic material does not match the recording / reproducing wavelength, and the recording / reproducing wavelength must be shifted to the longer wavelength side with respect to the maximum absorption wavelength. is there.

The difference between the maximum absorption wavelength and the recording / reproducing wavelength of this recording material is as follows. When one absorption spectrum exists alone, the maximum wavelength of the refractive index shifts from the maximum absorption wavelength to the longer wavelength side, This is because it is impossible to achieve high reflectance at a wavelength (that is, the real part n of the complex refractive index is small and the imaginary part k of the complex refractive index is very large near the maximum absorption wavelength).

The reason for adapting the recording / reproducing wavelength to the vicinity of the maximum wavelength of the refractive index is that the recording is basically performed by the change in the refractive index before and after the recording of the recording material. It is preferable to use a wavelength region with a high refractive index, and the vicinity of the wavelength of the maximum refractive index is located at the base of the absorption spectrum. In the case of a write-once optical information recording medium, high reflectivity, that is, compatibility with ROM, (The real part n of the complex refractive index is large,
Since the condition that the imaginary part k of the complex refractive index is small can be achieved, both high modulation and high reflectivity can be achieved).

The amount of deviation between the maximum absorption wavelength and the maximum refractive index wavelength varies depending on the width of the absorption band and the magnitude of the absorption coefficient, but is about 20 (nm). Further, k (imaginary part of the complex refractive index) suitable for recording is approximately 0.03 to 0.15.
Therefore, 380 to 500 (nm), especially 400
In order to adjust the laser wavelength to about 450 (nm), it is preferable that the maximum absorption wavelength of the absorption spectrum in the solution or film of the recording material is in the range of about 360 to 420 (nm).

Although there are many compounds having absorption in a short wavelength region, the conjugated system is usually very short, so that the molecular absorption coefficient is generally low (that is, the real part n of the complex refractive index is small). When these organic materials having a low molecular extinction coefficient are used, high reflectivity, which is the greatest feature of an optical information recording medium using an organic material, is impaired, that is, compatibility with a ROM disk cannot be maintained. The value will be halved. However, it has been found as a result of earnest studies that the recording material of the present invention has a maximum absorption wavelength in this wavelength region and a large molecular extinction coefficient.

The recording material of the present invention has a sufficient solubility in an organic solvent which can be generally used for an optical disk, and does not cause crystallization when a film is formed on a substrate by spin coating or the like. It was also found that it also had the feature. Therefore, an optical information recording medium having a high reflectance can be easily obtained, and compatibility with a ROM disk can be obtained.
There is a great merit that a write-once high-density optical information recording medium corresponding to a short wavelength of 0 to 500 (nm), particularly 400 to 450 (nm) can be obtained.

The compounds which can be used in the present invention include, for example, those having the structures represented by formulas (1) to (11). A pair of compounds having a substantially parallel face-to-face structure has the same skeleton and the same substituent. May be different.

Among these, corroles represented by the general formulas (2) to (6) are molecules in which one meso carbon atom is formally removed from porphyrin, and are large aromatic rings.
That is, as shown in [Chemical formula 1], porphyrin is a compound in which a pyrrole ring optionally having four substituents is bonded by one carbon atom (meso carbon atom) which may each have a substituent. However, the color derivative which can be used in the present invention has a pyrrole ring which may have a substituent at least at one of the four positions to which the four pyrrole rings are bonded, wherein the pyrrole ring which may have a substituent is directly bonded not via a carbon atom. Is a compound having the structure shown below.

Now, the number of carbon atoms which may be substituted at the four positions for bonding the pyrrole ring which may be substituted is
When represented by [a, b, c, d], the compound used in the present invention has [a, b, c, d] = 3, and any one of a, b, c, and d is 0 (porphyrin) If [1,
1,1,1] = 4). According to this notation, the compound of general formula (2) is [1,1,1,0], the compound of general formula (3) is [2,0,1,0], and the compound of general formula (4) Is [2,1,0,0], and the compound of general formula (5) is [3,
0,0,0], the compound of the general formula (6) is [3,0,0,
0].

The porphyrin isomers represented by the general formulas (7) to (11) are large aromatic rings like porphyrin. These porphyrin isomers which can be used in the present invention have a total of four carbon atoms which may have a substituent connecting the four pyrrole rings, and at least one of the porphyrin isomers in which the pyrrole ring is a carbon atom. Is a compound having a directly bonded structure.

According to the notation method similar to the above, the compound of the general formula (7) is represented by [2,0,2,0] and the general formula (8)
Is [2,1,1,0], the compound of formula (9) is [2,1,0,1], the compound of formula (10) is [3,0,1,0], The compound of the formula (11) is [3,
0, 1, 0].

In the present invention, R _{1 to} R ₈ and X _{1 to} X ₄ ,
Further, R ′ _{1 to} R ′ ₈ and X ₁ t, X ₂ u, X ₃ v, X ₄ w, X
₁ t ', X ₂ u', X ₃ v ', X ₄ w' (where t, t ', u,
u ′, v, v ′, w and w ′ are integers from 0 to 3) each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, Alternatively, it represents an unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group.

Examples of the alkyl group in the unsubstituted alkyl group and the unsubstituted alkoxy group include a linear or branched alkyl group.

The substituted alkyl group and the substituted alkyl group in the substituted alkoxy group include hydroxy-substituted alkyl groups such as 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group and 2-hydroxypropyl group; Carboxy-substituted alkyl groups such as methyl group, 2-carboxyethyl group and 3-carboxypropyl group; cyano-substituted alkyl groups such as 2-cyanoethyl group and cyanomethyl group; amino-substituted alkyl groups such as 2-aminoethyl group; 2-chloroethyl A halogen atom-substituted alkyl group such as a group, 3-chloropropyl group, 2-chloropropyl group or 2,2,2-trifluoroethyl group; a phenyl group such as a benzyl group, a p-chlorobenzyl group or a 2-phenylethyl group Alkyl group; 2-methoxyethyl group, 2-ethoxyethyl , 2- (n) propoxyethyl group, 2- (iso) propoxy ethyl group, 2- (n)
Butoxyethyl group, 2- (iso) butoxyethyl group,
Alkoxy-substituted alkyl groups such as 2- (2-ethylhexyloxy) ethyl group, 3-methoxypropyl group, 4-methoxybutyl group and 2-methoxypropyl group;
Methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2- (n) propoxyethoxy) ethyl group, 2- (2- (iso) propoxyethoxy) ethyl group, 2- (2- (N) butoxyethoxy) ethyl group, 2- (2- (iso) butoxyethoxy) ethyl group, 2- {2- (2-ethylhexyloxy) ethoxy} ethyl group or other alkoxyalkoxy-substituted alkyl group; aryloxyethyl group A substituted alkyl group such as, 2-phenoxyethyl group, 2-benzyloxyethyl group;
2-acetyloxyethyl group, 2-propionyloxyethyl group, 2- (n) butyryloxyethyl group, 2-
(Iso) an acyloxy-substituted alkyl group such as a butyryloxyethyl group or a 2-trifluoroacetyloxyethyl group; a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, (n) a propoxycarbonylmethyl group,
so) propoxycarbonylmethyl group, (n) butoxycarbonylmethyl group, (iso) butoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyl group, benzyloxycarbonylmethyl group, furfuryloxycarbonylmethyl group, tetrahydrofurfuryloxycarbonylmethyl group Group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2- (n) propoxycarbonylethyl group, 2- (iso) propoxycarbonylethyl group, 2- (n) butoxycarbonylethyl group, 2- (iso) ) Butoxycarbonylethyl group,
Substituted or unsubstituted alkoxycarbonyl-substituted alkyl groups such as 2- (2-ethylhexyloxycarbonyl) ethyl group, 2-benzyloxycarbonylethyl group, 2-furfuryloxycarbonylethyl group; 2-methoxycarbonyloxyethyl group; -Ethoxycarbonyloxyethyl group, 2- (n) propoxycarbonyloxyethyl group, 2- (iso) propoxycarbonyloxyethyl group, 2- (n) butoxycarbonyloxyethyl group, 2- (iso) butoxycarbonyloxyethyl group Substituted or unsubstituted alkoxycarbonyloxy-substituted alkyl groups such as, 2- (2-ethylhexyloxycarbonyloxy) ethyl group, 2-benzyloxycarbonyloxyethyl group, 2-furfuryloxycarbonyloxyethyl group; Furyl, such as heterocyclic-substituted alkyl group such as tetrahydrofurfuryl group.

Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.

The following are specific examples of the alkyl group in the alkyl group and the alkoxy group. Note that these alkyl groups may be substituted with a substituent such as a halogen atom. Methyl group, ethyl group, n
-Propyl, n-butyl, isobutyl, n-pentyl, neopentyl, isoamyl, 2-methylbutyl, n-hexyl, 2-methylpentyl, 3-
Methylpentyl group, 4-methylpentyl group, 2-ethylbutyl group, n-heptyl group, 2-methylhexyl group, 3
-Methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2-ethylpentyl group, 3-ethylpentyl group, n-octyl group, 2-methylheptyl group, 3-
Primary alkyl groups such as methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 2-ethylhexyl group, 3-ethylhexyl group, n-nonyl group, n-decyl group and n-dodecyl group; isopropyl group, sec -Butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1,
2-dimethylpropyl group, 1-methylheptyl group, 1-
Ethylbutyl group, 1,3-dimethylbutyl group, 1,2-
Dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1-methylhexyl group, 1-ethylheptyl group, 1
-Propylbutyl group, 1-isopropyl-2-methylpropyl group, 1-ethyl-2-methylbutyl group, 1-propyl-2-methylpropyl group, 1-methylheptyl group,
1-ethylhexyl group, 1-propylpentyl group, 1-
Isopropylpentyl group, 1-isopropyl-2-methylbutyl group, 1-isopropyl-3-methylbutyl group,
Secondary alkyl groups such as 1-methyloctyl group, 1-ethylheptyl group, 1-propylhexyl group, 1-isobutyl-3-methylbutyl group; tert-butyl group, tert
Tertiary alkyl groups such as -hexyl group, tert-amyl group and tert-octyl group; cyclohexyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4
And cycloalkyl groups such as -tert-butylcyclohexyl group, 4- (2-ethylhexyl) cyclohexyl group, bornyl group, isobornyl group and adamantane group.

Specific examples of the aryl group include a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a tert-butylphenyl group, a di (tert-butyl) phenyl group, a butylphenyl group and a methoxy group. Examples thereof include a phenyl group, a dimethoxyphenyl group, a trimethoxyphenyl group, and a butoxyphenyl group. These aryl groups may be substituted with a substituent such as halogen.

In the general formulas (1) to (11), M represents 2 or 3 hydrogen atoms, a divalent, trivalent or tetravalent metal atom which may have oxygen or halogen, or (OR ₉ )
p, (OSiR ₁₀ R ₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r,
Represents a metal atom which may have (OCOR ₁₅ ) s. R ₉ ~
R ₁₅ is independently a hydrogen atom, a substituted or unsubstituted aliphatic,
Represents an aromatic hydrocarbon group, and p, q, r, and s represent an integer of 0 to 1.

Specific examples of M include Ib group, IIa group, II
Group b, IIIa, IVa, IVb, Vb, VIb, VII
There are Group b and Group VIII metals, oxides of these metals, halides of these metals, hydroxides of these metals, and the like. Further, some of the above metals have a substituent.

The above metals include Cu, Zn, Mg,
Al, Ge, Ti, Sn, Pb, Cr, Mo, Mn, F
e, Co, Ni, In, Pt, Pd, etc., oxides include TiO, VO, etc., halides include AlCl, FeCl, InCl, etc., and hydroxides include Al (OH). Etc.

When the metal has a substituent, examples of the metal include Al, Ti, Si, Ge, and Sn.
Examples of the substituent include an aryloxyl group, an alkoxyl group, a trialkylsiloxyl group, a triarylsiloxyl group, a trialkoxysiloxyl group, a triaryloxysiloxyl group, a trityloxyl group, and an acyloxyl group.

In the case of a so-called sandwich structure in which two molecules form a substantially parallel facing structure with respect to one central metal, La, Ce, Pr, Nd, Pm,
Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Y
Lanthanoids such as b and Lu, and actinoids such as Th and U can be used.

The method for synthesizing the porphyrin isomer of the present invention is described, for example, in Angew. Chem. Int. Ed. Engl. 1993, 32, No. 11, p.
The method described in p.1600-1604 and the method for synthesizing corrole are described in, for example, TetRahedRon Letters, Vol.38, No.23,
pp. 4113-4116, 1977 can be used.

The optical information recording medium to which the present invention is applied has, for example, a structure as shown in FIG. That is, the recording layer 2 and the reflective layer 3 are sequentially formed on the substrate 1, and the protective layer 4 is further formed thereon. In this optical information recording medium, recording is performed by a heat mode method in which pits are formed by heat generated by irradiating the recording layer 2 with laser light.

(Recording Layer) The recording layer is basically composed of a porphyrin isomer, and if necessary, for example, a polymethine dye, a squarylium-based, a coronium-based, a pyrylium-based, a naphthoquinone-based, an anthraquinone (indanthrene) -based, or xanthene-based A dye, a triphenylmethane-based, an azulene-based, a tetrahydrocholine-based, a phenanthrene-based, a triphenothiazine-based dye, and a metal complex compound may be appropriately mixed and used.

In the above dyes, metals and metal compounds such as In, Te, Bi, Al, Be, TeO ₂ , SnO,
As, Cd and the like can be used in the form of dispersion mixing or lamination. Further, various materials such as a polymer material, for example, an ionomer resin, a polyamide resin, a vinyl resin, a natural polymer, silicone, and a liquid rubber, or a silane coupling agent may be dispersed and used in the dye. It can be used together with a stabilizer (for example, a transition metal complex), a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, a plasticizer, and the like for the purpose of improving the properties.

When the coating method is used, the above-mentioned dyes and the like are dissolved in an organic solvent, and the coating is performed by a conventional coating method such as spraying, roller coating, dipping, and spin coating. Spin coating is most preferred.

Examples of the organic solvent include alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, amides such as N, N-dimethylacetamide and N, N-dimethylformamide, and dimethyl sulfoxide. Sulfoxides, ethers such as tetrahydrofuran, dioxane, diethyl ether and ethylene glycol monomethyl ether; esters such as methyl acetate and ethyl acetate; and aliphatic halogenated carbons such as chloroform, methylene chloride, dichloroethane, carbon tetrachloride and trichloroethane. Or benzene, xylene,
Aromatic substances such as monochlorobenzene and dichlorobenzene, cellsolves such as methoxyethanol and ethoxyethanol, and hydrocarbons such as hexane, pentane, cyclohexane and methylcyclohexane can be used.

The thickness of the recording layer is suitably 100 to 10 μm, preferably 200 to 2000 μm.

(Substrate) The required characteristics of the substrate are that it must be transparent to the laser beam used only when recording / reproducing from the substrate side, and transparent when recording / reproducing from the recording layer side. No need.

As the substrate material, for example, polyester,
Plastic such as acrylic resin, polyamide, polycarbonate resin, polyolefin resin, phenol resin, epoxy resin, and polyimide, glass, ceramic, and metal can be used.

When only one substrate is used, or when two substrates are used in a sandwich form, guide grooves and guide pits for tracking and preformats such as address signals are formed on the surface of the substrate. There is a need.

(Intermediate Layer) Layers provided other than the substrate, the recording layer, the reflective layer, and the protective layer, including the undercoat layer and the like, are herein referred to as intermediate layers. This intermediate layer comprises (a) improved adhesion, (b) a barrier against water or gas, (c) improved storage stability of the recording layer, (d) improved reflectance, and (e) substrate from solvent. And (f) formation of guide grooves, guide pits, preformats, and the like.

For the purpose of (a), a polymer material, for example,
For example, ionomer resin, polyamide resin, vinyl resin,
Seeds of natural resin, natural polymer, silicone, liquid rubber, etc.
Uses various polymer substances and silane coupling agents
Can be. For the purposes of (b) and (c)
Is an inorganic compound other than the above polymer material, for example, Si
O _Two, MgF_Two, SiO, TiO_Two, ZnO, TiN, S
metals such as iN, or metalloids such as Zn, Cu, N
Use i, Cr, Ge, Se, Au, Ag, Al, etc.
be able to. For the purpose of (d), metal,
For example, Al, Ag, etc., or an organic thin film having metallic luster, such as
For example, methine dyes, xanthene dyes, etc. can be used.
You. UV curable trees for the purposes of (e) and (f)
Fat, thermosetting resin, thermoplastic resin, etc. can be used
You.

The thickness of the undercoat layer is suitably 0.01 to 30 μm, preferably 0.05 to 10 μm.

(Protective Layer / Hard Coat Layer on Substrate Surface) The protective layer or hard coat layer on the substrate surface (a) protects the recording layer (reflection / absorption layer) from scratches, dust, dirt, etc., (b)
It is used for the purpose of improving the storage stability of the recording layer (reflection / absorption layer) and (c) improving the reflectance. For these purposes, the materials shown in the undercoat layer can be used.

As the inorganic material, SiO, SiO ₂ or the like can be used. As the organic material, polymethyl acrylate, polycarbonate, epoxy resin, polystyrene, polyester resin, vinyl resin, cellulose, aliphatic hydrocarbon resin, aromatic resin, etc. Aromatic hydrocarbon resin, natural rubber, styrene butadiene resin, chloroprene rubber, wax, alkyd resin, drying oil, heat softening resin such as rosin, and heat melting resin can also be used. Among the above materials, the most preferable substance for the protective layer or the hard coat layer on the substrate surface is an ultraviolet curable resin having excellent productivity.

The thickness of the protective layer or the hard coat layer on the substrate surface is 0.01 to 30 μm, preferably 0.05 to 1 μm.
0 μm is appropriate.

In the present invention, the undercoat layer, the protective layer,
The hard coat layer on the substrate surface may contain a stabilizer, a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, a plasticizer, and the like, as in the case of the recording layer.

(Metal Reflective Layer) The reflective layer may be made of a metal, a semi-metal, etc., which can provide a high reflectivity by itself and are hardly corroded.
Examples of the material include Au, Ag, Cu, Cr, Ni, and Al, and preferably Ag and Al, which can achieve high reflectance even at a short wavelength. These metals and metalloids may be used alone or as two or more alloys. Further, a dielectric multilayer film may be used.

Examples of the film forming method include vapor deposition and sputtering, and the film thickness is 50 to 3000 °, preferably 100 to 1000 °.

(Adhesive Layer) An adhesive layer is necessary when two thin substrates are bonded together as seen in DVD media. Particularly preferred in the present invention is a hot-melt type (hot-melt type) adhesive or an ultraviolet curable type adhesive.

The ultraviolet curable adhesive is an adhesive which is cured by the initiation of radical polymerization upon irradiation with ultraviolet light. The composition is generally (1) acrylic oligomer, (2)
The oligomer comprises an acrylic monomer, (3) a photopolymerization initiator, and (4) a polymerization inhibitor.
Polyurethane-based, epoxy-based acrylate, etc.
Benzophenone, benzoin ether and the like can be used as the photopolymerization initiator.

A hot-melt adhesive is one in which a liquid adhesive is hardened by solvent volatilization or reaction and develops an adhesive force, whereas an ordinary-temperature solid thermoplastic resin develops an adhesive force by a physical change of heat melting and cooling and solidification. It is. Hot melt adhesive
EVA, polyester, polyamide, polyurethane and the like can be used.

[0088]

Next, the present invention will be described in detail with reference to examples. Compounds that can be used in the present invention (formula 28)
[Formula 30], [Formula 32]-[Formula 35], [Formula 37]-
The compound of [Formula 80] was selected. However, the maximum absorption wavelength and the molecular extinction coefficient in a dichloromethane solution in the structural formula (H atom was omitted) were measured (Tables 1 and 2: However, Table 1).
And in Table 2, there are compounds for which the molecular extinction coefficient could not be measured due to the problem of the amount of synthesis). As a comparison of the substantially parallel face-to-face structures of the present invention, the results of measuring the maximum absorption wavelengths of the single-molecule tetraphenylporphyrin derivatives ([Chemical Formula 82] to [Chemical Formula 85]) show that each has an absorption wavelength of 410 (nm) or more. However, by using the substantially parallel face-to-face structure of the present invention, it is possible to reduce the maximum absorption wavelength to 400 (nm) or less even when a tetraphenylporphyrin derivative is used (for example, [Formula 38]). You can see that it is. Therefore, it has been proved that the compound of the present invention can cope with shorter wavelengths and has a wide variety of substituents. Furthermore, in order to confirm the effect of shortening the wavelength associated with the substantially parallel face-to-face structure of the present invention, [Formula 30] (λmax = 393.0 n)
m) as a comparison of the non-parallel facing structure
= 414.0 nm) and [Formula 35] (λmax = 400.
0 nm) as a comparison [36] (λ
max = 404.0 nm). As a result,
It was confirmed that the substantially parallel facing structure of the present invention was very effective for shortening the wavelength.

[0089]

[Table 1]

[0090]

[Table 2]

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Next, a thin film was formed on the glass substrate (without grooves) using the compound of the above formula [Chemical Formula 30], and the change in reflection spectrum due to recording was examined. For confirmation of recording mark generation and measurement of the reflection spectrum of the recording material accompanying the recording mark generation, as shown in FIG.
The evaluation was performed by an evaluation system including an SHG laser 11, a pulse generator 12, an acousto-optic modulator (AOM) 13, an optical microscope 14, and a microspectrophotometer 15. In addition, SH
G Laser is Hitachi Metals' all-solid SHG laser ICD4
20, the wavelength of this laser is 420 (nm), and the output of the laser is about 10 mw. With the recording by the laser irradiation, the reflectance of the thin film sample became about 70% of the initial reflectance, and it was confirmed that recording was possible with laser light having a wavelength of 420 (nm). From these measurement results, the porphyrin isomers specified in the present invention have sufficient solubility and 380 to 500 (n
m), in particular, recording / reproduction is possible with a laser wavelength of 400 to 450 (nm), and a conventional CD-R, DVD-
It turned out that it has a molecular extinction coefficient almost equivalent to R material.

[0092]

According to the optical information recording medium using the compound of the present invention as a recording layer, the solubility is high, the film is not crystallized, and 380 to 500 (nm), especially 400
An optical information recording medium having high reflectivity and high contrast in a wavelength range of from 450 to 450 (nm) can be provided. The compound having a substantially parallel face-to-face structure of the present invention usually has 380 to 5
00 (nm), in particular, a material that cannot be adapted to the recording / reproducing wavelength of 400 to 450 (nm) can be shortened.
The variation of substituent introduction is dramatically improved, and it is possible to easily improve the problems of the conventional porphyrins such as shortening the wavelength, improving solubility, preventing crystallization, and reducing the decomposition temperature. . Further, a pair of compounds having a substantially parallel face-to-face structure may be the same or different from each other, and when the two are different from each other, it is necessary to shorten the wavelength, improve the solubility, and prevent crystallization, which are the characteristics required for an optical information recording medium. It is also possible to individually provide different functions in order to improve the decomposition temperature, improve the weather resistance, and the like, and to provide an optical information recording medium with excellent reliability. Further, by an optical information recording medium using the compound of the present invention as a recording layer,
As before, 380 to 500 (nm), especially 40
An optical information recording medium that is compatible with ROM even in a short wavelength range of 0 to 450 (nm) can be provided.

[Brief description of the drawings]

FIG. 1 is a diagram showing a layer configuration of an example of an optical information recording medium of the present invention.

FIGS. 2 (a), (b) and (c) are ksha model diagrams relating to bimolecular exciton action.

FIG. 3 is a diagram showing a method of measuring a reflection spectrum of a recording material.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Recording layer 3 Reflective layer 4 Protective layer

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yasunobu Ueno 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Tatsuya Tomura 1-3-6 Nakamagome, Ota-ku, Tokyo Stock In Ricoh Company (72) Inventor Tsutomu Sato 1-3-6 Nakamagome, Ota-ku, Tokyo F-term in Ricoh Company (reference) 2H111 EA03 EA12 EA22 EA32 EA41 FA01 FB42 4C050 PA01 PA02 PA03 PA05 PA06 PA20 5D029 JA04

Claims (8)

[Claims] 1. A cyclic compound having a structure in which at least four pyrrole rings which may have a substituent are bonded at least on a substrate via a carbon atom which may have a substituent or directly bonded thereto. The above-mentioned cyclic compounds which may be the same or different from each other are provided with a recording layer made of a compound having a substantially parallel facing structure (bridge structure) via a bonding site,
An optical information recording medium having a recording / reproducing wavelength of 380 to 500 (nm). 2. A cyclic compound having a structure in which at least four pyrrole rings which may have a substituent are bonded at least on a substrate via a carbon atom which may have a substituent or directly bonded thereto. The above-mentioned cyclic compounds which may be the same or different from each other are provided with a recording layer made of a compound having a substantially parallel facing structure (bridge structure) via a bonding site introduced into the pyrrole ring, and a recording / reproducing wavelength. 3
An optical information recording medium having a thickness of 80 to 450 (nm). 3. A cyclic compound having a structure in which at least four pyrrole rings which may have a substituent are bonded at least on a substrate via a carbon atom which may have a substituent or directly bonded thereto. The above-mentioned cyclic compounds which may be the same or different from each other are provided with a recording layer made of a compound having a substantially parallel facing structure (sandwich structure) via a metal atom, and have a recording / reproducing wavelength of 380 to 500 (nm). An optical information recording medium characterized in that: 4. A cyclic compound having a structure in which at least four pyrrole rings which may have a substituent are bonded at least on a substrate via a carbon atom which may have a substituent or directly bonded thereto. The above-mentioned cyclic compounds which may be the same or different from each other are provided with a recording layer made of a compound having a substantially parallel facing structure (bridge structure) via a bonding site and a metal atom, and have a recording / reproducing wavelength of 380 to 500 ( n
m) An optical information recording medium characterized in that: 5. A cyclic compound having a structure in which at least four pyrrole rings which may have a substituent are bonded at least on a substrate via a carbon atom which may have a substituent or directly bonded thereto. The above-mentioned cyclic compounds which may be the same or different from each other are provided with a recording layer made of a compound having a substantially parallel facing structure (bridge structure) via a bonding site and a metal atom introduced into the pyrrole ring, and An optical information recording medium having a recording / reproducing wavelength of 380 to 500 (nm). 6. The optical information recording medium according to claim 1, wherein the four pyrrole rings which may have a substituent are bonded via a carbon atom which may have a substituent, or An optical information recording medium, wherein the cyclic compound having a directly bonded structure is a porphyrin derivative represented by the following general formula (1). Embedded image R _{1 to} R ₈ and X _{1 to} X ₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted Represents an unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group. M is two hydrogen atoms, or a metal atom which may have oxygen or halogen, or (OR ₉ )
p, (OSiR ₁₀ R ₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r,
Represents a metal atom which may have (OCOR ₁₅ ) s. R ₉ ~
R ₁₅ is independently a hydrogen atom, a substituted or unsubstituted aliphatic,
Represents an aromatic hydrocarbon group, and p, q, r, and s represent an integer of 0 to 1. ) 7. The optical information recording medium according to claim 1, wherein the four pyrrole rings which may have a substituent are bonded via a carbon atom which may have a substituent, or An optical information recording medium, wherein the cyclic compound having a directly bonded structure is a corrole derivative represented by the following general formulas (2) to (6). Embedded image Embedded image Embedded image Embedded image Embedded image R _{1 to} R ₈ and X _{1 to} X ₃ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted Represents an unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group. M is three hydrogen atoms, or a metal atom which may have oxygen or halogen, or (OR ₉ )
p, (OSiR ₁₀ R ₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r,
Represents a metal atom which may have (OCOR ₁₅ ) s. R ₉ ~
R ₁₅ is independently a hydrogen atom, a substituted or unsubstituted aliphatic,
Represents an aromatic hydrocarbon group, and p, q, r, and s represent an integer of 0 to 1. ) 8. The optical information recording medium according to claim 1, wherein the four pyrrole rings which may have a substituent are bonded via a carbon atom which may have a substituent, or Cyclic compounds having a directly bonded structure are represented by general formulas (7) to (7):
An optical information recording medium, which is a porphyrin isomer represented by (11). Embedded image Embedded image Embedded image Embedded image Embedded image R _{1 to} R ₈ and X _{1 to} X ₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted Represents an unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group. M is two hydrogen atoms, or a metal atom which may have oxygen or halogen, or (OR ₉ )
p, (OSiR ₁₀ R ₁₁ R ₁₂ ) q, (OPOR ₁₃ R ₁₄ ) r,
Represents a metal atom which may have (OCOR ₁₅ ) s. R ₉ ~
R ₁₅ is independently a hydrogen atom, a substituted or unsubstituted aliphatic,
Represents an aromatic hydrocarbon group, and p, q, r, and s represent an integer of 0 to 1.