JP2003103932A - Azaporphyrin compound and its application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an additional recording type optical recording medium capable of good recording and regeneration by leaser beams 300-500 nm and/or 500-700 nm and/or 700-900 nm in wavelength and coloring matter for additional recording type optical recording. SOLUTION: In the optical recording medium, at least one compound is selected from azaporphyrin compounds in which a central metal is coordinated with two azaporphyrin rings to be incorporated in a recording layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye, a pigment, a photoelectric functional material, and a recording / storing material, and more particularly to recording / reproducing information by blue and / or red laser light and / or near infrared laser light. The present invention relates to an azaporphyrin-based compound useful as a recording dye for a possible large-capacity write-once type optical recording medium. The present invention also relates to an optical recording medium containing the azaporphyrin compound.

In addition, the present invention is particularly applicable to wavelengths 400-41.
The present invention relates to an optical information recording medium having a recording layer capable of high density recording for recording with a 0 nm blue-violet laser.

[0003]

2. Description of the Related Art CD-R is a write-once type optical recording medium compatible with the compact disc (hereinafter abbreviated as CD) standard.
It is known that (CD-Recordable) has been proposed and developed, and is widely used for music reproduction and information terminals.

Recording / reproducing of this optical recording medium is generally performed by 7
A near infrared semiconductor laser of 70 nm to 840 nm is used, and signal recording is performed in a heat mode on a recording layer made of an organic dye or the like on a substrate. That is, when the recording layer is irradiated with laser light, the organic dye generates heat due to light absorption, and the generated heat forms pits in the recording layer. Then, the recording signal is detected by the difference in reflectance between the portion where the pit is formed and the portion where the pit is not formed when the laser beam is irradiated.

Since it conforms to the CD standard of Red Book, Orange Book, etc.
Since it has a feature of being compatible with a D-ROM player and has been rapidly and inexpensively provided in recent years, it has become widely used explosively for image storage and backup of personal computers and for music. At present, with the improvement of the laser power of the CD-R player, it has become possible to record at 12x speed and 16x speed, and the time required for 70 minutes or more per disc at first is shortened to 5 minutes or less. In high-speed recording, it is necessary to irradiate high-power laser because pits are formed in a short time. However, high-power laser irradiation imposes a heavy burden on the player, and in order to enable higher-speed recording, A dye that is well decomposed even at low power, that is, a highly sensitive dye is desired.

A write-once recordable optical recording medium in which a dye is used as a recording layer and a reflective layer is provided on the recording layer in order to increase the reflectivity is, for example, Optical Data Storage 1989 Techni
Since it was disclosed in calDigest Series Vol. 1, 45 ('89), a write-once compact disc (Compact Disc Record) using a cyanine dye or a phthalocyanine dye in the recording layer was used.
able: CD-R) is widely used in the market. These media can be recorded with a 780 nm semiconductor laser, and are equipped with a 780 nm semiconductor laser,
Commercially available CD players and CDs widely used in the market
It has the feature that it can be played on a ROM player.

A technique of using a phthalocyanine compound for a recording layer of a recording medium such as an optical disk or an optical card is disclosed in Japanese Patent Laid-Open No. 61-61160.
-154888, 61-197280, 61-246091, 62-39286, 63-37991, 63-39388, etc., but these phthalocyanines are sensitive. However, it was insufficient for optical recording media in terms of refractive index and recording characteristics. A compound that improves it is disclosed in
Although it is described in Japanese Patent Laid-Open No. 3-62878, there is a problem with the recording characteristics when writing with a laser beam, and it is still not sufficient for practical use. In addition, JP-A-4-214388 and JP-A-5-238150
JP-A No. 5-247363 discloses a phthalocyanine compound having a fluorine atom introduced, but the introduction of a fluorine group improves the adhesion to a substrate resin but has a low sensitivity.
In the compound described in JP-A No. 7-90186, the compound having a bromine atom introduced into the phthalocyanine ring cannot be said to have sufficient performance in high-speed and high-density recording. When bromine and iodine groups are introduced, there is a problem that the solubility is lowered and the solubility in the spin coat solvent at the time of producing the recording medium is lowered.

Further, WO 98/14520 describes a compound in which a phthalocyanine compound is modified with a substituent such as a formyl group, but there is no description of a metal-based compound, and the bonding of an organic group is sufficient to improve the sensitivity. Was not.

In addition, the recording capacity of the above-mentioned existing medium is about 680 MB, and the capacity is not sufficient when recording moving pictures. In recent years, along with the dramatic increase in the amount of information, there is an increasing demand for higher density and larger capacity of information recording media.

As a means for increasing the density of the recording medium,
The beam spot can be reduced by shortening the laser wavelength used for recording / reproducing and increasing the numerical aperture (NA: Numerical Aperture) of the objective lens. Then, as a short wavelength laser used in an optical disc system, 500 nm to 700 nm, further 630 nm to 690 nm, specifically 680
nm, 670 nm, 660 nm, 650 nm, 635n
Red lasers such as m have been put to practical use. Thus, it has become possible to manufacture an optical recording medium capable of recording a moving image and recording a large amount of information by shortening the wavelength of a semiconductor laser, increasing the numerical aperture of an objective lens, and data compression technology. The optical recording media proposed to date include magneto-optical recording media, phase change recording media, chalcogen oxide optical recording media, organic dye optical recording media, and the like.
The organic dye-based optical recording medium is considered to be superior in that it is inexpensive and easy in the process. In consideration of such a situation, as an optical recording medium capable of recording and reproducing a moving image with a density higher than that of a CD and a quality comparable to that of a TV, it can be reproduced by a commercially available DVD video player or DVD-ROM player, which has an oscillation wavelength of 630 to 630. A write-once type digital multipurpose disc (hereinafter abbreviated as DVD-R) was developed as a write-once type optical recording medium capable of recording with a red semiconductor laser of 690 nm. DVD-R
Is a once-writable optical recording medium having a recording capacity of 3.9 GB or 4.7 GB, and particularly recently, a DVD-R medium having a single-sided 4.7 GB capacity has begun to be supplied to the market. The DVD-R medium also has a laminated structure in which a cyanine-based dye, an azo-based dye, etc. are used as a recording layer and a reflective layer is provided, and is characterized by a disc structure in which two 0.6 mm-thick substrates are bonded together. I am trying. For optical discs having good recording characteristics suitable for this capacity, media for high-speed recording are being actively developed at present.

Further, it is expected that higher density recording will be required in the future, and the amount of information is 15 to 30 GB.
It is expected to reach. It is unavoidable to use a laser having a shorter wavelength as a means for realizing the recording density. Therefore, as a recording dye to be used in future organic dye-based optical recording media, a dye having good recording characteristics in the wavelength range of 300 nm to 500 nm is desired.

By the way, a DVD having an organic dye as a recording layer
Japanese Patent Application Laid-Open No. HEI 10-104, regarding a medium capable of recording at a higher density than -R.
-302310 discloses that a laser having an oscillation wavelength of 680 nm or less is used to achieve a recording capacity of 8 GB or more. According to the proposal of the publication, it is 10 to 177 μm.
Large-capacity recording of 8 GB or more is achieved by converging laser light of 680 nm or less with an objective lens having a high numerical aperture of 0.7 or more through a thick light transmission layer.

On the other hand, in recent years, the oscillation wavelengths 390 to 390
A 410 nm laser using a GaN-based material as a 430 nm blue laser and an SHG laser having a wavelength of 425 nm by combining a semiconductor laser and an optical waveguide element have been developed [eg, Nikkei Electronics, No. 708, p. 117, January 26, 1998], the development of a dye for a blue semiconductor laser adapted to such a laser is currently being developed.

Furthermore, since the beginning of 1999, an oscillation wavelength of 400
As a GaN-based semiconductor laser with blue-violet emission of ~ 410nm is being tested (Nichia Corporation), HDTV (high definiti) with higher density capacity of 15GB or more per side.
Studies have begun on a medium (hereinafter referred to as an HD-DVD-R medium) capable of recording a moving image for about two hours with an image quality comparable to that of broadcasting. With HD-DVD-R media having such a high-density capacity, it is possible to record for about 6 hours if the image quality is similar to that of current broadcasts, so it is possible to use a VTR for home use.
It is also attracting attention as a new recording medium to replace.
As a proposal using a phase change type inorganic recording film, Nikkei Electronics September 6, 1999 issue (No. 75) has already been proposed.
The technical outline is introduced on page 117 of 1).

Until now, as dyes which can be recorded by a blue laser of 400 nm to 500 nm, for example, JP-A-4-
Cyanine dye compounds described in JP-A-74690 and JP-A-6-40161, and JP-A-7-304256.
JP-A-7-304257 and JP-A-8-1
No. 27174, JP-A Nos. 11-334207 and 2001-39032, and other polyene dye compounds described in JP-A-4-78576 and JP-A-4-89279. Azo dye compounds described in JP-A-11-334204 and JP-A-11-334205, dicyanovinylphenyl dye compounds described in JP-A-11-304206, JP-A-2000-43423 and JP-A-2001-96918. Coumarin compound disclosed in JP-A-2000-163799, pyrimidine compound disclosed in JP-A-2000-328028, naphthalocyanine compound disclosed in JP-A-2000-228028, hetero five-membered ring compound disclosed in JP-A-2000-335110, JP-A 2000-343824. Bisazole compound Aminopyridine compound of JP 2000-343825, JP 2001-6321
Bispyridinium compound disclosed in JP-A No.
Oxonol compounds disclosed in JP 1638, JP 2001-2001
The styryl compound of 71639 gazette etc. are mentioned.

Further, as an organic dye for forming a recording layer, there are formed two layers of a recording layer mainly containing a porphyrin type dye or a cyanine type dye and a metal reflection layer mainly containing silver, and JP-A-11-53758. By recording the optical recording medium described in 1 or the medium structure, and having a blue laser sensitive dye layer containing a cyanine dye sensitive to blue laser and a red laser sensitive dye layer, it is possible to record in two wavelength regions. The optical recording medium described in JP-A No. 11-203729 and an indigoid dye compound capable of recording in two wavelength regions by mixing two kinds of dyes, a blue laser dye and a red laser dye, are used. The optical recording medium described in JP-A-11-78239 and the optical recording medium described in JP-A-11-105423 using a cyanoethene dye. And optical recording medium of JP-A-11-110815 JP using squarylium dye compound has been proposed.

On the other hand, as an example of recording an organic dye film in the blue region of 400 to 500 nm, Japanese Patent Application Laid-Open No. 7-30425
No. 6, JP-A-7-304257, by mixing with a molecular compound and a polymer that coordinate to the central metal of a porphyrin-based compound, or a polymer having a molecular structure that coordinates the central metal in a side chain. , The Soret band of the porphyrin-based compound is shifted to the long wavelength side,
Proposals have been made to reduce the manufacturing cost by making it possible to form a film by spin coating while supporting an Ar laser of 88 nm. In addition, JP-A-4-7857
The polyene dye compounds disclosed in Japanese Patent Laid-Open No. 6-89279 and Japanese Patent Laid-Open No. 4-89279 have poor photostability according to the studies by the present inventors, and a device such as a quencher blend is required for practical use. Is.

Further, as an optical recording medium capable of recording on both wavelength region lasers, Japanese Patent Laid-Open No. 10-10195 is known.
Porphyrin-based compounds described in JP-A-3,
Tetraazaporphyrin dye compounds described in JP 144312 A, metal chelate compounds of JP 2000-242968 A, corol compounds of JP 2000-343823 AA, porphyrin compounds of JP 2001-80217 A, JP 2001-84594 A
There is an optical recording medium using the (aza) porphyrin compound disclosed in Japanese Patent Laid-Open Publication. That is, the porphyrin-based compound and the azaporphyrin-based dye having a similar structure are characterized by having absorption called Q band in the long wavelength side of the visible region and strong absorption in the short wavelength side region of the visible region called Soret band. With respect to cyclic organic compounds such as porphyrin, which are widely used as dyes, pigments, photoelectric functional materials, and the like as applications, in this publication, it is possible to perform high-density recording as a dye for DVD-R and corresponding to 15 to 30 GB. It has been proposed as a compound having properties as a dye for various optical recording media.

[0019]

As a recent situation, it is possible to put a blue-violet semiconductor laser having a wavelength of 400 nm to 410 nm into practical use, and a large-capacity write-once type optical recording medium using the laser is actively developed. In particular, there is a demand for the development of a dye having high light resistance and good high-speed recording characteristics in heat mode.

However, in reality, the above-mentioned optical recording medium is not sufficiently adapted to laser light having a wavelength of 400 nm to 410 nm. That is, in the medium using the organic dye described above, regarding reproduction of the recorded signal,
We have found a problem that the signal cannot be read out satisfactorily because the carrier-to-noise ratio (C / N) is not always a good value. Overcoming this problem, wavelength 4
There has been an urgent need to develop an optical recording medium capable of high density recording / reproduction with a laser beam of 00 nm to 410 nm.

Further, in the case of supporting a 4.7 GB capacity DVD-R which is strongly demanded as a recording / reproducing medium for digital moving images, a laser wavelength of 630n is included in the recording layer of the medium.
It is essential to have an organic dye that is sensitive to m-690 nm. For that purpose, the purpose cannot be achieved only by the above-mentioned recording dye dedicated to the blue laser wavelength.

Further, the optical recording medium described in Japanese Patent Application Laid-Open No. 11-203729, which is capable of recording / reproducing in two wavelength ranges of blue laser wavelength range and red laser wavelength range, has a multilayer recording layer. 11-78239, JP-A-11-105423, JP-A-11-
The optical recording medium described in Japanese Patent No. 110815 is complicated in medium preparation such that two or more kinds of recording dyes must be used without fail, and there is still room for improvement in recording characteristics. The above-mentioned optical recording medium compatible with blue / red laser dual wavelength recording is 40
At present, there is still room for further optimization regarding recording / reproduction with each laser beam selected from both wavelength ranges of 0 nm to 410 nm and 630 nm to 690 nm, and storage stability of a recording portion. .

The present inventors have studied the recording material suitable for the write-once type optical recording medium, and have obtained the following two findings. (1) The large-capacity write-once type optical recording medium is 300 to 500 nm and / or 500 to 7 nm for writing and reading of recording.
Since a laser beam of 00 nm is used, it is important for the recording material to control the absorption coefficient, the refractive index, and the reflectance in the vicinity of the laser wavelength. (2) As described above, a large-capacity write-once type optical recording medium using the laser has been actively developed, and in particular, development of a dye having high light resistance and good high-speed recording characteristics has been desired. As a recording material capable of recording / reproducing with respect to laser beams in both wavelength regions, the above-mentioned dye compound has not yet obtained sufficient characteristics, and there is room for improvement at present. In addition, one of the advantageous characteristics when manufacturing a medium by a coating method such as a spin coating method, which is easy to form a recording film, is as follows.
It has high solubility in a coating solvent, and it is necessary to consider this point as well.

Generally, in order to increase the recording capacity,
Since it is necessary to perform recording with higher density, it is essential to increase the numerical aperture of the objective lens for narrowing the optical beam used for recording and to shorten the laser wavelength of the optical system. However, the narrowed optical beam is diffraction limited and its minimum beam diameter is determined.

By the way, since the recording is performed when the beam intensity exceeds a certain threshold value, a recording pit smaller than the narrowed beam spot can be obtained as shown in FIG. 6A. The area around this recording pit corresponds to the base of the beam intensity peak, but in the current situation of shorter wavelengths,
The photochemical reaction of the recording layer is also promoted around the recording pits, and in particular, in the wavelength range of the above-mentioned blue-violet laser, since the photochemical reaction of the organic compound easily occurs, the pit edge deteriorates during recording, There is a problem that the signal characteristics deteriorate. That is, as shown in FIG. 6B, the recording information that should originally be formed corresponding to the rectangular wave (see FIG.
The solid line in (b) becomes a broad waveform (broken line portion in FIG. 6B) due to deterioration of the pit edge. Further, when the reproduction is performed with the same blue-violet laser wavelength as that at the time of recording, there is a problem that the photoreaction is promoted even by irradiation with a weak light such as reproduction light, and the deterioration progresses with each reproduction. Thirty
In Japanese Patent No. 4256 and Japanese Patent Laid-Open No. 7-304257,
It is necessary to take measures to make the recording light and the reproducing light have different wavelengths, in effect, to make the reproducing light a longer wavelength than the recording light, and as a result, it is not possible to meet the demand for sufficient high density. Is. Also, to make the recording wavelength and the reproducing light wavelength different, it is necessary to prepare a recording device and a reproducing device separately,
Two optical systems and their control systems must be provided in one device, which limits the use as an optical recording medium, increases the size of the device, and increases the cost, resulting in poor versatility. . Further, conventionally, in an optical recording medium such as a CD-R, recording is turned on / off at a definite thermal threshold such as a melting point, a sublimation point, a phase transition point or a thermal decomposition point of the organic dye film. In contrast to what has been produced, the interposition of a photodegradation mode by blue-violet laser excitation makes this contrast ambiguous, and especially in high-density recording systems where fine recording pits smaller than the optical beam must be formed.
There was a concern that recording signal quality would be significantly impaired.

Further, since writing and reading to and from the CD-R utilize a laser beam in the vicinity of 780 nm, it is important to control the absorption coefficient and the refractive index in the vicinity of the laser oscillation wavelength and to form pits with high accuracy during writing. is there.
This is particularly important in high speed recording and high density recording. Therefore, it is necessary to develop a dye for an optical recording medium that has high structural stability, a high refractive index with respect to light near the laser oscillation wavelength, a good decomposition property, and a high sensitivity. However, when used in recording media, the conventionally developed dyes are not sufficient in terms of sensitivity (C / N ratio, optimum recording power) and recording characteristics (jitter, deviation), especially at high speeds. was there.

The object of the present invention is to create a dye compound which is optimum for recording / reproducing information by light and has storage stability and further reproduction light stability. In order to provide an optical recording medium capable of excellent optical recording and reproduction.

[0028]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides (1): an optical recording medium in which at least one compound is selected from the azaporphyrin compounds in which the central metal is coordinated to two azaporphyrin rings and contained in the recording layer. (2): In an optical recording medium having an organic dye layer as a recording layer on a substrate, at least one kind of azaporphyrin compound in which a central metal is coordinated to two azaporphyrin rings in the organic dye layer An optical recording medium containing the above compounds selectively; (3): An optical recording medium in which the azaporphyrin compound is represented by the general formula (0).

[0029]

[Chemical 4] [In the formula, rings A, B, C, D, A ′, B ′, C ′ and D ′ each independently represent a pyrrole ring optionally having a substituent, and T ^{1 to} T ⁶ are each independently Represents a nitrogen atom or an optionally substituted methine group, and M represents a trivalent metal atom and one hydrogen atom, or a tetravalent metal atom. Each substituent of each ring of rings A, B, C, D is a substituent of each ring of rings A, B, C, D and / or rings A ′, B ′, C ′, D via a linking group. It may be bonded to each substituent of each ring of '. ]

(4): An optical recording medium in which the azaporphyrin compound is represented by the general formula (1).

[0031]

[Chemical 5] [Wherein, E ^{1 to} E ¹⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxy group, a substituted or unsubstituted amino group , A substituted or unsubstituted mercapto group, a substituted carbonyl group or a substituted or unsubstituted heterocyclic group, wherein t ^{1 to} t ⁶ are each independently a nitrogen atom or any group represented by E ^{1 to} E ¹⁶ or Representing a methine group having an atom, E ^{1 to} E ¹⁶ and the respective substituents on the methine group are bonded together through the respective linking groups with the respective substituents of the same azaporphyrin ring or the facing azaporphyrin ring. Of course, M ¹ represents a trivalent metal atom and one hydrogen atom, or a tetravalent metal atom. ]

(5): wavelength 300 nm to 500 nm and / or 500 nm to 700 nm and / or 7
Optical recording medium capable of recording and reproducing with respect to laser light selected from the range of 00 nm to 900 nm; (6): wavelength 390 nm to 500 nm and / or 600 nm to 700 nm and / or 750 nm to 8
Optical recording medium capable of recording and reproducing with respect to laser light selected from the range of 50 nm; (7): wavelength 400 nm to 410 nm and / or 630 nm to 690 nm and / or 770 nm to 8
An optical recording medium capable of recording and reproducing with respect to a laser beam selected from the range of 40 nm;

(8): A compound of the formula (1), wherein any one or more of t ^{1 to} t ^{6 is} an optionally substituted methine group.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to an optical recording medium characterized in that the recording layer of the optical recording medium contains an azaporphyrin compound which may be complexed with a metal, and particularly to a wavelength of 300 nm to 500 nm and / or Or from 500 nm
700 nm and / or 700 nm to 900 nm, and further wavelengths 390 nm to 500 nm and / or 600
nm-700 nm and / or 750 nm-850 n
m, especially 400 nm to 410 nm and / or 6
30 nm to 690 nm and / or 770 nm to 84
The present invention relates to a novel optical recording medium capable of recording and reproducing with a laser beam selected from the range of 0 nm.

The optical recording medium according to the present invention is an optical recording medium capable of recording / storing and reproducing information. However, an optical recording medium of the present invention having a recording layer and a reflective layer on a substrate will be described here as a suitable example.
In the following description, the optical recording medium is an optical disk, and has, for example, a guide groove on a supporting substrate, a reflection film and a recording layer containing an organic dye as a main component on the guide groove, and a wavelength of 3
The medium for recording / reproducing a signal by irradiating an ultraviolet / blue laser beam having a wavelength of 0 to 500 nm will be described, but the optical recording medium of the present invention is not limited to such a shape and configuration, and a card shape, It can be applied to various other shapes such as a sheet, those without a reflection layer, and recording / reproducing with a laser having a shorter wavelength which will be developed in the future.

The optical recording medium of the present invention has, for example, a four-layer structure in which a substrate 1, a recording layer 2, a reflective layer 3 and a protective layer 4 are sequentially laminated as shown in FIG. It has a bonding structure as shown in FIG. That is, the recording layer 2 is formed on the substrate 1, and the recording layer 2 is closely adhered on the recording layer 2 to form the reflective layer 3.
Is provided, and the protective layer 4 is further bonded thereto via the adhesive layer 5. However, another layer may be provided below or above the recording layer 2, and another layer may be provided above the reflective layer 3. Further, as shown in FIG. 3, a structure may be adopted in which the substrate 1, the reflective layer 3, the recording layer 2, and the protective layer 4 are laminated in this order, and recording / reproducing is performed from the protective layer side. Further, two identical or different optical recording media, one side of which is recordable, may be bonded together via an adhesive layer to form an optical recording medium of the present invention which is recordable on both sides. At that time, a known optical recording medium may be used on one side. The recording layer of the optical recording medium of the present invention may be the entire recording surface or a partial surface portion. Further, as described in Japanese Patent Application Laid-Open No. 10-326435, the thickness of the light transmissive layer depends on the N.V. A. And a medium structure defined by the laser wavelength λ.
In addition, the optical recording medium of the present invention is disclosed in Japanese Patent Laid-Open No.
It may have a structure having two or more kinds of recording layers as described in JP-A-203729.

As an example in which the present invention is applied to an optical disk, a substrate 11, a recording layer 12, a reflective layer 13 and a protective layer 14 are laminated in this order as shown in FIG. 4, and a protective layer also serving as an adhesive layer is provided. An example in which a dummy substrate 15 is bonded onto 14 is given. Of course, the structure without the substrate 15 may be used, and between the substrate 11 and the recording layer 12, between the recording layer 12 and the reflective layer 13, between the reflective layer 13 and the protective layer 14, between the protective layer 14 and the dummy substrate 15. Other layers may be present between and. In the optical disc of FIG. 4, recording / reproduction is performed from the substrate 11 side.

As another embodiment, Japanese Patent Laid-Open No. 10-3
As disclosed in Japanese Patent No. 02310, for example, as shown in FIG. 5, a reflective layer 13 ′ and a recording layer 12 ′ containing an organic dye as a main component are provided in this order on a support substrate 11 ′ having guide grooves. A light transmission layer 15 'is formed on the recording layer 12' via a transparent protective layer 14 'that is arbitrarily formed, and recording and reproduction of information is performed from the light transmission layer 15' side. . On the contrary, a guide groove may be formed on the side of the light transmitting layer 15 ', the transparent protective layer 14', the recording layer 12 ', and the reflective layer 13' may be laminated on the guide groove and bonded to the supporting substrate 11 '. .

In the present invention, the recording layer is provided on the substrate. In the recording layer of the present invention, at least one azaporphyrin compound having a central metal coordinated to two azaporphyrin rings is selected. It is contained. The azaporphyrin-based compound of the present invention in which the central metal is coordinated to two azaporphyrin rings, in other words, two or more azaporphyrin rings, which may be the same or different from each other, are bonded to each other via central metal atoms shared by each other. And a compound having a sandwich-type structure of facing in parallel with each other, and particularly containing at least one compound represented by the general formula (0). And a wavelength of 300 nm to 500 nm and / or 500 nm to 700 nm and / or 700
It is possible to record / reproduce at a recording laser wavelength and a reproducing laser wavelength selected from nm to 900 nm.
Among them, the wavelength is 390 nm to 500 nm and / or 6
00 nm to 700 nm and / or 750 nm to 85
0 nm, further 400 nm to 410 nm and / or 630 nm to 690 nm and / or 770 nm
Optical recording medium capable of obtaining a good C / N ratio with respect to a recording laser wavelength and a reproducing laser wavelength selected from the range of ˜840 nm, good reproducing light stability, and high-quality signal characteristics Is.

The compound represented by the general formula (0) according to the present invention has a dimer structure in which two azaporphyrin rings are bonded to a trivalent metal or a tetravalent metal, and the substituent is selected. Since the absorption wavelength can be arbitrarily selected while maintaining the absorption coefficient, it is a compound which is extremely useful as an organic dye because it can satisfy the optical constant required for the recording layer at the wavelength of the laser beam.

Examples of the azaporphyrin ring include, for example, a monoazaporphyrin ring, a diazaporphyrin ring,
Examples thereof include a triazaporphyrin ring and a tetraazaporphyrin ring. Further, each of the pyrrole rings in these ring structures may have a condensed ring. Suitable examples include compounds having a condensed benzene ring, such as dibenzotetraazaporphyrin, phthalocyanine, and naphthalocyanine.

The present invention will be described in more detail below.

The compound represented by the general formula (0) according to the present invention may have a substituent represented by ring A, B, C, D, A ', B', C ', D'. For a good pyrrole ring, examples of specific substituents include a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxy group, a substituted or unsubstituted amino group. Group, a substituted or unsubstituted mercapto group, a substituted carbonyl group, a substituted or unsubstituted heterocyclic group and the like.

Specific examples of the optionally substituted methine group represented by T ^{1 to} T ⁶ of the azaporphyrin skeleton of the general formula (0) are represented by the formula (8) and the formula (9), Expression (10), Expression (11), Expression (12), Expression (1
3)

[0045]

[Chemical 6] [In the formula, G ¹ , G ² , G ³ , G ⁴ , G ⁵ and G ⁶ have the same meanings as the substituents which may be substituted on the pyrrole ring. ]
And the optionally substituted methine group and the like.

In the substituents on the pyrrole ring, the substituents on the methine group represented by T ^{1 to} T ⁶ , the substituents on the pyrrole ring or the pyrrole ring are bonded via a linking group. The above substituent and the substituent on the methine group may be linked, and specifically, ring formation by aliphatic condensation or aromatic condensation, or a linking group such as a hetero atom or a metal complex residue Formation of a heterocycle containing a hetero atom can be mentioned.

In the formula (0), M represents a trivalent metal atom and one hydrogen atom, or a tetravalent metal atom.

Further, the above-mentioned substituents which are substituted on the pyrrole rings A, B, C and D, or the substituents on the methine group represented by T ^{1 to} T ³ are the pyrrole rings A ′, B ',
C ', D' may be linked to the substituents on the methine groups represented by the substituent or T ⁴ through T ⁶ substituting on, specifically aliphatic, aromatic, heteroatom or a metal, Examples of the method include connection by an atom chain composed of a complex residue or the like, or formation of a ring.

In the present invention, as the compound represented by the general formula (0), the compound represented by the general formula (1) is further preferred.

[0050]

[Chemical 7] [Wherein, E ^{1 to} E ¹⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxy group, a substituted or unsubstituted amino group , A substituted or unsubstituted mercapto group, a substituted carbonyl group or a substituted or unsubstituted heterocyclic group, wherein t ^{1 to} t ⁶ are each independently a nitrogen atom or any group represented by E ^{1 to} E ¹⁶ or Representing a methine group having an atom, E ^{1 to} E ¹⁶ and the respective substituents on the methine group are bonded together through the respective linking groups with the respective substituents of the same azaporphyrin ring or the facing azaporphyrin ring. Of course, M ¹ represents a trivalent metal atom and one hydrogen atom, or a tetravalent metal atom. ]

Specific examples of the substituent represented by the general formula (1) include substituted or unsubstituted hydrogen atom, halogen atom, nitro group, cyano group, alkyl group, aralkyl group, aryl group, alkenyl group and the like. A hydrocarbon group; a substituted or unsubstituted hydroxy group such as a hydroxyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an alkenyloxy group, an acyloxy group and a heteroaryloxy group; an unsubstituted amino group, a monosubstituted amino group, Substituted or unsubstituted amino group such as di-substituted amino group; substituted or unsubstituted mercapto group such as mercapto group, alkylthio group, aralkylthio group, arylthio group, alkenylthio group, heteroarylthio group; carboxyl group, acyl group , Alkoxycarbonyl groups, aralkyloxycarbonyl groups, aryloxy groups Boniru group, alkenyloxycarbonyl group, monosubstituted aminocarbonyl group, a substituted carbonyl group such as a di-substituted amino group; and the like heteroaryl group or a substituted or unsubstituted heterocyclic group nonaromatic, and the like.

Specific examples of the optionally substituted methine group represented by t ¹ to t ⁶ of the azaporphyrin skeleton of the formula (1) include T ^{1 of the} formula (0). ~ T ⁶
And the same methine group as.

In the above-mentioned substituents for substituting on the pyrrole ring, the substituents on the methine group represented by t ^{1 to} t ⁶ , preferably the substituents on the pyrrole ring are bonded to each other or via the linking group. The substituent on the pyrrole ring and the substituent on the adjacent methine group may be linked to each other. Specifically, a ring is formed by aliphatic condensation or aromatic condensation, or the linking group is a hetero atom or a metal complex. Formation of a heterocycle containing a heteroatom such as a residue may be mentioned.

Further, M ¹ in the formula (1) represents a trivalent metal atom and one hydrogen atom, or a tetravalent metal atom.

The substituents represented by E ^{1 to} E ⁸ or the substituents on the methine group represented by t ^{1 to} t ³ are the substituents represented by E ^{9 to} E ¹⁶ via the linking group. Alternatively, it may be linked to a substituent on the methine group represented by t ^{4 to} t ⁶ , and specifically, it is linked by an atom chain composed of an aliphatic, aromatic, heteroatom, metal complex residue or the like. , Or formation of a ring and the like.

As the compound represented by the general formula (1),
Further, the compound exemplified by the general formula (2) is mentioned as a preferable example.

[0057]

[Chemical 8]

[Wherein R¹~ R¹⁶Each independently, water
Elementary atom, halogen atom, nitro group, cyano group, hydroxy
Syl group, amino group, carboxyl group, mercapto group,
A substituted or unsubstituted alkyl group, aralkyl group, aryl
Group, alkenyl group, alkoxy group, aralkyloxy
Group, aryloxy group, alkenyloxy group, alkyl
Thio group, aralkylthio group, arylthio group, alkene
Ruthio group, mono-substituted amino group, di-substituted amino group, acyl
Group, alkoxycarbonyl group, aralkyloxycarbo
Nyl group, aryloxycarbonyl group, alkenyloxy
Sicarbonyl group, mono-substituted aminocarbonyl group, di-substituted
Aminocarbonyl group, acyloxy group, heteroaryl
Group, heteroaryloxy group or heteroarylthio
Represents a group, X ¹Is a nitrogen atom or C-R¹⁷(R¹⁷Is R¹~
R¹⁶Represents any of the groups shown in
Represents a methine group which may be¹Is a nitrogen atom
Is CR¹⁸(R¹⁸Is R¹~ R¹⁶Any of the groups shown in
Represents an optionally substituted methine group
Represent, Z¹Is a nitrogen atom or C-R¹⁹(R¹⁹Is R¹~ R
¹⁶Represents any of the groups shown in
Represents an optionally contained methine group, X²Is a nitrogen atom or
C-R²⁰(R²⁰Is R¹~ R¹⁶Any of the groups shown in
Represents an optionally substituted methine group represented by
Then Y²Is a nitrogen atom or C-R^{twenty one}(R^{twenty one}Is R¹~ R¹⁶To
Substituted for any of the groups shown)
Represents a methine group which may be present, Z²Is a nitrogen atom or C
-R^{twenty two}(R^{2 2}Is R¹~ R¹⁶Table of any of the groups shown in
The optionally substituted methine group represented by
And R¹~ R^{twenty two}Each substituent of is a linking group with an adjacent substituent.
And R may together form a ring,¹~
R⁸, R¹⁷~ R¹⁹Each substituent of R is⁹~ R¹⁶, R²⁰~ R^{twenty two}
Each of the substituents may be bonded to each other via a linking group.
Ku, M²Is a trivalent metal atom and one hydrogen atom, or
Represents a tetravalent metal atom. However, X¹, Y¹, Z¹, X²,
Y², Z²When all are nitrogen atoms, R¹~ R², R ³
~ R^Four, R^Five~ R⁶, R⁷~ R⁸, R⁹~ R^Ten, R¹¹~ R¹²,
R¹³~ R¹⁴, R¹⁵~ R^{1 6}Each substituent of
It does not form an aromatic ring at the same time by being linked. ]

In the compound represented by the general formula (2) of the present invention, specific examples of R ^{1 to} R ¹⁶ include hydrogen atom; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; nitro group A cyano group; a hydroxyl group; an amino group; a carboxyl group; a mercapto group and the like.

The substituted or unsubstituted alkyl group represented by R ^{1 to} R ¹⁶ includes a methyl group, an ethyl group, an n-propyl group, and i.
so-propyl group, n-butyl group, iso-butyl group,
sec-butyl group, t-butyl group, n-pentyl group, i
so-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclopentyl group,
n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethyl Butyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group,
1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl-2
-Methylpropyl group, cyclohexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4
-Methylhexyl group, 5-methylhexyl group, 2,4-
Dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentyl group, 2,4-dimethylhexyl group,
2,2,4-trimethylpentyl group, 3,5,5-trimethylhexyl group, n-nonyl group, n-decyl group, 4-
Ethyloctyl group, 4-ethyl-4,5-methylhexyl group, n-undecyl group, n-dodecyl group, 1,3,3
5,7-tetraethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group,
6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5, 5-tetramethylhexyl group,
1-cyclopentyl-2,2-dimethylpropyl group, 1
An unsubstituted linear, branched or cyclic alkyl group having 1 to 15 carbon atoms such as cyclohexyl-2,2-dimethylpropyl group;

Chloromethyl group, chloroethyl group, bromoethyl group, iodoethyl group, dichloromethyl group, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, 2,2,2.
2-trichloroethyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, nonafluorobutyl group, perfluorodecyl group, or other alkyl group having 1 to 10 carbon atoms substituted with a halogen atom ;

Hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 2-hydroxy-3-methoxypropyl group, 2-
Hydroxy-3-chloropropyl group, 2-hydroxy-
With a hydroxyl group such as 3-ethoxypropyl group, 3-butoxy-2-hydroxypropyl group, 2-hydroxy-3-cyclohexyloxypropyl group, 2-hydroxypropyl group, 2-hydroxybutyl group, 4-hydroxydecalyl group. A substituted alkyl group having 1 to 10 carbon atoms;

Hydroxymethoxymethyl group, hydroxyethoxyethyl group, 2- (2'-hydroxy-1'-methylethoxy) -1-methylethyl group, 2- (3'-fluoro-2'-hydroxypropoxy) ethyl group , 2-
(3'-chloro-2'-hydroxypropoxy) ethyl group, an alkyl group having 2 to 10 carbon atoms substituted with a hydroxyalkoxy group such as hydroxybutoxycyclohexyl group;

Hydroxymethoxymethoxymethyl group, hydroxyethoxyethoxyethyl group, [2 '-(2'-
Hydroxy-1′-methylethoxy) -1′-methylethoxy] ethoxyethyl group, [2 ′-(2′-fluoro-
1'-hydroxyethoxy) -1'-methylethoxy]
An alkyl group having 3 to 10 carbon atoms substituted with a hydroxyalkoxyalkoxy group such as an ethoxyethyl group or a [2 '-(2'-chloro-1'-hydroxyethoxy) -1'-methylethoxy] ethoxyethyl group;

Cyanomethyl group, 2-cyanoethyl group, 3
-Cyanopropyl group, 4-cyanobutyl group, 2-cyano-3-methoxypropyl group, 2-cyano-3-chloropropyl group, 2-cyano-3-ethoxypropyl group, 3-
Butoxy-2-cyanopropyl group, 2-cyano-3-cyclohexylpropyl group, 2-cyanopropyl group, 2-
2 to 1 carbon atoms substituted with a cyano group such as a cyanobutyl group
An alkyl group of 0;

Methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, n-hexyloxyethyl group, (4-methylpentoxy) ethyl Group, (1,3-dimethylbutoxy)
Ethyl group, (2-ethylhexyloxy) ethyl group, n
-Octyloxyethyl group, (3,5,5-trimethylhexyloxy) ethyl group, (2-methyl-1-iso
-Propylpropoxy) ethyl group, (3-methyl-1-
iso-propylbutyloxy) ethyl group, 2-ethoxy-1-methylethyl group, 3-methoxybutyl group,
(3,3,3-trifluoropropoxy) ethyl group,
An alkyl group having 2 to 15 carbon atoms substituted with an alkoxy group such as (3,3,3-trichloropropoxy) ethyl group;

Methoxymethoxymethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propoxyethoxyethyl group, butoxyethoxyethyl group, cyclohexyloxyethoxyethyl group, decalyloxypropoxyethoxy group, (1,2-dimethylpropoxy) ethoxy Ethyl group, (3-methyl-1-iso-butylbutoxy) ethoxyethyl group, (2-methoxy-1-methylethoxy) ethyl group, (2-butoxy-1-methylethoxy) ethyl group, 2- (2 ′) -Ethoxy-1'-methylethoxy) -1-methylethyl group, (3,3,3-trifluoropropoxy) ethoxyethyl group, (3,3,3
An alkyl group having 3 to 15 carbon atoms substituted with an alkoxyalkoxy group such as 3-trichloropropoxy) ethoxyethyl group;

Methoxymethoxymethoxymethyl group, methoxyethoxyethoxyethyl group, ethoxyethoxyethoxyethyl group, butoxyethoxyethoxyethyl group, cyclohexyloxyethoxyethoxyethyl group, propoxypropoxypropoxyethyl group, (2,2,2-trifluoroethoxy ) Ethoxyethoxyethyl group,
An alkyl group having 4 to 15 carbon atoms substituted with an alkoxyalkoxyalkoxy group such as (2,2,2-trichloroethoxy) ethoxyethoxyethyl group;

Formylmethyl group, 2-oxobutyl group,
3-oxobutyl group, 4-oxobutyl group, 2,6-dioxocyclohexan-1-yl group, 2-oxo-5-
an alkyl group having 2 to 10 carbon atoms substituted with an acyl group such as t-butylcyclohexane-1-yl group;

Formyloxymethyl group, acetoxyethyl group, propionyloxyethyl group, butanoyloxyethyl group, valeryloxyethyl group, (2-ethylhexanoyloxy) ethyl group, (3,5,5-trimethylhexanoyl) Number of carbon atoms substituted with an acyloxy group such as (oxy) ethyl group, (3,5,5-trimethylhexanoyloxy) hexyl group, (3-fluorobutyryloxy) ethyl group, (3-chlorobutyryloxy) ethyl group Two
~ 15 alkyl groups;

Formyloxymethoxymethyl group, acetoxyethoxyethyl group, propionyloxyethoxyethyl group, valeryloxyethoxyethyl group, (2-ethylhexanoyloxy) ethoxyethyl group, (3,5,5
5-trimethylhexanoyl) oxybutoxyethyl group, (3,5,5-trimethylhexanoyloxy) ethoxyethyl group, (2-fluoropropionyloxy)
Ethoxyethyl group, (2-chloropropionyloxy)
An alkyl group having 3 to 15 carbon atoms substituted with an acyloxyalkoxy group such as an ethoxyethyl group;

Acetoxymethoxymethoxymethyl group, acetoxyethoxyethoxyethyl group, propionyloxyethoxyethoxyethyl group, valeryloxyethoxyethoxyethyl group, (2-ethylhexanoyloxy)
Ethoxyethoxyethyl group, (3,5,5-trimethylhexanoyloxy) ethoxyethoxyethyl group, (2
An alkyl group having 5 to 15 carbon atoms, which is substituted with an acyloxyalkoxyalkoxyalkoxy group such as -fluoropropionyloxy) ethoxyethoxyethyl group and (2-chloropropionyloxy) ethoxyethoxyethyl group;

Methoxycarbonylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylethyl group, butoxycarbonylethyl group, (p-ethylcyclohexyloxycarbonyl) cyclohexyl group, (2,
An alkyl group having 3 to 15 carbon atoms substituted with an alkoxycarbonyl group such as a 2,3,3-tetrafluoropropoxycarbonyl) methyl group or a (2,2,3,3-tetrachloropropoxycarbonyl) methyl group;

8 to 15 carbon atoms substituted with an aryloxycarbonyl group such as a phenoxycarbonylmethyl group, a phenoxycarbonylethyl group, a (4-t-butylphenoxycarbonyl) ethyl group, a naphthyloxycarbonylmethyl group and a biphenyloxycarbonylethyl group. An alkyl group of

An alkyl group having 9 to 15 carbon atoms substituted with an aralkyloxycarbonyl group such as a benzyloxycarbonylmethyl group, a benzyloxycarbonylethyl group, a phenethyloxycarbonylmethyl group and a (4-cyclohexyloxybenzyloxycarbonyl) methyl group;

C4-10 substituted with an alkenyloxycarbonyl group such as a vinyloxycarbonylmethyl group, a vinyloxycarbonylethyl group, an allyloxycarbonylmethyl group, a cyclopentadienyloxycarbonylmethyl group and an octenoxycarbonylmethyl group. An alkyl group of

Methoxycarbonyloxymethyl group, methoxycarbonyloxyethyl group, ethoxycarbonyloxyethyl group, butoxycarbonyloxyethyl group,
An alkyl group having 3 to 15 carbon atoms substituted with an alkoxycarbonyloxy group such as a (2,2,2-trifluoroethoxycarbonyloxy) ethyl group and a (2,2,2-trichloroethoxycarbonyloxy) ethyl group;

Methoxymethoxycarbonyloxymethyl group, methoxyethoxycarbonyloxyethyl group, ethoxyethoxycarbonyloxyethyl group, butoxyethoxycarbonyloxyethyl group, (2,2,2-trifluoroethoxy) ethoxycarbonyloxyethyl group,
An alkyl group having 4 to 15 carbon atoms substituted with an alkoxyalkoxycarbonyloxy group such as (2,2,2-trichloroethoxy) ethoxycarbonyloxyethyl group;

Dimethylaminomethyl group, diethylaminomethyl group, di-n-butylaminomethyl group, di-n-hexylaminomethyl group, di-n-octylaminomethyl group, di-n-decylaminomethyl group, N- Isoamyl-
N-methylaminomethyl group, piperidinomethyl group, di (methoxymethyl) aminomethyl group, di (methoxyethyl) aminomethyl group, di (ethoxymethyl) aminomethyl group, di (ethoxyethyl) aminomethyl group, di (propoxyethyl) ) Aminomethyl group, di (butoxyethyl)
Aminomethyl group, bis (2-cyclohexyloxyethyl) aminomethyl group, dimethylaminoethyl group, diethylaminoethyl group, di-n-butylaminoethyl group, di-n-hexylaminoethyl group, di-n-octylaminoethyl Group, di-n-decylaminoethyl group, N-isoamyl-N-methylaminoethyl group, piperidinoethyl group, di (methoxymethyl) aminoethyl group, di (methoxyethyl) aminoethyl group, di (ethoxymethyl) aminoethyl Group, di (ethoxyethyl) aminoethyl group, di (propoxyethyl) aminoethyl group, di (butoxyethyl) aminoethyl group, bis (2-cyclohexyloxyethyl) aminoethyl group, dimethylaminopropyl group, diethylaminopropyl group, Di-n-butylaminopropyl group, di-n Hexyl aminopropyl group, di -
n-octylaminopropyl group, di-n-decylaminopropyl group, N-isoamyl-N-methylaminopropyl group, piperidinopropyl group, di (methoxymethyl) aminopropyl group, di (methoxyethyl) aminopropyl group , Di (ethoxymethyl) aminopropyl group, di (ethoxyethyl) aminopropyl group, di (propoxyethyl) aminopropyl group, di (butoxyethyl) aminopropyl group, bis (2-cyclohexyloxyethyl) aminopropyl group, dimethyl Aminobutyl group, diethylaminobutyl group, di-n-butylaminobutyl group, di-n
-Hexylaminobutyl group, di-n-octylaminobutyl group, di-n-decylaminobutyl group, N-isoamyl-N-methylaminobutyl group, piperidinobutyl group,
Di (methoxymethyl) aminobutyl group, di (methoxyethyl) aminobutyl group, di (ethoxymethyl) aminobutyl group, di (ethoxyethyl) aminobutyl group, di (propoxyethyl) aminobutyl group, di (butoxyethyl) An alkyl group having 3 to 20 carbon atoms, which is substituted with a dialkylamino group such as an aminobutyl group and a bis (2-cyclohexyloxyethyl) aminobutyl group;

Substituted with an acylamino group such as acetylaminomethyl group, acetylaminoethyl group, propionylaminoethyl group, butanoylaminoethyl group, cyclohexanecarbonylaminoethyl group, p-methylcyclohexanecarbonylaminoethyl group and succiniminoethyl group. An alkyl group having 3 to 10 carbon atoms;

An alkyl group having 2 to 10 carbon atoms, which is substituted with an alkylsulfonamino group such as a methylsulfonaminomethyl group, a methylsulfonaminoethyl group, an ethylsulfonaminoethyl group, a propylsulfonaminoethyl group, an octylsulfonaminoethyl group;

Methylsulfonylmethyl group, ethylsulfonylmethyl group, butylsulfonylmethyl group, methylsulfonylethyl group, ethylsulfonylethyl group, butylsulfonylethyl group, 2-ethylhexylsulfonylethyl group, 2,2,3,3-tetrafluoro C2-C10 alkyl group substituted with an alkylsulfonyl group such as propylsulfonylmethyl group, 2,2,3,3-tetrachloropropylsulfonylmethyl group; benzenesulfonylmethyl group, benzenesulfonylethyl group, benzenesulfonylpropyl group , Benzenesulfonylbutyl group, toluenesulfonylmethyl group, toluenesulfonylethyl group, toluenesulfonylpropyl group, toluenesulfonylbutyl group, xylenesulfonylmethyl group, xylenesulfonylethyl group, Cyclohexylene sulfonyl propyl group, an alkyl group having 7 to 12 carbon atoms which is substituted by an arylsulfonyl group such as xylene sulfonyl butyl group;

Thiadiazolinomethyl group, pyrrolinomethyl group, pyrrolidinomethyl group, pyrazolidinomethyl group, imidazolidinomethyl group, oxazolyl group, triazolinomethyl group, morpholinomethyl group, indolinomethyl group,
An alkyl group having 2 to 13 carbon atoms substituted with a heterocyclic group such as a benzimidazolinomethyl group or a carbazolinomethyl group;

Ferrocenylmethyl group, ferrocenylethyl group, ferrocenyl-n-propyl group, ferrocenyl-
iso-propyl group, ferrocenyl-n-butyl group, ferrocenyl-iso-butyl group, ferrocenyl-sec
-Butyl group, ferrocenyl-t-butyl group, ferrocenyl-n-pentyl group, ferrocenyl-iso-pentyl group, ferrocenyl-2-methylbutyl group, ferrocenyl-1-methylbutyl group, ferrocenyl neopentyl group,
Ferrocenyl-1,2-dimethylpropyl group, ferrocenyl-1,1-dimethylpropyl group, ferrocenylcyclopentyl group, ferrocenyl-n-hexyl group, ferrocenyl-4-methylpentyl group, ferrocenyl-3-methylpentyl group, ferrocenyl -2-methylpentyl group, ferrocenyl-1-methylpentyl group, ferrocenyl-3,3-dimethylbutyl group, ferrocenyl-2,3
-Dimethylbutyl group, ferrocenyl-1,3-dimethylbutyl group, ferrocenyl-2,2-dimethylbutyl group,
Ferrocenyl-1,2-dimethylbutyl group, ferrocenyl-1,1-dimethylbutyl group, ferrocenyl-3-ethylbutyl group, ferrocenyl-2-ethylbutyl group, ferrocenyl-1-ethylbutyl group, ferrocenyl-1,
2,2-trimethylbutyl group, ferrocenyl-1,1,
2-trimethylbutyl group, ferrocenyl-1-ethyl-
2-methylpropyl group, ferrocenylcyclohexyl group, ferrocenyl-n-heptyl group, ferrocenyl-2
-Methylhexyl group, ferrocenyl-3-methylhexyl group, ferrocenyl-4-methylhexyl group, ferrocenyl-5-methylhexyl group, ferrocenyl-2,4-
Dimethylpentyl group, ferrocenyl-n-octyl group,
Ferrocenyl-2-ethylhexyl group, ferrocenyl-
2,5-dimethylhexyl group, ferrocenyl-2,5
5-trimethylpentyl group, ferrocenyl-2,4-dimethylhexyl group, ferrocenyl-2,2,4-trimethylpentyl group, ferrocenyl-3,5,5-trimethylhexyl group, ferrocenyl-n-nonyl group, ferrocenyl-n -Decyl group,

Cobaltcenylmethyl group, cobaltcenylethyl group, cobaltcenyl-n-propyl group, cobaltcenyl-iso-propyl group, cobaltcenyl-n-butyl group, cobaltcenyl-iso-butyl group, cobaltcenyl-sec-butyl group, Cobalt cenyl-t-butyl group, cobalt cenyl-n-pentyl group, cobalt cenyl-iso-pentyl group, cobalt cenyl-2-methylbutyl group, cobalt cenyl-1-methylbutyl group, cobalt cenyl neopentyl group, cobalt cenyl-1,2-
Dimethylpropyl group, cobaltcenyl-1,1-dimethylpropyl group, cobaltcenylcyclopentyl group, cobaltcenyl-n-hexyl group, cobaltcenyl-4-methylpentyl group, cobaltcenyl-3-methylpentyl group, cobaltcenyl-2-methylpentyl group , Cobaltcenyl-1-methylpentyl group, cobaltcenyl-3,
3-dimethylbutyl group, cobaltcenyl-2,3-dimethylbutyl group, cobaltcenyl-1,3-dimethylbutyl group, cobaltcenyl-2,2-dimethylbutyl group, cobaltcenyl-1,2-dimethylbutyl group, cobaltcenyl-1, 1-dimethylbutyl group, cobalt cenyl-3
-Ethylbutyl group, cobaltcenyl-2-ethylbutyl group, cobaltcenyl-1-ethylbutyl group, cobaltcenyl-1,2,2-trimethylbutyl group, cobaltcenyl-1,1,2-trimethylbutyl group, cobaltcenyl-1-ethyl-2- Methylpropyl group, cobaltcenylcyclohexyl group, cobaltcenyl-n-heptyl group,
Cobalt cenyl-2-methylhexyl group, cobalt cenyl-3-methylhexyl group, cobalt cenyl-4-methylhexyl group, cobalt cenyl-5-methylhexyl group, cobalt cenyl-2,4-dimethylpentyl group, cobalt cenyl-n-octyl group, cobalt cenyl -2-
Ethylhexyl group, cobaltcenyl-2,5-dimethylhexyl group, cobaltcenyl-2,5,5-trimethylpentyl group, cobaltcenyl-2,4-dimethylhexyl group, cobaltcenyl-2,2,4-trimethylpentyl group, cobaltcenyl-3 , 5,5-trimethylhexyl group, cobaltcenyl-n-nonyl group, cobaltcenyl-n-decyl group,

Nickelocenylmethyl group, nickelocenylethyl group, nickelocenyl-n-propyl group, nickelocenyl-iso-propyl group, nickelocenyl-n-butyl group, nickelocenyl-iso-butyl group, nickelocenyl-sec-butyl group, Nickelocenyl-t-butyl group, nickelocenyl-n-pentyl group, nickelocenyl-iso-pentyl group, nickelocenyl-2-methylbutyl group, nickelocenyl-1-methylbutyl group, nickelocenyl neopentyl group, nickelocenyl-1,2-
Dimethylpropyl group, nickelocenyl-1,1-dimethylpropyl group, nickelocenylcyclopentyl group, nickelocenyl-n-hexyl group, nickelocenyl-4-methylpentyl group, nickelocenyl-3-methylpentyl group, nickelocenyl-2-methylpentyl group , Nickelocenyl-1-methylpentyl group, nickelocenyl-3,
3-dimethylbutyl group, nickelocenyl-2,3-dimethylbutyl group, nickelocenyl-1,3-dimethylbutyl group, nickelocenyl-2,2-dimethylbutyl group, nickelocenyl-1,2-dimethylbutyl group, nickelocenyl-1, 1-dimethylbutyl group, nickelocenyl-3
-Ethylbutyl group, nickelocenyl-2-ethylbutyl group, nickelocenyl-1-ethylbutyl group, nickelocenyl-1,2,2-trimethylbutyl group, nickelocenyl-1,1,2-trimethylbutyl group, nickelocenyl-1-ethyl-2- Methylpropyl group, nickelocenylcyclohexyl group, nickelocenyl-n-heptyl group,
Nickelocenyl-2-methylhexyl group, nickelocenyl-3-methylhexyl group, nickelocenyl-4-methylhexyl group, nickelocenyl-5-methylhexyl group, nickelocenyl-2,4-dimethylpentyl group, nickelocenyl-n-octyl group, nickelocenyl -2-
Ethylhexyl group, nickelocenyl-2,5-dimethylhexyl group, nickelocenyl-2,5,5-trimethylpentyl group, nickelocenyl-2,4-dimethylhexyl group, nickelocenyl-2,2,4-trimethylpentyl group, nickelocenyl-3 , 5,5-trimethylhexyl group, nickelocenyl-n-nonyl group, nickelocenyl-n-decyl group;

Dichlorotitanocenylmethyl group, trichlorotitanium cyclopentadienylmethyl group, bis (trifluoromethanesulfonato) titanocene methyl group, dichlorozirconocenylmethyl group, dimethylzirconocenylmethyl group, diethoxyzirconocenylmethyl group. Group, bis (cyclopentadienyl) chromium methyl group, bis (cyclopentadienyl) dichloromolybdenum methyl group, bis (cyclopentadienyl) dichlorohafnium methyl group, bis (cyclopentadienyl) dichloroniobium methyl group, bis An alkyl group having 11 to 20 carbon atoms substituted with a metallocenyl group such as a (cyclopentadienyl) rutheniummethyl group, a bis (cyclopentadienyl) vanadium methyl group, a bis (cyclopentadienyl) dichlorovanadiummethyl group;

Ferrocenyl methoxymethyl group, ferrocenyl methoxyethyl group, ferrocenyl methoxypropyl group, ferrocenyl methoxybutyl group, ferrocenyl methoxypentyl group, ferrocenyl methoxyhexyl group, ferrocenyl methoxyheptyl group Group, ferrocenyl methoxyoctyl group, ferrocenyl methoxynonyl group, ferrocenyl methoxydecyl group, ferrocenyl ethoxymethyl group, ferrocenyl ethoxyethyl group, ferrocenyl ethoxypropyl group, ferrocenyl ethoxybutyl group , Ferrocenylethoxypentyl group, ferrocenylethoxyhexyl group, ferrocenylethoxyheptyl group, ferrocenylethoxyoctyl group, ferrocenylethoxynonyl group, ferrocenylethoxydecyl group, ferrocenylpropoxymethyl group, F Rose cycloalkenyl propoxyethyl group, ferrocenyl propoxypropyl group, ferrocenyl-propoxybutyl group, ferrocenyl propoxy pentyl group, ferrocenyl propoxy hexyl, ferrocenyl propoxy heptyl group, ferrocenyl propoxy octyl group,
Ferrocenylpropoxynonyl group, ferrocenylpropoxydecyl group, ferrocenylbutoxymethyl group, ferrocenylbutoxyethyl group, ferrocenylbutoxypropyl group, ferrocenylbutoxybutyl group, ferrocenylbutoxypentyl group, ferroc Cenylbutoxyhexyl group,
Ferrocenylbutoxyheptyl group, ferrocenylbutoxyoctyl group, ferrocenylbutoxynonyl group, ferrocenylbutoxydecyl group, ferrocenyldecyloxymethyl group, ferrocenyldecyloxyethyl group, ferrocenyldecyloxypropyl group Group, ferrocenyldecyloxybutyl group, ferrocenyldecyloxypentyl group, ferrocenyldecyloxyhexyl group, ferrocenyldecyloxyheptyl group, ferrocenyldecyloxyoctyl group, ferrocenyldecyloxynonyl group, Ferrocenyldecyloxydecyl group;

Cobalt cenyl methoxymethyl group, cobalt cenyl methoxyethyl group, cobalt cenyl methoxypropyl group, cobalt cenyl methoxybutyl group, cobalt cenyl methoxypentyl group, cobalt cenyl methoxyhexyl group, cobalt cenyl methoxyheptyl group. Group, cobalt cenyl methoxyoctyl group, cobalt cenyl methoxy nonyl group, cobalt cenyl methoxydecyl group, cobalt cenyl ethoxymethyl group, cobalt cenyl ethoxyethyl group, cobalt cenyl ethoxypropyl group, cobalt cenyl ethoxybutyl group , Cobaltcenylethoxypentyl group, cobaltcenylethoxyhexyl group, cobaltcenylethoxyheptyl group, cobaltcenylethoxyoctyl group, cobaltcenylethoxynonyl group, cobaltcenylethoxydecyl group Group, cobaltcenylpropoxymethyl group, cobaltcenylpropoxyethyl group, cobaltcenylpropoxypropyl group, cobaltcenylpropoxybutyl group, cobaltcenylpropoxypentyl group, cobaltcenylpropoxyhexyl group, cobaltcenylpropoxyheptyl group , A cobalt cenyl propoxyoctyl group, a cobalt cenyl propoxy nonyl group, a cobalt cenyl propoxydecyl group, a cobalt cenyl butoxymethyl group, a cobalt cenyl butoxyethyl group, a cobalt cenyl butoxypropyl group, a cobalt cenyl butoxybutyl group, Cobalt cenyl butoxypentyl group, cobalt cenyl butoxy hexyl group, cobalt cenyl butoxy heptyl group, cobalt cenyl butoxy octyl group, cobalt cenyl butoxy nonyl group, cobalt ceni Butokishideshiru group, cobalt Se sulfonyl decyl oxymethyl group, cobalt Se sulfonyl decyl oxyethyl groups, cobalt Se sulfonyl decyloxy propyl, cobalt Se sulfonyl decyloxy-butyl group,
Cobalt cenyldecyloxypentyl group, cobaltcenyldecyloxyhexyl group, cobaltcenyldecyloxyheptyl group, cobaltcenyldecyloxyoctyl group, cobaltcenyldecyloxynonyl group, cobaltcenyldecyloxydecyl group;

Nickelocenyl methoxymethyl group, nickelocenyl methoxyethyl group, nickelocenyl methoxypropyl group, nickelocenyl methoxybutyl group, nickelocenyl methoxypentyl group, nickelocenyl methoxyhexyl group, nickelocenyl methoxyheptyl group. Group, nickelocenylmethoxyoctyl group, nickelocenylmethoxynonyl group, nickelocenylmethoxydecyl group, nickelocenylethoxymethyl group, nickelocenylethoxyethyl group, nickelocenylethoxypropyl group, nickelocenylethoxybutyl group , Nickelocenylethoxypentyl group, nickelocenylethoxyhexyl group, nickelocenylethoxyheptyl group, nickelocenylethoxyoctyl group, nickelocenylethoxynonyl group, nickelocenylethoxydecyl group Group, nickelocenylpropoxymethyl group, nickelocenylpropoxyethyl group, nickelocenylpropoxypropyl group, nickelocenylpropoxybutyl group, nickelocenylpropoxypentyl group, nickelocenylpropoxyhexyl group, nickelocenylpropoxyheptyl group , Nickelocenylpropoxyoctyl group, nickelocenylpropoxynonyl group, nickelocenylpropoxydecyl group, nickelocenylbutoxymethyl group, nickelocenylbutoxyethyl group, nickelocenylbutoxypropyl group, nickelocenylbutoxybutyl group, Nickelocenyl butoxypentyl group, nickelocenyl butoxyhexyl group, nickelocenyl butoxyheptyl group, nickelocenyl butoxyoctyl group, nickelocenyl butoxynonyl group, nickelocenyl Butokishideshiru group, nickel Rose sulfonyl decyl oxymethyl group, nickel Rose sulfonyl decyl oxyethyl group, nickel Rose sulfonyl decyloxy propyl, nickel Rose sulfonyl decyloxy-butyl group,
Nickelocenyldecyloxypentyl group, nickelocenyldecyloxyhexyl group, nickelocenyldecyloxyheptyl group, nickelocenyldecyloxyoctyl group, nickelocenyldecyloxynonyl group, nickelocenyldecyloxydecyl group;

A dichlorotitanocenyl methoxymethyl group,
Trichlorotitanium cyclopentadienyl methoxyethyl group, bis (trifluoromethanesulfonato) titanocene methoxypropyl group, dichlorozirconocenyl methoxybutyl group, dimethylzirconocenyl methoxypentyl group, diethoxyzirconocenyl methoxymethyl group, bis (cyclo Pentadienyl) chromium methoxyhexyl group,
Bis (cyclopentadienyl) dichlorohafnium methoxymethyl group, bis (cyclopentadienyl) dichloroniobium methoxyoctyl group, bis (cyclopentadienyl) ruthenium methoxymethyl group, bis (cyclopentadienyl) vanadium methoxymethyl group, An alkyl group having 12 to 30 carbon atoms substituted with a metallocenylalkyloxy group such as a bis (cyclopentadienyl) dichlorovanadium methoxyethyl group or an osmocenylmethoxyethyl group;

Ferrocenecarbonyloxymethyl group, ferrocenecarbonyloxyethyl group, ferrocenecarbonyloxypropyl group, ferrocenecarbonyloxybutyl group, ferrocenecarbonyloxypentyl group, ferrocenecarbonyloxyhexyl group, ferrocenecarbonyloxyheptyl group, ferrocenecarbonyloxyoctyl group , Ferrocenecarbonyloxynonyl group, ferrocenecarbonyloxydecyl group;

Cobaltsencarbonyloxymethyl group,
Cobaltcene carbonyloxyethyl group, Cobaltcene carbonyloxypropyl group, Cobaltcene carbonyloxybutyl group, Cobaltcene carbonyloxypentyl group, Cobaltcene carbonyloxyhexyl group, Cobaltcene carbonyloxyheptyl group, Cobaltcene carbonyloxyoctyl group, Cobalt Sencarbonyloxynonyl group, cobalt sencarbonyloxydecyl group,

A nickelocenecarbonyloxymethyl group,
Nickelocene carbonyloxyethyl group, nickelocene carbonyloxypropyl group, nickelocene carbonyloxybutyl group, nickelocene carbonyloxypentyl group, nickelocene carbonyloxyhexyl group, nickelocene carbonyloxyheptyl group, nickelocene carbonyloxyoctyl group, nickel Rosenecarbonyloxynonyl group, nickelocenecarbonyloxydecyl group,

Dichlorotitanocenylcarbonyloxymethyl group, trichlorotitanium cyclopentadienylcarbonyloxyethyl group, bis (trifluoromethanesulfonato) titanocenecarbonyloxymethoxypropyl group, dichlorozirconocenecarbonyloxybutyl group,
Dimethylzirconocene carbonyloxypentyl group, diethoxyzirconocene carbonyloxymethyl group, bis (cyclopentadienyl) chromium carbonyloxyhexyl group, bis (cyclopentadienyl) dichlorohafnium carbonyloxymethyl group, bis (cyclopentadienyl) dichloro Niobium carbonyloxyoctyl group,
Bis (cyclopentadienyl) ruthenium carbonyloxymethyl group, bis (cyclopentadienyl) vanadium carbonyloxymethyl group, bis (cyclopentadienyl) dichlorovanadium carbonyloxyethyl group,
Examples thereof include an alkyl group having 12 to 30 carbon atoms which is substituted with a metallocenylcarbonyloxy group such as a bis (cyclopentadienyl) osmium carbonyloxyethyl group.

Examples of the substituted or unsubstituted aralkyl group of R ^{1 to} R ¹⁶ are aralkyl groups which may have the same substituents as the above-mentioned alkyl groups, and preferably,
Benzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzyl group, trifluoromethylbenzyl group, naphthylmethyl group, nitronaphthylmethyl group, cyanonaphthylmethyl group, hydroxynaphthylmethyl group, methylnaphthylmethyl group, triphenyl group Examples thereof include an aralkyl group having 7 to 15 carbon atoms such as a fluoromethylnaphthylmethyl group and a fluoren-9-ylethyl group.

Examples of the substituted or unsubstituted aryl group represented by R ^{1 to} R ¹⁶ include aryl groups which may have the same substituents as the above-mentioned alkyl groups, preferably a phenyl group and a nitro group. Phenyl group, cyanophenyl group, hydroxyphenyl group, methylphenyl group, trifluoromethylphenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, trifluoromethylnaphthyl group, methoxycarbonylphenyl group , 4- (5'-methylbenzoxazole-
Examples include aryl groups having 6 to 15 carbon atoms such as 2′-yl) phenyl group and dibutylaminocarbonylphenyl group.

Examples of the substituted or unsubstituted alkenyl group represented by R ^{1 to} R ¹⁶ are alkenyl groups which may have the same substituents as the above-mentioned alkyl groups, and preferably,
Vinyl group, propenyl group, 1-butenyl group, iso-butenyl group, 1-pentenyl group, 2-pentenyl group, 2-
Methyl-1-butenyl group, 3-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-methylcarboxylvinyl group, 2-cyano-2- 2 to 2 carbon atoms such as methylsulfone vinyl group, styryl group, 4-phenyl-2-butenyl group
There may be mentioned 10 alkenyl groups.

Examples of the substituted or unsubstituted alkoxy group of R ^{1 to} R ¹⁶ include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec. -Butoxy group, n-pentyloxy group, isopentyloxy group, t
ert-pentyloxy group, sec-pentyloxy group, cyclopentyloxy group, n-hexyloxy group,
1-methylpentyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, 4-methylpentyloxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group Base 2,
3-dimethylbutoxy group, 1,1,2-trimethylpropoxy group, 1,2,2-trimethylpropoxy group, 1-
Ethylbutoxy group, 2-ethylbutoxy group, 1-ethyl-2-methylpropoxy group, cyclohexyloxy group,
Methylcyclopentyloxy group, n-heptyloxy group, 1-methylhexyloxy group, 2-methylhexyloxy group, 3-methylhexyloxy group, 4-methylhexyloxy group, 5-methylhexyloxy group, 1,1
-Dimethylpentyloxy group, 1,2-dimethylpentyloxy group, 1,3-dimethylpentyloxy group, 1,
4-dimethylpentyloxy group, 2,2-dimethylpentyloxy group, 2,3-dimethylpentyloxy group,
2,4-dimethylpentyloxy group, 3,3-dimethylpentyloxy group, 3,4-dimethylpentyloxy group, 1-ethylpentyloxy group, 2-ethylpentyloxy group, 3-ethylpentyloxy group, 1, 1,2-
Trimethylbutoxy group, 1,1,3-trimethylbutoxy group, 1,2,3-trimethylbutoxy group, 1,2,2
-Trimethylbutoxy group, 1,3,3-trimethylbutoxy group, 2,3,3-trimethylbutoxy group, 1-ethyl-1-methylbutoxy group, 1-ethyl-2-methylbutoxy group, 1-ethyl-3 -Methylbutoxy group, 2-ethyl-1-methylbutoxy group, 2-ethyl-3-methylbutoxy group, 1-n-propylbutoxy group, 1-isopropylbutoxy group, 1-isopropyl-2-methylpropoxy group, methyl Cyclohexyloxy group, n-octyloxy group, 1-methylheptyloxy group, 2-methylheptyloxy group, 3-methylheptyloxy group, 4-
Methylheptyloxy group, 5-methylheptyloxy group, 6-methylheptyloxy group, 1,1-dimethylhexyloxy group, 1,2-dimethylhexyloxy group,
1,3-dimethylhexyloxy group, 1,4-dimethylhexyloxy group, 1,5-dimethylhexyloxy group, 2,2-dimethylhexyloxy group, 2,3-dimethylhexyloxy group, 2,4-dimethyl Hexyloxy group, 2,5-dimethylhexyloxy group, 3,3-dimethylhexyloxy group, 3,4-dimethylhexyloxy group, 3,5-dimethylhexyloxy group, 4,4-
Dimethylhexyloxy group, 4,5-dimethylhexyloxy group, 1-ethylhexyloxy group, 2-ethylhexyloxy group, 3-ethylhexyloxy group, 4-ethylhexyloxy group, 1-n-propylpentyloxy group, 2-n -Propylpentyloxy group, 1-isopropylpentyloxy group, 2-isopropylpentyloxy group, 1-ethyl-1-methylpentyloxy group, 1
-Ethyl-2-methylpentyloxy group, 1-ethyl-
3-methylpentyloxy group, 1-ethyl-4-methylpentyloxy group, 2-ethyl-1-methylpentyloxy group, 2-ethyl-2-methylpentyloxy group, 2
-Ethyl-3-methylpentyloxy group, 2-ethyl-
4-methylpentyloxy group, 3-ethyl-1-methylpentyloxy group, 3-ethyl-2-methylpentyloxy group, 3-ethyl-3-methylpentyloxy group, 3
-Ethyl-4-methylpentyloxy group, 1,1,2-
Trimethylpentyloxy group, 1,1,3-trimethylpentyloxy group, 1,1,4-trimethylpentyloxy group, 1,2,2-trimethylpentyloxy group,
1,2,3-trimethylpentyloxy group, 1,2,4
-Trimethylpentyloxy group, 1,3,4-trimethylpentyloxy group, 2,2,3-trimethylpentyloxy group, 2,2,4-trimethylpentyloxy group,
2,3,4-trimethylpentyloxy group, 1,3,3
-Trimethylpentyloxy group, 2,3,3-trimethylpentyloxy group, 3,3,4-trimethylpentyloxy group, 1,4,4-trimethylpentyloxy group,
2,4,4-trimethylpentyloxy group, 3,4,4
-Trimethylpentyloxy group, 1-n-butylbutoxy group, 1-isobutylbutoxy group, 1-sec-butylbutoxy group, 1-tert-butylbutoxy group, 2-t
ert-butylbutoxy group, 1-n-propyl-1-methylbutoxy group, 1-n-propyl-2-methylbutoxy group, 1-n-propyl-3-methylbutoxy group, 1-
Isopropyl-1-methylbutoxy group, 1-isopropyl-2-methylbutoxy group, 1-isopropyl-3-methylbutoxy group, 1,1-diethylbutoxy group, 1,2
-Diethylbutoxy group, 1-ethyl-1,2-dimethylbutoxy group, 1-ethyl-1,3-dimethylbutoxy group, 1-ethyl-2,3-dimethylbutoxy group, 2-ethyl-1,1-dimethyl Butoxy group, 2-ethyl-1,
2-dimethylbutoxy group, 2-ethyl-1,3-dimethylbutoxy group, 2-ethyl-2,3-dimethylbutoxy group, 1,1,3,3-tetramethylbutoxy group, 1,2
-Dimethylcyclohexyloxy group, 1,3-dimethylcyclohexyloxy group, 1,4-dimethylcyclohexyloxy group, ethylcyclohexyloxy group, n-nonyloxy group, 3,5,5-trimethylhexyloxy group, n-decyloxy group, n-undecyloxy group, n
-Dodecyloxy group, 1-adamantyloxy group, n-
A linear, branched or cyclic unsubstituted alkoxy group having 1 to 15 carbon atoms such as a pentadecyloxy group;

Methoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, n-propoxyethoxy group,
Isopropoxyethoxy group, n-butoxyethoxy group,
Isobutoxyethoxy group, tert-butoxyethoxy group, sec-butoxyethoxy group, n-pentyloxyethoxy group, isopentyloxyethoxy group, tert
-Pentyloxyethoxy group, sec-pentyloxyethoxy group, cyclopentyloxyethoxy group, n-hexyloxyethoxy group, ethylcyclohexyloxyethoxy group, n-nonyloxyethoxy group, (3,5,5
5-trimethylhexyloxy) ethoxy group, (3,
5,5-trimethylhexyloxy) butoxy group, n-
Decyloxyethoxy group, n-undecyloxyethoxy group, n-dodecyloxyethoxy group, 3-methoxypropoxy group, 3-ethoxypropoxy group, 3- (n-propoxy) propoxy group, 2-isopropoxypropoxy group, 2 -Methoxybutoxy group, 2-ethoxybutoxy group, 2- (n-propoxy) butoxy group, 4-isopropoxybutoxy group, decalyloxyethoxy group, adamantyloxyethoxy group and the like, having 2 carbon atoms substituted with an alkoxy group. ~ 15 alkoxy groups;

Methoxymethoxymethoxy group, ethoxymethoxymethoxy group, propoxymethoxymethoxy group, butoxymethoxymethoxy group, methoxyethoxymethoxy group, ethoxyethoxymethoxy group, propoxyethoxymethoxy group, butoxyethoxymethoxy group, methoxypropoxymethoxy group, ethoxypropoxy. Methoxy group,
Propoxypropoxymethoxy group, butoxypropoxymethoxy group, methoxybutoxymethoxy group, ethoxybutoxymethoxy group, propoxybutoxymethoxy group, butoxybutoxymethoxy group, methoxymethoxyethoxy group, ethoxymethoxyethoxy group, propoxymethoxyethoxy group, butoxymethoxyethoxy group, Methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propoxyethoxyethoxy group, butoxyethoxyethoxy group, methoxypropoxyethoxy group, ethoxypropoxyethoxy group, propoxypropoxyethoxy group, butoxypropoxyethoxy group, methoxybutoxyethoxy group, ethoxybutoxyethoxy group, Propoxy butoxy ethoxy group, butoxy butoxy ethoxy group, methoxy methoxy propoxy , Ethoxy methoxypropoxy group,
Propoxymethoxypropoxy group, butoxymethoxypropoxy group, methoxyethoxypropoxy group, ethoxyethoxypropoxy group, propoxyethoxypropoxy group, butoxyethoxypropoxy group, methoxypropoxypropoxy group, ethoxypropoxypropoxy group, propoxypropoxypropoxy group, butoxypropoxypropoxy group, Methoxybutoxypropoxy group, ethoxybutoxypropoxy group, propoxybutoxypropoxy group, butoxybutoxypropoxy group, methoxymethoxybutoxy group, ethoxymethoxybutoxy group, propoxymethoxybutoxy group, butoxymethoxybutoxy group,
Methoxyethoxy butoxy group, ethoxy ethoxy butoxy group, propoxy ethoxy butoxy group, butoxy ethoxy butoxy go, methoxy propoxy butoxy group, ethoxy propoxy butoxy group, propoxy propoxy butoxy group, butoxy propoxy butoxy group, methoxy butoxy butoxy group, ethoxy butoxy butoxy group , Propoxybutoxybutoxy group, butoxybutoxybutoxy group, (4-ethylcyclohexyloxy) ethoxyethoxy group, (2-ethyl-1-hexyloxy) ethoxypropoxy group, [4- (3,5,5-trimethylhexyloxy) Butoxy] ethoxy group or the like, which is substituted with an alkoxyalkoxy group, and has a linear, branched, or cyclic carbon number 3
~ 15 alkoxy groups;

Methoxycarbonylmethoxy group, ethoxycarbonylmethoxy group, n-propoxycarbonylmethoxy group, isopropoxycarbonylmethoxy group, (4 '
3 to 1 carbon atoms substituted with an alkoxycarbonyl group such as -ethylcyclohexyloxy) carbonylmethoxy group
An alkoxy group of 0;

C3-10 alkoxy group substituted with an acyl group such as acetylmethoxy group, ethylcarbonylmethoxy group, octylcarbonylmethoxy group and phenacyloxy group; acetyloxymethoxy group, acetyloxyethoxy group, acetyloxy C3-C10 alkoxy group substituted with an acyloxy group such as hexyloxy group, butanoyloxycyclohexyloxy group; methylaminomethoxy group, 2-methylaminoethoxy group, 2
-(2-methylaminoethoxy) ethoxy group, 4-methylaminobutoxy group, 1-methylaminopropan-2-yloxy group, 3-methylaminopropoxy group, 2-methylamino-2-methylpropoxy group, 2-ethyl Aminoethoxy group, 2- (2-ethylaminoethoxy) ethoxy group, 3-ethylaminopropoxy group, 1-ethylaminopropoxy group, 2-isopropylaminoethoxy group, 2
-(N-Butylamino) ethoxy group, 3- (n-hexylamino) propoxy group, 4- (cyclohexylamino) butyloxy group and like alkylamino group-substituted alkoxy groups having 2 to 10 carbon atoms; methylaminomethoxy Alkoxy having 3 to 10 carbon atoms substituted with an alkylaminoalkoxy group such as a methoxy group, a methylaminoethoxyethoxy group, a methylaminoethoxypropoxy group, an ethylaminoethoxypropoxy group and a 4- (2'-isobutylaminopropoxy) butoxy group. Group;

Dimethylaminomethoxy group, 2-dimethylaminoethoxy group, 2- (2-dimethylaminoethoxy)
Ethoxy group, 4-dimethylaminobutoxy group, 1-dimethylaminopropan-2-yloxy group, 3-dimethylaminopropoxy group, 2-dimethylamino-2-methylpropoxy group, 2-diethylaminoethoxy group, 2-
(2-diethylaminoethoxy) ethoxy group, 3-diethylaminopropoxy group, 1-diethylaminopropoxy group, 2-diisopropylaminoethoxy group, 2- (di-
an n-butylamino) ethoxy group, a 2-piperidylethoxy group, a 3- (di-n-hexylamino) propoxy group, or another alkoxy group having 3 to 15 carbon atoms, which is substituted with a dialkylamino group; a dimethylaminomethoxymethoxy group, An alkoxy group having 4 to 15 carbon atoms substituted with a dialkylaminoalkoxy group such as a dimethylaminoethoxyethoxy group, a dimethylaminoethoxypropoxy group, a diethylaminoethoxypropoxy group and a 4- (2'-diisobutylaminopropoxy) butoxy group;

Methylthiomethoxy group, 2-methylthioethoxy group, 2-ethylthioethoxy group, 2-n-propylthioethoxy group, 2-isopropylthioethoxy group,
A 2-n-butylthioethoxy group, a 2-isobutylthioethoxy group, a (3,5,5-trimethylhexylthio) hexyloxy group, or another alkoxy group having 2 to 15 carbon atoms, which is substituted with an alkylthio group; Preferably,
Methoxy group, ethoxy group, n-propoxy group, iso-
Propoxy group, n-butoxy group, iso-butoxy group,
sec-butoxy group, t-butoxy group, n-pentoxy group, iso-pentoxy group, neopentoxy group, 2-methylbutoxy group, 2-ethylhexyloxy group, 3,
Examples thereof include alkoxy groups having 1 to 10 carbon atoms such as 5,5-trimethylhexyloxy group, decalyloxy group, methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, and ethoxyethoxyethoxy group.

Examples of the substituted or unsubstituted aralkyloxy group for R ^{1 to} R ¹⁶ are aralkyloxy groups which may have the same substituents as the above-mentioned alkyl groups,
Preferably, benzyloxy group, nitrobenzyloxy group, cyanobenzyloxy group, hydroxybenzyloxy group, methylbenzyloxy group, trifluoromethylbenzyloxy group, naphthylmethoxy group, nitronaphthylmethoxy group, cyanonaphthylmethoxy group, hydroxynaphthyl Examples thereof include an aralkyloxy group having 7 to 15 carbon atoms such as a methoxy group, a methylnaphthylmethoxy group, a trifluoromethylnaphthylmethoxy group, and a fluoren-9-ylethoxy group.

Examples of the substituted or unsubstituted aryloxy group represented by R ^{1 to} R ¹⁶ include aryloxy groups which may have the same substituents as the above-mentioned alkyl groups, and preferably a phenoxy group. , 2-methylphenoxy group, 4-
Methylphenoxy group, 4-t-butylphenoxy group, 2
-Methoxyphenoxy group, 4-iso-propylphenoxy group, naphthoxy group, ferrocenyloxy group, cobaltcenyloxy group, nickelocenyloxy group, octamethylferrocenyloxy group, octamethylcobaltcenyloxy group, Examples thereof include an aryloxy group having 6 to 18 carbon atoms such as an octamethyl nickelocenyloxy group.

Examples of the substituted or unsubstituted alkenyloxy group of R ^{1 to} R ¹⁶ are alkenyloxy groups which may have the same substituents as the above-mentioned alkyl groups,
Preferably, a vinyloxy group, a propenyloxy group, 1
-Butenyloxy group, iso-butenyloxy group, 1-
Pentenyloxy group, 2-pentenyloxy group, 2-methyl-1-butenyloxy group, 3-methyl-1-butenyloxy group, 2-methyl-2-butenyloxy group, cyclopentadienyloxy group, 2,2-dicyanovinyl group An oxy group, a 2-cyano-2-methylcarboxyl vinyloxy group, a 2-cyano-2-methylsulfone vinyloxy group, a styryloxy group, a 4-phenyl-2-butenyloxy group, a cinnamylalkoxy group and the like having 2 to 2 carbon atoms. 10
Alkenyloxy groups of

Examples of the substituted or unsubstituted alkylthio groups represented by R ^{1 to} R ¹⁶ include alkylthio groups which may have the same substituents as the above-mentioned alkyl groups, preferably a methylthio group and an ethylthio group. Group, n-propylthio group, iso-propylthio group, n-butylthio group, is
o-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, neopentylthio group, 2-methylbutylthio group, methylcarboxyethylthio group, 2-ethylhexylthio group, 3 And an alkylthio group having 1 to 10 carbon atoms such as a 5,5,5-trimethylhexylthio group and a decalylthio group.

Examples of the substituted or unsubstituted aralkylthio group represented by R ^{1 to} R ¹⁶ include an aralkylthio group which may have a substituent similar to the above-mentioned alkyl group, and preferably a benzylthio group. , Nitrobenzylthio group, cyanobenzylthio group, hydroxybenzylthio group, methylbenzylthio group, trifluoromethylbenzylthio group,
Naphthylmethylthio group, nitronaphthylmethylthio group,
Examples thereof include an aralkylthio group having 7 to 12 carbon atoms such as a cyanonaphthylmethylthio group, a hydroxynaphthylmethylthio group, a methylnaphthylmethylthio group, a trifluoromethylnaphthylmethylthio group and a fluoren-9-ylethylthio group.

Examples of the substituted or unsubstituted arylthio group represented by R ^{1 to} R ¹⁶ include arylthio groups which may have the same substituents as the above-mentioned alkyl groups, preferably a phenylthio group and 4- Methylphenylthio group, 2-
Methoxyphenylthio group, 4-t-butylphenylthio group, naphthylthio group, ferrocenylthio group, cobaltcenylthio group, nickelocenylthio group, octamethylferrocenylthio group, octamethylcobaltcenylthio group,
C6-10 carbon atoms such as octamethyl nickelocenylthio group
And the arylthio group.

Examples of the substituted or unsubstituted alkenylthio group for R ^{1 to} R ¹⁶ are alkenylthio groups which may have the same substituents as the above-mentioned alkyl groups, preferably a vinylthio group, Allylthio group, butenylthio group,
Examples thereof include alkenylthio groups having 2 to 10 carbon atoms such as hexanedienylthio group, cyclopentadienylthio group, styrylthio group, cyclohexenylthio group and decenylthio group.

Examples of the mono-substituted amino group represented by R ^{1 to} R ¹⁶ include mono-substituted amino groups which may have the same substituents as the above-mentioned alkyl groups, preferably a methylamino group and an ethyl group. Amino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, (2-ethylhexyl)
A monoalkylamino group having 1 to 10 carbon atoms such as an amino group, a cyclohexylamino group, a (3,5,5-trimethylhexyl) amino group, a nonylamino group and a decylamino group;

Benzylamino group, phenethylamino group,
(3-Phenylpropyl) amino group, (4-ethylbenzyl) amino group, (4-isopropylbenzyl) amino group, (4-methylbenzyl) amino group, (4-ethylbenzyl) amino group, (4-allylbenzyl) ) An amino group,
[4- (2-cyanoethyl) benzyl] amino group, [4
A monoaralkylamino group having 7 to 10 carbon atoms such as-(2-acetoxyethyl) benzyl] amino group; anilino group, naphthylamino group, toluidino group, xylidino group,
Ethylanilino group, isopropylanilino group, methoxyanilino group, ethoxyanilino group, chloroanilino group,
Acetylanilino group, methoxycarbonylanilino group,
Ethoxycarbonylanilino group, propoxycarbonylanilino group, 4-methylanilino group, 4-ethylanilino group, ferrocenylamino group, cobaltcenylamino group, nickelocenylamino group, zirconocenylamino group, octamethylferrocene group Nylamino group, octamethylcobaltcenylamino group, octamethylnickerocenylamino group, octamethylzirconocenylamino group, etc.
A monoarylamino group having 6 to 10 carbon atoms;

A carbon number of 2 to 10 such as vinylamino group, allylamino group, butenylamino group, pentenylamino group, hexenylamino group, cyclohexenylamino group, cyclopentadienylamino group, octadienylamino group and adamantenylamino group. A monoalkenylamino group of:

Formylamino group, methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, iso-propylcarbonylamino group,
n-butylcarbonylamino group, iso-butylcarbonylamino group, sec-butylcarbonylamino group, t
-Butylcarbonylamino group, n-pentylcarbonylamino group, iso-pentylcarbonylamino group, neopentylcarbonylamino group, 2-methylbutylcarbonylamino group, benzoylamino group, methylbenzoylamino group, ethylbenzoylamino group, tolylcarbonyl Amino group, propylbenzoylamino group, 4-t-butylbenzoylamino group, nitrobenzylcarbonylamino group, 3-butoxy-2-naphthoylamino group, cinnamoylamino group, ferrocenecarbonylamino group, 1
Examples of the amino group include an acylamino group having 1 to 16 carbon atoms such as a -methylferrocene-1'-carbonylamino group, a cobaltocenecarbonylamino group and a nickelocenecarbonylamino group.

Examples of the di-substituted amino group of R ^{1 to} R ¹⁶ are di-substituted amino groups which may have the same substituents as the above-mentioned alkyl groups, preferably dimethylamino group and diethylamino group. Group, methylethylamino group, dipropylamino group, dibutylamino group, di-n-hexylamino group, dicyclohexylamino group, dioctylamino group, bis (methoxyethyl) amino group, bis (ethoxyethyl) amino group, bis ( Propoxyethyl) amino group, bis (butoxyethyl) amino group, di (acetyloxyethyl) amino group, di (hydroxyethyl) amino group, N-ethyl-N- (2-cyanoethyl) amino group,
A dialkylamino group having 2 to 16 carbon atoms such as a di (propionyloxyethyl) amino group;

Dibenzylamino group, diphenethylamino group, bis (4-ethylbenzyl) amino group, bis (4-
14 to 2 carbon atoms such as isopropylbenzyl) amino group
0 diaralkylamino group; diphenylamino group, ditolylamino group, N-phenyl-N-tolylamino group and other diarylamino groups having 12 to 14 carbon atoms; divinylamino group, diallylamino group, dibutenylamino group, dipentenylamino group, A dialkenylamino group having 4 to 12 carbon atoms such as dihexenylamino group, bis (cyclopentadienyl) amino group, N-vinyl-N-allylamino group; diformylamino group, di (methylcarbonyl) amino group, di (Ethylcarbonyl) amino group, di (n-propylcarbonyl) amino group, di (iso-propylcarbonyl) amino group, di (n-butylcarbonyl) amino group, di (iso-butylcarbonyl) amino group, di (s
ec-butylcarbonyl) amino group, di (t-butylcarbonyl) amino group, di (n-pentylcarbonyl) amino group, di (iso-pentylcarbonyl) amino group,
Di (neopentylcarbonyl) amino group, di (2-methylbutylcarbonyl) amino group, di (benzoyl) amino group, di (methylbenzoyl) amino group, di (ethylbenzoyl) amino group, di (tolylcarbonyl) amino group , Di (propylbenzoyl) amino group, di (4-t-
Butylbenzoyl) amino group, di (nitrobenzylcarbonyl) amino group, di (3-butoxy-2-naphthoyl) amino group, di (cinnamoyl) amino group, diacylamino group having 2 to 30 carbon atoms such as imino succinate group ;

N-phenyl-N-allylamino group, N-
(2-acetyloxyethyl) -N-ethylamino group,
N-tolyl-N-methylamino group, N-vinyl-N-methylamino group, N-benzyl-N-allylamino group, N
-Methyl-ferrocenylamino group, N-ethyl-cobaltcenylamino group, N-butyl-nickelocenylamino group, N-hexyl-octamethylferrocenylamino group, N-methyl-octamethylcobaltcenyl group C3-C24 di-substituted amino group having a substituent selected from a substituted or unsubstituted alkyl group such as amino group and N-methyl-octamethyl nickelocenylamino group, aralkyl group, aryl group and alkenyl group. Is mentioned.

Examples of the substituted or unsubstituted acyl group represented by R ^{1 to} R ¹⁶ include an acyl group which may have the same substituent as the above-mentioned alkyl group, preferably a formyl group and a methyl group. Carbonyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group,
n-butylcarbonyl group, iso-butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neopentylcarbonyl group, 2-methylbutylcarbonyl group, benzoyl group , Methylbenzoyl group, ethylbenzoyl group, tolylcarbonyl group, propylbenzoyl group, 4-t-butylbenzoyl group, nitrobenzylcarbonyl group, 3-butoxy-2-naphthoyl group, cinnamoyl group, ferrocenecarbonyl group, 1-methylferrocene 1 to 1 carbon atoms such as carbonyl group
There may be mentioned 15 acyl groups.

Examples of the substituted or unsubstituted alkoxycarbonyl group of R ^{1 to} R ¹⁶ are alkoxycarbonyl groups which may have the same substituents as the above-mentioned alkyl groups, and preferably a methoxycarbonyl group. , Ethoxycarbonyl group, n-propoxycarbonyl group, iso-propoxycarbonyl group, n-butoxycarbonyl group, i
so-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-pentoxycarbonyl group, iso-pentoxycarbonyl group, neopentoxycarbonyl group, 2-pentoxycarbonyl group,
2-ethylhexyloxycarbonyl group, 3,5,5-
Trimethylhexyloxycarbonyl group, decalyloxycarbonyl group, cyclohexyloxycarbonyl group,
A C2-C11 alkoxycarbonyl group such as a chloroethoxycarbonyl group, a hydroxymethoxycarbonyl group, and a hydroxyethoxycarbonyl group;

Methoxymethoxycarbonyl group, methoxyethoxycarbonyl group, ethoxyethoxycarbonyl group, propoxyethoxycarbonyl group, butoxyethoxycarbonyl group, pentoxyethoxycarbonyl group, hexyloxyethoxycarbonyl group, butoxybutoxycarbonyl group, hexyloxybutoxycarbonyl group. ,
C3-C11 alkoxycarbonyl group substituted with an alkoxy group such as hydroxymethoxymethoxycarbonyl group and hydroxyethoxyethoxycarbonyl group; methoxymethoxymethoxycarbonyl group, methoxyethoxyethoxycarbonyl group, ethoxyethoxyethoxycarbonyl group, propoxyethoxyethoxycarbonyl Base,
An alkoxycarbonyl group having 4 to 11 carbon atoms, which is substituted with an alkoxyalkoxy group such as butoxyethoxyethoxycarbonyl group, pentoxyethoxyethoxycarbonyl group, hexyloxyethoxyethoxycarbonyl group;

Ferrocenylmethoxycarbonyl group, ferrocenylethoxycarbonyl group, ferrocenylpropoxycarbonyl group, ferrocenylbutoxycarbonyl group,
Ferrocenylpentyloxycarbonyl group, ferrocenylhexyloxycarbonyl group, ferrocenylheptyloxycarbonyl group, ferrocenyloctyloxycarbonyl group, ferrocenylnonyloxycarbonyl group, ferrocenyldecyloxycarbonyl group, cobaltcenyl Methoxycarbonyl group, cobaltcenylethoxycarbonyl group, cobaltcenylpropoxycarbonyl group, cobaltcenylbutoxycarbonyl group, cobaltcenylpentyloxycarbonyl group, cobaltcenylhexyloxycarbonyl group, cobaltcenylheptyloxycarbonyl group, cobaltoce Nyloctyloxycarbonyl group,
Cobalt cenyl nonyloxycarbonyl group, cobalt cenyldecyloxycarbonyl group, nickelocenylmethoxycarbonyl group, nickelocenylethoxycarbonyl group, nickelocenylpropoxycarbonyl group, nickelocenylbutoxycarbonyl group, nickelocenylpentyloxycarbonyl group Group, nickelocenylhexyloxycarbonyl group, nickelocenylheptyloxycarbonyl group, nickelocenyloctyloxycarbonyl group, nickelocenylnonyloxycarbonyl group, nickelocenyldecyloxycarbonyl group,

Dichlorotitanocenyl methoxycarbonyl group, trichlorotitanium cyclopentadienyl methoxycarbonyl group, bis (trifluoromethanesulfonato) titanocene methoxycarbonyl group, dichlorozirconocenyl methoxycarbonyl group, dimethylzirconocenyl methoxycarbonyl group, dichlorozirconocenyl methoxycarbonyl group, Ethoxyzirconocenyl methoxycarbonyl group, bis (cyclopentadienyl) chromium methoxycarbonyl group, bis (cyclopentadienyl) dichlorohafnium methoxycarbonyl group, bis (cyclopentadienyl) dichloroniobium methoxycarbonyl group, bis (cyclopenta Dienyl) ruthenium methoxycarbonyl group, bis (cyclopentadienyl) vanadium methoxycarbonyl group, bis (cyclopentadienyl) dichlorovanadiu Methoxycarbonyl group, bis carbon atoms substituted with metallocenyl group such as (cyclopentadienyl) osmium-methoxycarbonyl group 11-20
Alkoxycarbonyl group;

Examples of the substituted or unsubstituted aralkyloxycarbonyl group for R ^{1 to} R ¹⁶ are aralkyloxycarbonyl groups which may have the same substituents as the above-mentioned alkyl groups, and preferably, Benzyloxycarbonyl group, nitrobenzyloxycarbonyl group, cyanobenzyloxycarbonyl group, hydroxybenzyloxycarbonyl group, methylbenzyloxycarbonyl group,
Trifluoromethylbenzyloxycarbonyl group, naphthylmethoxycarbonyl group, nitronaphthylmethoxycarbonyl group, cyanonaphthylmethoxycarbonyl group, hydroxynaphthylmethoxycarbonyl group, methylnaphthylmethoxycarbonyl group, trifluoromethylnaphthylmethoxycarbonyl group, fluoren-9-yl Examples thereof include an aralkyloxycarbonyl group having 8 to 16 carbon atoms such as an ethoxycarbonyl group.

Examples of the substituted or unsubstituted aryloxycarbonyl group represented by R ^{1 to} R ¹⁶ include aryloxycarbonyl groups which may have the same substituents as the above-mentioned aryl groups, and preferably, Phenoxycarbonyl group, 2-methylphenoxycarbonyl group, 4-methylphenoxycarbonyl group, 4-t-butylphenoxycarbonyl group, 2-methoxyphenoxycarbonyl group, 4-
iso-propylphenoxycarbonyl group, naphthoxycarbonyl group, ferrocenyloxycarbonyl group, cobaltcenyloxycarbonyl group, nickelocenyloxycarbonyl group, zirconocenyloxycarbonyl group, octamethylferrocenyloxycarbonyl group, octa Examples thereof include an aryloxycarbonyl group having 7 to 11 carbon atoms such as a methylcobaltcenyloxycarbonyl group, an octamethylnickerocenyloxycarbonyl group and an octamethylzirconocenyloxycarbonyl group.

Examples of the substituted or unsubstituted alkenyloxycarbonyl group of R ^{1 to} R ¹⁶ are alkenyloxycarbonyl groups which may have the same substituents as the above-mentioned alkyl groups, and preferably, Vinyloxycarbonyl group, propenyloxycarbonyl group, 1-butenyloxycarbonyl group, iso-butenyloxycarbonyl group, 1-pentenyloxycarbonyl group, 2-pentenyloxycarbonyl group, cyclopentadienyloxycarbonyl group, 2- Methyl-1-butenyloxycarbonyl group, 3-methyl-1-butenyloxycarbonyl group, 2-methyl-2-butenyloxycarbonyl group,
2,2-dicyanovinyloxycarbonyl group, 2-cyano-2-methylcarboxylvinyloxycarbonyl group, 2-cyano-2-methylsulfone vinyloxycarbonyl group, styryloxycarbonyl group, 4-phenyl-2-butenyloxy 3 to 1 carbon atoms such as carbonyl group
1 alkenyloxycarbonyl group.

Examples of the mono-substituted aminocarbonyl group represented by R ^{1 to} R ¹⁶ include mono-substituted aminocarbonyl groups which may have the same substituents as the above-mentioned alkyl groups, preferably methylaminocarbonyl. Group, ethylaminocarbonyl group, propylaminocarbonyl group, butylaminocarbonyl group, pentylaminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group,
Octylaminocarbonyl group, (2-ethylhexyl)
Aminoalkyl group, cyclohexylaminocarbonyl group, (3,5,5-trimethylhexyl) aminocarbonyl group, nonylaminocarbonyl group, decylaminocarbonyl group and other monoalkylaminocarbonyl groups having 2 to 11 carbon atoms; benzylaminocarbonyl group , Phenethylaminocarbonyl group, (3-phenylpropylaminocarbonyl group, (4-ethylbenzyl) aminocarbonyl group, (4-isopropylbenzyl) aminocarbonyl group, (4-methylbenzyl) aminocarbonyl group, (4
-Ethylbenzyl) aminocarbonyl group, (4-allylbenzyl) aminocarbonyl group, [4- (2-cyanoethyl) benzyl] aminocarbonyl group, [4- (2-acetoxyethyl) benzyl] aminocarbonyl group, and the like. 8-11 monoaralkylaminocarbonyl groups;

Anilinocarbonyl group, naphthylaminocarbonyl group, toluidinocarbonyl group, xylidinocarbonyl group, ethylanilinocarbonyl group, isopropylanilinocarbonyl group, methoxyanilinocarbonyl group, ethoxyanilinocarbonyl group, chloroani Rinocarbonyl group, acetylanilinocarbonyl group, methoxycarbonylanilinocarbonyl group, ethoxycarbonylanilinocarbonyl group, propoxycarbonylanilinocarbonyl group, 4-methylanilinocarbonyl group, 4-
Monoarylaminocarbonyl group having 7 to 11 carbon atoms such as ethylanilinocarbonyl group; vinylaminocarbonyl group, allylaminocarbonyl group, butenylaminocarbonyl group, pentenylaminocarbonyl group, hexenylaminocarbonyl group, cyclohexenylaminocarbonyl group , An octadienylaminocarbonyl group, an adamantenylaminocarbonyl group, and the like, and a monoalkenylaminocarbonyl group having 3 to 11 carbon atoms.

Examples of the di-substituted aminocarbonyl group represented by R ^{1 to} R ¹⁶ include a di-substituted aminocarbonyl group which may have the same substituent as the above-mentioned alkyl group, and preferably dimethylaminocarbonyl. Group, diethylaminocarbonyl group, methylethylaminocarbonyl group, dipropylaminocarbonyl group, dibutylaminocarbonyl group, di-n-hexylaminocarbonyl group, dicyclohexylaminocarbonyl group, dioctylaminocarbonyl group, pyrrolidinocarbonyl group, piperidino Carbonyl group, morpholino carbonyl group, bis (methoxyethyl)
Aminocarbonyl group, bis (ethoxyethyl) aminocarbonyl group, bis (propoxyethyl) aminocarbonyl group, bis (butoxyethyl) aminocarbonyl group, di (acetyloxyethyl) aminocarbonyl group, di (hydroxyethyl) aminocarbonyl group, N-ethyl-N
A dialkylaminocarbonyl group having 3 to 17 carbon atoms such as a-(2-cyanoethyl) aminocarbonyl group and a di (propionyloxyethyl) aminocarbonyl group;

Dibenzylaminocarbonyl group, diphenethylaminocarbonyl group, bis (4-ethylbenzyl)
C15 to C21 diaralkylaminocarbonyl group such as aminocarbonyl group and bis (4-isopropylbenzyl) aminocarbonyl group; diphenylaminocarbonyl group, ditolylaminocarbonyl group, N-phenyl-
13 to 15 carbon atoms such as N-tolylaminocarbonyl group
A diarylaminocarbonyl group; a divinylaminocarbonyl group, a diallylaminocarbonyl group, a dibutenylaminocarbonyl group, a dipentenylaminocarbonyl group,
Dialkenylaminocarbonyl group having 5 to 13 carbon atoms such as dihexenylaminocarbonyl group and N-vinyl-N-allylaminocarbonyl group; N-phenyl-N-allylaminocarbonyl group, N- (2-acetyloxyethyl) -N-ethylaminocarbonyl group, N-tolyl-N
-Substituted group selected from substituted or unsubstituted alkyl groups such as methylaminocarbonyl group, N-vinyl-N-methylaminocarbonyl group, N-benzyl-N-allylaminocarbonyl group, aralkyl group, aryl group, alkenyl group And a di-substituted aminocarbonyl group having 4 to 11 carbon atoms.

Examples of the substituted or unsubstituted acyloxy group of R ^{1 to} R ¹⁶ include an acyloxy group which may have a substituent similar to the above-mentioned alkyl group, preferably a formyloxy group, Methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, n-butylcarbonyloxy group, iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group Group, n-pentylcarbonyloxy group, iso-pentylcarbonyloxy group, neopentylcarbonyloxy group, 2-methylbutylcarbonyloxy group, benzoyloxy group, methylbenzoyloxy group, ethylbenzoyloxy group, tolylcarbonyloxy group, propyl Ben Yloxy group, 4-t-butylbenzoyloxy group, nitrobenzylcarbonyloxy group, 3-butoxy-2-naphthoyloxy group, cinnamoyloxy group, ferrocenecarbonyloxy group, 1-methylferrocene-1′-carbonyloxy group , An acyloxy group having 2 to 16 carbon atoms such as a cobaltocenecarbonyloxy group and a nickelocenecarbonyloxy group.

Examples of the substituted or unsubstituted heteroaryl group of R ^{1 to} R ¹⁶ are heteroaryl groups which may have the same substituents as the above-mentioned alkyl groups, and preferably a furanyl group. , Pyrrolyl group, 3-pyrrolino group, pyrazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, 1,2,3-oxadiazolyl group, 1,2,3
-Triazolyl group, 1,2,4-triazolyl group, 1,
3,4-thiadiazolyl group, pyridinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, piperazinyl group, triazinyl group, benzofuranyl group, indolyl group, thionaphthenyl group, benzimidazolyl group, benzothiazolyl group, benzotriazol-2-yl group, Benzotriazol-1-yl group, purinyl group, quinolinyl group, isoquinolinyl group, coumarinyl group, cinnolinyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group, phenanthronylyl group, phenothiazinyl group,
An unsubstituted heteroaryl group such as a flavonyl group, a phthalimidyl group, a naphthylimidyl group;

Alternatively, the following substituents, that is, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano group; methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and heptyl group. , Octyl group, decyl group, methoxymethyl group, ethoxyethyl group,
Alkyl groups such as ethoxyethyl group and trifluoromethyl group; aralkyl groups such as benzyl group and phenethyl group; aryl groups such as phenyl group, tolyl group, naphthyl group, xylyl group, mesyl group, chlorophenyl group, methoxyphenyl group; methoxy Group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, 2-ethylhexyloxy group, 3,5,5-trimethylhexyloxy group, ferrocene Alkoxy groups such as methoxy group, cobaltene methoxy group and nickelocene methoxy group; aralkyloxy groups such as benzyloxy group, phenethyloxy group; phenoxy group, tolyloxy group, naphthoxy group, xylyloxy group, mesityloxy group, chlorophenoxy group Group, an aryloxy group such as a methoxyphenoxy group; vinyloxy group; a vinyl group, an allyl group, butenyl group, butadienyl group, pentenyl group, cyclopentadienyl group, an alkenyl group such as octenyl
Alkenyloxy groups such as allyloxy group, butenyloxy group, butadienyloxy group, pentenyloxy group, cyclopentadienyloxy group, octenyloxy group; methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group , Heptylthio group, octylthio group, decylthio group, methoxymethylthio group, ethoxyethylthio group, ethoxyethylthio group,
Alkylthio group such as trifluoromethylthio group; Aralkylthio group such as benzylthio group and phenethylthio group;
Arylthio groups such as phenylthio group, tolylthio group, naphthylthio group, xylylthio group, mesylthio group, chlorophenylthio group, methoxyphenylthio group; dialkylamino groups such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group; acetyl Groups, propionyl groups, butanoyl groups, ferrocenecarbonyl groups, cobaltocenecarbonyl groups, nickelocenecarbonyl groups, and other acyl groups; methoxycarbonyl groups, ethoxycarbonyl groups, ferrocenemethoxycarbonyl groups, 1-methylferrocene-1′-ylmethoxycarbonyl Group, an alkoxycarbonyl group such as a cobaltcenylmethoxycarbonyl group and a nickelocenylmethoxycarbonyl group; an aralkyloxy group such as a benzyloxycarbonyl group and a phenethyloxycarbonyl group Sicarbonyl group; phenoxycarbonyl group, tolyloxycarbonyl group, naphthoxycarbonyl group, xylyloxycarbonyl group, mesyloxycarbonyl group, chlorophenoxycarbonyl group, methoxyphenoxycarbonyl group and other aryloxycarbonyl groups; vinyloxycarbonyl group, Alkenyloxycarbonyl groups such as allyloxycarbonyl group, butenyloxycarbonyl group, butadienyloxycarbonyl group, cyclopentadienyloxy group, pentenyloxycarbonyl group, octenyloxycarbonyl group; methylaminocarbonyl group, ethylaminocarbonyl group Group, propylaminocarbonyl group, butylaminocarbonyl group, pentylaminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group, octyl Aminoalkyl group, nonylaminocarbonyl group, 3,5,5-trimethylhexylaminocarbonyl group, 2-ethylhexylaminocarbonyl group or other monoalkylaminocarbonyl group having 2 to 10 carbon atoms, dimethylaminocarbonyl group, diethylaminocarbonyl group , Dipropylaminocarbonyl group, dibutylaminocarbonyl group, dipentylaminocarbonyl group, dihexylaminocarbonyl group,
Dialkylaminocarbonyl group having 3 to 20 carbon atoms such as diheptylaminocarbonyl group, dioctylaminocarbonyl group, piperidinocarbonyl group, morpholinocarbonyl group, 4-methylpiperazinocarbonyl group, 4-ethylpiperazinocarbonyl group An alkylaminocarbonyl group such as furanyl group, pyrrolyl group, 3-pyrrolino group, pyrrolidino group, 1,3-oxolanyl group, pyrazolyl group, 2-
A pyrazolinyl group, a pyrazolidinyl group, an imidazolyl group,
Oxazolyl group, thiazolyl group, 1,2,3-oxadiazolyl group, 1,2,3-triazolyl group, 1,2,4
-Triazolyl group, 1,3,4-thiadiazolyl group, 4
H-pyranyl group, pyridinyl group, piperidinyl group, dioxanyl group, morpholinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, piperazinyl group, triazinyl group, benzofuranyl group, indolyl group, thionaphthenyl group, benzimidazolyl group, benzothiazolyl group,
Purinyl group, quinolinyl group, isoquinolinyl group, coumarinyl group, cinnolinyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group, phenanthronylyl group,
Heteroaryl groups substituted with a substituent such as a heterocyclic group such as a phenothiazinyl group and a flavonyl group; a metallocenyl group such as a ferrocenyl group, a cobaltcenyl group, a nickelocenyl group, a ruthenocenyl group, an osmocenyl group and a titanocenyl group;

Examples of the substituted or unsubstituted heteroaryloxy group for R ^{1 to} R ¹⁶ are heteroaryloxy groups which may have the same substituents as the above-mentioned alkyl groups, and preferably, Furanyloxy group, pyrrolyloxy group, 3-pyrrolinooxy group, pyrazolyloxy group, imidazolyloxy group, oxazolyloxy group, thiazolyloxy group, 1,2,3-oxadiazolyloxy group,
1,2,3-triazolyloxy group, 1,2,4-triazolyloxy group, 1,3,4-thiadiazolyloxy group, pyridinyloxy group, pyridazinyloxy group, pyrimidinyloxy group, Pyrazinyloxy group, piperazinyloxy group, triazinyloxy group, benzofuranyloxy group, indolyloxy group, thionaphthenyloxy group, benzimidazolyloxy group, benzothiazolyloxy group, benzotriazol-2- Yloxy group, benzotriazol-1-yloxy group, purinyloxy group, quinolinyloxy group, isoquinolinyloxy group, coumarinyloxy group, cinnolinyloxy group, quinoxalinyloxy group, dibenzofuranyloxy group, carbazolyl Group, phenanthronylyloxy group, phenothiazinyloxy group, Niruokishi group, phthalic succinimidyl group, unsubstituted heteroaryloxy groups, such as naphthyl succinimidyl group;

Alternatively, the following substituents, that is, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano group; methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and heptyl group. , Octyl group, decyl group, methoxymethyl group, ethoxyethyl group,
Alkyl groups such as ethoxyethyl group and trifluoromethyl group; aralkyl groups such as benzyl group and phenethyl group; aryl groups such as phenyl group, tolyl group, naphthyl group, xylyl group, mesyl group, chlorophenyl group, methoxyphenyl group; methoxy Group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, 2-ethylhexyloxy group, 3,5,5-trimethylhexyloxy group, ferrocene Alkoxy groups such as methoxy group, cobaltene methoxy group and nickelocene methoxy group; aralkyloxy groups such as benzyloxy group, phenethyloxy group; phenoxy group, tolyloxy group, naphthoxy group, xylyloxy group, mesityloxy group, chlorophenoxy group Group, an aryloxy group such as a methoxyphenoxy group; vinyloxy group; a vinyl group, an allyl group, butenyl group, butadienyl group, pentenyl group, cyclopentadienyl group, an alkenyl group such as octenyl
Alkenyloxy groups such as allyloxy group, butenyloxy group, butadienyloxy group, pentenyloxy group, cyclopentadienyloxy group, octenyloxy group; methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group , Heptylthio group, octylthio group, decylthio group, methoxymethylthio group, ethoxyethylthio group, ethoxyethylthio group,
Alkylthio group such as trifluoromethylthio group; Aralkylthio group such as benzylthio group and phenethylthio group;
Arylthio groups such as phenylthio group, tolylthio group, naphthylthio group, xylylthio group, mesylthio group, chlorophenylthio group, methoxyphenylthio group; dialkylamino groups such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group; acetyl Groups, propionyl groups, butanoyl groups, ferrocenecarbonyl groups, cobaltocenecarbonyl groups, nickelocenecarbonyl groups, and other acyl groups; methoxycarbonyl groups, ethoxycarbonyl groups, ferrocenemethoxycarbonyl groups, 1-methylferrocene-1′-ylmethoxycarbonyl Group, an alkoxycarbonyl group such as a cobaltcenylmethoxycarbonyl group and a nickelocenylmethoxycarbonyl group; an aralkyloxy group such as a benzyloxycarbonyl group and a phenethyloxycarbonyl group Sicarbonyl group; phenoxycarbonyl group, tolyloxycarbonyl group, naphthoxycarbonyl group, xylyloxycarbonyl group, mesyloxycarbonyl group, chlorophenoxycarbonyl group, methoxyphenoxycarbonyl group and other aryloxycarbonyl groups; vinyloxycarbonyl group, Alkenyloxycarbonyl groups such as allyloxycarbonyl group, butenyloxycarbonyl group, butadienyloxycarbonyl group, cyclopentadienyloxy group, pentenyloxycarbonyl group, octenyloxycarbonyl group; methylaminocarbonyl group, ethylaminocarbonyl group Group, propylaminocarbonyl group, butylaminocarbonyl group, pentylaminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group, octyl Aminoalkyl group, nonylaminocarbonyl group, 3,5,5-trimethylhexylaminocarbonyl group, 2-ethylhexylaminocarbonyl group or other monoalkylaminocarbonyl group having 2 to 10 carbon atoms, dimethylaminocarbonyl group, diethylaminocarbonyl group , Dipropylaminocarbonyl group, dibutylaminocarbonyl group, dipentylaminocarbonyl group, dihexylaminocarbonyl group,
Dialkylaminocarbonyl group having 3 to 20 carbon atoms such as diheptylaminocarbonyl group, dioctylaminocarbonyl group, piperidinocarbonyl group, morpholinocarbonyl group, 4-methylpiperazinocarbonyl group, 4-ethylpiperazinocarbonyl group An alkylaminocarbonyl group such as furanyl group, pyrrolyl group, 3-pyrrolino group, pyrrolidino group, 1,3-oxolanyl group, pyrazolyl group, 2-
A pyrazolinyl group, a pyrazolidinyl group, an imidazolyl group,
Oxazolyl group, thiazolyl group, 1,2,3-oxadiazolyl group, 1,2,3-triazolyl group, 1,2,4
-Triazolyl group, 1,3,4-thiadiazolyl group, 4
H-pyranyl group, pyridinyl group, piperidinyl group, dioxanyl group, morpholinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, piperazinyl group, triazinyl group, benzofuranyl group, indolyl group, thionaphthenyl group, benzimidazolyl group, benzothiazolyl group,
Purinyl group, quinolinyl group, isoquinolinyl group, coumarinyl group, cinnolinyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group, phenanthronylyl group,
Examples of the heteroaryloxy group include a heterocyclic group such as a phenothiazinyl group and a flavonyl group;

Examples of the substituted or unsubstituted heteroarylthio group for R ^{1 to} R ¹⁶ are heteroarylthio groups which may have the same substituents as the above-mentioned alkyl groups, and preferably, Furanylthio group, pyrrolylthio group, 3
-Pyrrolinothio group, pyrazolylthio group, imidazolylthio group, oxazolylthio group, thiazolylthio group, 1,
2,3-oxadiazolylthio group, 1,2,3-triazolylthio group, 1,2,4-triazolylthio group, 1,
3,4-thiadiazolylthio group, pyridinylthio group, pyridazinylthio group, pyrimidinylthio group, pyrazinylthio group, piperazinylthio group, triazinylthio group, benzofuranylthio group, indolylthio group, thionaphthenylthio group, benzimidazolylthio group, benzo Thiazolylthio group, benzotriazol-2-ylthio group, benzotriazol-1-ylthio group, purinylthio group, quinolinylthio group, isoquinolinylthio group, coumarinylthio group, cinnolinylthio group, quinoxalinylthio group, dibenzofuranylthio group An unsubstituted heteroarylthio group such as a carbazolylthio group, a phenanthronylylthio group, a phenothiazinylthio group, a flavonylthio group, a phthalimidylthio group and a naphthylimidylthio group;

Alternatively, the following substituents, ie, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano group; methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group. , Octyl group, decyl group, methoxymethyl group, ethoxyethyl group,
Alkyl groups such as ethoxyethyl group and trifluoromethyl group; aralkyl groups such as benzyl group and phenethyl group; aryl groups such as phenyl group, tolyl group, naphthyl group, xylyl group, mesyl group, chlorophenyl group, methoxyphenyl group; methoxy Group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, 2-ethylhexyloxy group, 3,5,5-trimethylhexyloxy group, ferrocene Alkoxy groups such as methoxy group, cobaltene methoxy group and nickelocene methoxy group; aralkyloxy groups such as benzyloxy group, phenethyloxy group; phenoxy group, tolyloxy group, naphthoxy group, xylyloxy group, mesityloxy group, chlorophenoxy group Group, an aryloxy group such as a methoxyphenoxy group; vinyloxy group; a vinyl group, an allyl group, butenyl group, butadienyl group, pentenyl group, cyclopentadienyl group, an alkenyl group such as octenyl
Alkenyloxy groups such as allyloxy group, butenyloxy group, butadienyloxy group, pentenyloxy group, cyclopentadienyloxy group, octenyloxy group; methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group , Heptylthio group, octylthio group, decylthio group, methoxymethylthio group, ethoxyethylthio group, ethoxyethylthio group,
Alkylthio group such as trifluoromethylthio group; Aralkylthio group such as benzylthio group and phenethylthio group;
Arylthio groups such as phenylthio group, tolylthio group, naphthylthio group, xylylthio group, mesylthio group, chlorophenylthio group, methoxyphenylthio group; dialkylamino groups such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group; acetyl Groups, propionyl groups, butanoyl groups, ferrocenecarbonyl groups, cobaltocenecarbonyl groups, nickelocenecarbonyl groups, and other acyl groups; methoxycarbonyl groups, ethoxycarbonyl groups, ferrocenemethoxycarbonyl groups, 1-methylferrocene-1′-ylmethoxycarbonyl Group, an alkoxycarbonyl group such as a cobaltcenylmethoxycarbonyl group and a nickelocenylmethoxycarbonyl group; an aralkyloxy group such as a benzyloxycarbonyl group and a phenethyloxycarbonyl group Sicarbonyl group; phenoxycarbonyl group, tolyloxycarbonyl group, naphthoxycarbonyl group, xylyloxycarbonyl group, mesyloxycarbonyl group, chlorophenoxycarbonyl group, methoxyphenoxycarbonyl group and other aryloxycarbonyl groups; vinyloxycarbonyl group, Alkenyloxycarbonyl groups such as allyloxycarbonyl group, butenyloxycarbonyl group, butadienyloxycarbonyl group, cyclopentadienyloxy group, pentenyloxycarbonyl group, octenyloxycarbonyl group; methylaminocarbonyl group, ethylaminocarbonyl group Group, propylaminocarbonyl group, butylaminocarbonyl group, pentylaminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group, octyl Aminoalkyl group, nonylaminocarbonyl group, 3,5,5-trimethylhexylaminocarbonyl group, 2-ethylhexylaminocarbonyl group or other monoalkylaminocarbonyl group having 2 to 10 carbon atoms, dimethylaminocarbonyl group, diethylaminocarbonyl group , Dipropylaminocarbonyl group, dibutylaminocarbonyl group, dipentylaminocarbonyl group, dihexylaminocarbonyl group,
Dialkylaminocarbonyl group having 3 to 20 carbon atoms such as diheptylaminocarbonyl group, dioctylaminocarbonyl group, piperidinocarbonyl group, morpholinocarbonyl group, 4-methylpiperazinocarbonyl group, 4-ethylpiperazinocarbonyl group An alkylaminocarbonyl group such as furanyl group, pyrrolyl group, 3-pyrrolino group, pyrrolidino group, 1,3-oxolanyl group, pyrazolyl group, 2-
A pyrazolinyl group, a pyrazolidinyl group, an imidazolyl group,
Oxazolyl group, thiazolyl group, 1,2,3-oxadiazolyl group, 1,2,3-triazolyl group, 1,2,4
-Triazolyl group, 1,3,4-thiadiazolyl group, 4
H-pyranyl group, pyridinyl group, piperidinyl group, dioxanyl group, morpholinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, piperazinyl group, triazinyl group, benzofuranyl group, indolyl group, thionaphthenyl group, benzimidazolyl group, benzothiazolyl group,
Purinyl group, quinolinyl group, isoquinolinyl group, coumarinyl group, cinnolinyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group, phenanthronylyl group,
Examples of the heteroarylthio group include a heterocyclic group such as a phenothiazinyl group and a flavonyl group;

Examples of the substituent R ^{17 to} R ²² of the optionally substituted methine group represented by X ¹ , Y ¹ , Z ¹ , X ² , Y ² and Z ² are R ^{1 to} R The same substituents as ¹⁶ can be mentioned.
Examples of preferable substituents include a hydrogen atom; a fluorine atom,
Halogen atom such as chlorine atom, bromine atom, iodine atom;
A cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aralkyl group; a substituted or unsubstituted aryl group; an acyloxy group and the like.

The linking group for R ^{1 to} R ²² to form a ring together with the adjacent substituent and the linking group includes a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a metal atom, and a half atom. A group obtained by appropriately selecting and combining a hetero atom such as a metal atom and a carbon atom, and examples of a preferable linking group include -O-, -S-, -C (= O)-, or even a substituted group. Examples thereof include a methylene group, a methine group, an ethynylene group, a phenylene group, an amino group, an imino group, and a metal atom, which can be appropriately combined to obtain a desired ring. Examples of the ring formed by the linking group include a chain-shaped, planar, or three-dimensional ring linked by the linking group. As a preferable example of the linked skeleton, —CH ₂ —CH _{2
-CH 2 -CH 2 -, - CH} 2 (NO 2) -CH 2 -CH 2 -
_{CH 2 -, - CH (CH} 3) -CH 2 -CH 2 -CH 2 -,
_{-CH (Cl) -CH 2 -CH 2} -, aliphatic condensed equal; -CH = CH-CH = CH -, - C (NO 2) = CH-
CH = CH -, - C ( CH 3) = CH-CH = CH-,
_{-C (CH 3) = CH-} CH = CH -, - C (CH 3) =
_{CH-CH = C (CH 3} ) -, - C (OCH 3) = CH-
_{CH = C (OCH 3) -} , - C (OCH 2 CH 2 CH (C
_{H 3) - (OCH 3)} ) = C (Cl) -C (Cl) = C
_{(OCH 2 CH 2 CH (CH} 3) - (OCH 3)) -, - C
_{(OCH 2 CH 2 CH (CH} 3) 2) = C (Cl) -C (C
_{l) = C (OCH 2 CH} 2 CH (CH 3) 2) -, - CH =
_{C (CH 3) -C (CH} 3) = CH -, - C (Cl) = C
H-CH = CH-, -C {OCH [CH (C
H _{3) 2] 2} = CH-CH = CH} -, - C {OCH [C
H (CH _{3) 2] 2} = C (Br) -CH} = CH -, - C
{OCH [CH (CH _{3) 2] 2} = CH-C (Br} ) =
CH -, - C {OCH [CH (CH _{3) 2] 2}} = CH-
CH = C (Br)-, -C (C2H5) = CH-CH = C
_{H -, - C (C 2} H 5) = CH-CH = C (C 2 H 5) -,
_{-CH = C (C 2 H 5} ) -C (C 2 H 5) = CH -, - C
(Cl) = CH-CH = CH- or other aromatic condensed ring; -O
_{-CH 2 -CH 2 -O -, -} O-CH (CH 3) -CH
_{(CH 3) -O -, -} COO-CH 2 -CH 2 -, - CO
_{O-CH 2 -, - CONH} -CH 2 -CH 2 -, - CON
_{H-CH 2 -, - CON} (CH 3) -CH 2 -CH 2 -, -
CON (CH ₃₎ -CH ₂ -, etc. chain linked heterocycle or,

[0141]

[Chemical 9]

(M 'is Fe, Ru, Co, Ni, Os
Or M "R '₂(M "is Ti, Zr, Hf, Nb, M
o, V, R'is CO, F, Cl, Br, I, above
R of the above ¹~ R¹⁶C1 which may have the same substituent as
-10 alkyl group, alkoxy group, aryl group, ari
Group, aralkyl group, aralkyloxy group
You ) Represents. ) Etc. metal complex residues; etc.
You can

When R ^{1 to} R ²² are connected to adjacent substituents via a linking group, a suitable combination of linkages is R ¹
And R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , R
¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁵ and R ¹⁶ , R ² and R ¹⁷ , R ³ and R ¹⁷ , R ⁴ and R ¹⁸ , R ⁵ and R ¹⁸ , R ⁶ and R ¹⁹ , R ⁷ and R ¹⁹ ,
R ¹⁰ and R ²⁰ , R ¹¹ and R ²⁰ , R ¹² and R ²¹ , R ¹³ and R ²¹ , R
¹⁴ and R ²² , R ¹⁵ and R ^{22, and the} like.

R ^{1 to} R ⁸ and R ^{17 to} R ¹⁹ are linked via a linking group,
The linking group when respectively binding to ^{R 9 ~R 16, R 20 ~R} 22, nitrogen atom, oxygen atom, sulfur atom, phosphorus atom,
It is a group formed by appropriately selecting and combining a hetero atom such as a metal atom and a metalloid atom, and a carbon atom, and may be chain-like or may form a ring. Examples of preferred linking groups include-
Examples thereof include O-, -S-, -C (= O)-, or an optionally substituted methylene group, methine group, ethynylene group, phenylene group, amino group, imino group, metal atom and the like. As a preferable example of the linked skeleton, —CH ₂ —CH _{2
-CH 2 -CH 2 -, - CH} 2 (NO 2) -CH 2 -CH 2 -
_{CH 2 -, - CH (CH} 3) -CH 2 -CH 2 -CH 2 -,
_{-CH (Cl) -CH 2 -CH 2} -, - CH 2 -CH 2 -C
_{H 2 -CH 2 -CH 2 -,} - CH 2 -CH 2 -CH 2 -CH 2
Saturated aliphatic linking group such as —CH ₂ —CH ₂ —; —CH═CH—CH═CH—, —C (NO ₂ ) ═CH—
CH = CH -, - C ( CH 3) = CH-CH = CH-,
_{-C (CH 3) = CH-} CH = CH -, - C (CH 3) =
_{CH-CH = C (CH 3} ) -, - C (OCH 3) = CH-
_{CH = C (OCH 3) -} , - C (OCH 2 CH 2 CH (C
_{H 3) - (OCH 3)} ) = C (Cl) -C (Cl) = C
_{(OCH 2 CH 2 CH (CH} 3) - (OCH 3)) -, - C
_{(OCH 2 CH 2 CH (CH} 3) 2) = C (Cl) -C (C
_{l) = C (OCH 2 CH} 2 CH (CH 3) 2) -, - CH =
_{C (CH 3) -C (CH} 3) = CH -, - C (Cl) = C
H-CH = CH-, -C {OCH [CH (C
H _{3) 2] 2} = CH-CH = CH} -, - C {OCH [C
H (CH _{3) 2] 2} = C (Br) -CH} = CH -, - C
{OCH [CH (CH _{3) 2] 2} = CH-C (Br} ) =
CH -, - C {OCH [CH (CH _{3) 2] 2}} = CH-
CH = C (Br) -, - C (C 2 H 5) = CH-CH = C
_{H -, - C (C 2} H 5) = CH-CH = C (C 2 H 5) -,
_{-CH = C (C 2 H 5} ) -C (C 2 H 5) = CH -, - C
(Cl) = CH-CH = CH-, -C≡C-C≡C-,
_{-C≡C-CH 2 -CH 2 -C≡C -} , - CH 2 -C≡C
Unsaturated aliphatic linking group -CH ₂ -CH ₂ -C≡C- _{like; -CH 2 - (p-C} 6 H 4) -CH 2 -, - CH 2 - (m-
_{C 6 H 4) -CH 2 -} , - CH 2 -CH 2 - (p-C 6 H 4)
_{-CH 2 -CH 2 -, - CH} 2 -CH 2 - (m-C 6 H 4) -
_{CH 2 -CH 2 -, - CH} = CH 2 - (m-C 6 H 4) -C
H ₂ = CH ₂ - and the like aromatic linking group _{containing; -O-CH 2 -CH 2 -O} -, - O-CH (CH 3) -C
_{H (CH 3) -O -,} - COO-CH 2 -CH 2 -, - C
_{OO-CH 2 -, - CONH} -CH 2 -CH 2 -, - CO
_{NH-CH 2 -, - CON} (CH 3) -CH 2 -CH 2 -,
-CON (CH ₃₎ -CH ₂ - hetero atom-containing linking groups such as or,

[0145]

[Chemical 10]

(M 'is Fe, Ru, Co, Ni, Os
Or M "R '₂(M "is Ti, Zr, Hf, Nb, M
o, V, R'is CO, F, Cl, Br, I, above
R of the above ¹~ R¹⁶C1 which may have the same substituent as
-10 alkyl group, alkoxy group, aryl group, ari
Group, aralkyl group, aralkyloxy group
You ) Represents. ) And other metal complex residues;
You can

The trivalent metal atom used in M ² together with one hydrogen atom is, for example, a group IIIA to VIIA or VI of the periodic table.
Examples thereof include Group II and Group IB to VIIB metal atoms. Suitable examples include Sc, Ti, V, Cr, Mn, Mo, Ag,
U, Fe, Co, Ni, Cu, Y, Nb, Ru, Rh,
La, Ta, Ir, Au, In, Tl, Pb, Bi, C
e, Pr, Nd, Pm, Sm, Eu, Gd, Tb, D
Examples thereof include trivalent unsubstituted metal atoms such as y, Ho, Er, Tm, Yb and Lu. More preferably, Lu, Ce, S
m, Ru, Eu, Y, Rh and the like.

As the tetravalent metal atom represented by M ² ,
Examples include metal atoms of Group IIIA to VIIA, Group VIII, and Group IB to VIIB of the periodic table. Suitable examples include Ti, V, Cr,
Mn, Mo, Zr, Nb, Ru, Rh, Ta, Ir, P
b, Ce, Pr, Nd, Pm, Sm, Eu, Gd, T
Examples thereof include trivalent unsubstituted metal atoms such as b, Dy, Ho, Er, Tm, Yb and Lu. More preferably, Zr, L
u, Ce, Ru, Rh and the like can be mentioned.

Further, in the present invention, as the compound represented by the general formula (1), the compound further exemplified by the general formula (3) is mentioned as a preferable example.

[0150]

[Chemical 11]

[In the formula, R^{twenty three}~ R³⁸Each independently, water
Elementary atom, halogen atom, nitro group, cyano group, hydroxy
Syl group, amino group, carboxyl group, mercapto group,
A substituted or unsubstituted alkyl group, aralkyl group, aryl
Group, alkenyl group, alkoxy group, aralkyloxy
Group, aryloxy group, alkenyloxy group, alkyl
Thio group, aralkylthio group, arylthio group, alkene
Ruthio group, mono-substituted amino group, di-substituted amino group, acyl
Group, alkoxycarbonyl group, aralkyloxycarbo
Nyl group, aryloxycarbonyl group, alkenyloxy
Sicarbonyl group, mono-substituted aminocarbonyl group, di-substituted
Aminocarbonyl group, acyloxy group, heteroaryl
Group, heteroaryloxy group or heteroarylthio
Represents a group, X ³Is a nitrogen atom or C-R³⁹(R³⁹Is R^{twenty three}
~ R³⁸Represents any of the groups shown in
Represents a methine group which may be substituted, Y³Is a nitrogen atom
Or C-R⁴⁰(R⁴⁰Is R^{twenty three}~ R³⁸One of
An optionally substituted methine group represented by
Represents Z³Is a nitrogen atom or C-R⁴¹(R⁴¹Is R^{twenty three}
~ R³⁸Represents any of the groups shown in
Represents a methine group which may be substituted, X^FourIs a nitrogen atom
Or C-R⁴²(R⁴²Is R^{twenty three}~ R³⁸One of
An optionally substituted methine group represented by
Represents Y^FourIs a nitrogen atom or C-R⁴³(R⁴³Is R^{twenty three}~
R³⁸Represents any of the groups shown in
Represents an optionally substituted methine group, Z^FourIs the nitrogen atom
Or C-R^{Four Four}(R⁴⁴Is R^{twenty three}~ R³⁸One of
An optionally substituted methine group represented by
Represents R^{twenty three}~ R⁴⁴Each substituent of is linked to the adjacent substituent
R may be combined together via a group to form a ring.^{twenty three}
~ R³⁰, R³⁹~ R⁴¹Each substituent of R is⁹~ R¹⁶, R⁴²~
R⁴⁴Each of which is linked via a substituent and each substituent of
Well, M³Is a trivalent metal atom and one hydrogen atom,
Or represents a tetravalent metal atom. However, X³, Y³, Z³But
When all are nitrogen atoms, R^{twenty three}~ R^{twenty four}, R^{twenty five}~ R²⁶,
R²⁷~ R²⁸, R²⁹~ R³⁰Each substituent of
X, without forming an aromatic ring at the same time.^Four, Y^Four, Z^FourBut
When all are nitrogen atoms, R³¹~ R³², R³³~ R³⁴,
R³⁵~ R³⁶, R³⁷~ R³⁸Each substituent of
It does not form an aromatic ring at the same time by being linked. ]

In the compound represented by the general formula (3) of the present invention, specific examples of R ^{23 to} R ³⁸ include hydrogen atom; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; nitro group A cyano group; a hydroxyl group; an amino group; a carboxyl group; a mercapto group and the like.

A substituted or unsubstituted alkyl group, aralkyl group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group of R ^{23 to} R ³⁸ ;
Arylthio group, alkenylthio group, mono-substituted amino group, di-substituted amino group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, mono-substituted aminocarbonyl group, di-substituted aminocarbonyl group Examples of the acyloxy group, heteroaryl group, heteroaryloxy group or heteroarylthio group include R ^{1 to} R
Alkyl group similar to ¹⁶ , an aralkyl group, an aryl group, an alkenyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an alkenyloxy group, an alkylthio group,
Aralkylthio group, arylthio group, alkenylthio group, mono-substituted amino group, di-substituted amino group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, mono-substituted aminocarbonyl group, di- A substituted aminocarbonyl group, an acyloxy group, a heteroaryl group,
Examples thereof include a heteroaryloxy group and a heteroarylthio group.

Examples of the linking group for R ^{23 to} R ⁴⁴ to form a ring together via the linking group include the same linking groups as R ^{1 to} R ²² .

As R ^{23 to} R ³⁰ , R ^{39 to} R ⁴¹ , which are bonded to R ^{31 to} R ³⁸ and R ^{42 to} R ⁴⁴ via a linking group, respectively, are the same as R ^{1 to} R ^22. The linking group of is mentioned.

Examples of the trivalent to tetravalent metal atom represented by M ³ include the same metal atom as M ¹ described above.

Further, in the present invention, as the compound represented by the general formula (1), the compound further exemplified by the general formula (4) is mentioned as a preferable example.

[0158]

[Chemical 12]

[In the formula, R⁴⁵~ R⁶⁰Each independently, water
Elementary atom, halogen atom, nitro group, cyano group, hydroxy
Syl group, amino group, carboxyl group, mercapto group,
A substituted or unsubstituted alkyl group, aralkyl group, aryl
Group, alkenyl group, alkoxy group, aralkyloxy
Group, aryloxy group, alkenyloxy group, alkyl
Thio group, aralkylthio group, arylthio group, alkene
Ruthio group, mono-substituted amino group, di-substituted amino group, acyl
Group, alkoxycarbonyl group, aralkyloxycarbo
Nyl group, aryloxycarbonyl group, alkenyloxy
Sicarbonyl group, mono-substituted aminocarbonyl group, di-substituted
Aminocarbonyl group, acyloxy group, heteroaryl
Group, heteroaryloxy group or heteroarylthio
Represents a group, R ⁴⁵~ R⁶⁰Each substituent of
R may be combined with each other via a bonding group to form a ring.
⁴⁵~ R⁵²Each substituent of R is⁵³~ R⁶⁰Each substituent and linking group of
M may be bonded to each other via^FourIs trivalent gold
Represents a group atom and one hydrogen atom or a tetravalent metal atom
You However, R⁴⁵~ R⁴⁶, R⁴⁷~ R⁴⁸, R⁴⁹~ R⁵⁰, R
⁵¹~ R⁵²Each substituent of is linked to the adjacent substituent,
R does not form an aromatic ring in ⁵³~ R⁵⁴, R⁵⁵~ R⁵⁶, R⁵⁷~
R⁵⁸, R⁵⁹~ R⁶⁰Each substituent of is linked to an adjacent substituent
And do not form an aromatic ring at the same time. ]

In the compound represented by the general formula (4) of the present invention, specific examples of R ^{45 to} R ⁶⁰ are hydrogen atom; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; nitro group A cyano group; a hydroxyl group; an amino group; a carboxyl group; a mercapto group and the like.

A substituted or unsubstituted alkyl group of R ^{45 to} R ⁶⁰ , an aralkyl group, an aryl group, an alkenyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an alkenyloxy group, an alkylthio group, an aralkylthio group,
Arylthio group, alkenylthio group, mono-substituted amino group, di-substituted amino group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, mono-substituted aminocarbonyl group, di-substituted aminocarbonyl group Examples of the acyloxy group, heteroaryl group, heteroaryloxy group or heteroarylthio group include R ^{1 to} R
Alkyl group similar to ¹⁶ , an aralkyl group, an aryl group, an alkenyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an alkenyloxy group, an alkylthio group,
Aralkylthio group, arylthio group, alkenylthio group, mono-substituted amino group, di-substituted amino group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, mono-substituted aminocarbonyl group, di- A substituted aminocarbonyl group, an acyloxy group, a heteroaryl group,
Examples thereof include a heteroaryloxy group and a heteroarylthio group.

Examples of the linking group when R ^{45 to} R ⁶⁰ form a ring together through the linking group include the same linking groups as R ^{1 to} R ²² .

R ^{45 to} R ⁵² are bonded to each other via R ^{53 to} R ⁶⁰ via a linking group.
Examples of the linking group at the time of bonding with each other include the same linking groups as R ^{1 to} R ²² .

Examples of the trivalent to tetravalent metal atom used for M ⁴ include the same metal atom as M ¹ described above.

Further, in the present invention, as the compound represented by the general formula (1), the compound further exemplified by the general formula (5) is mentioned as a preferable example.

[0166]

[Chemical 13]

[In the formula, R⁶¹~ R⁸⁰Each independently, water
Elementary atom, halogen atom, nitro group, cyano group, hydroxy
Syl group, amino group, carboxyl group, mercapto group,
A substituted or unsubstituted alkyl group, aralkyl group, aryl
Group, alkenyl group, alkoxy group, aralkyloxy
Group, aryloxy group, alkenyloxy group, alkyl
Thio group, aralkylthio group, arylthio group, alkene
Ruthio group, mono-substituted amino group, di-substituted amino group, acyl
Group, alkoxycarbonyl group, aralkyloxycarbo
Nyl group, aryloxycarbonyl group, alkenyloxy
Sicarbonyl group, mono-substituted aminocarbonyl group, di-substituted
Aminocarbonyl group, acyloxy group, heteroaryl
Group, heteroaryloxy group or heteroarylthio
Represents a group, R ⁶¹~ R⁸⁰Each substituent of
R may be combined with each other via a bonding group to form a ring.
⁶¹~ R⁷⁰Each substituent of R is⁷¹~ R⁸⁰Each substituent and linking group of
M may be bonded to each other via^FiveIs trivalent gold
Represents a group atom and one hydrogen atom or a tetravalent metal atom
You ]

In the compound represented by the general formula (5) of the present invention, specific examples of R ^{61 to} R ⁸⁰ include hydrogen atom; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; nitro group A cyano group; a hydroxyl group; an amino group; a carboxyl group; a mercapto group and the like.

A substituted or unsubstituted alkyl group, aralkyl group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group of R ^{61 to} R ⁸⁰ ;
Arylthio group, alkenylthio group, mono-substituted amino group, di-substituted amino group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, mono-substituted aminocarbonyl group, di-substituted aminocarbonyl group Examples of the acyloxy group, heteroaryl group, heteroaryloxy group or heteroarylthio group include R ^{1 to} R
Alkyl group similar to ¹⁶ , an aralkyl group, an aryl group, an alkenyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an alkenyloxy group, an alkylthio group,
Aralkylthio group, arylthio group, alkenylthio group, mono-substituted amino group, di-substituted amino group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, mono-substituted aminocarbonyl group, di- A substituted aminocarbonyl group, an acyloxy group, a heteroaryl group,
Examples thereof include a heteroaryloxy group and a heteroarylthio group.

Examples of the linking group when R ^{61 to} R ⁸⁰ form a ring together via the linking group include the same linking groups as R ^{1 to} R ²² .

R ^{61 to} R ⁷⁰ are bonded to each other via R ^{71 to} R ⁸⁰ via a linking group.
Examples of the linking group at the time of bonding with each other include the same linking groups as R ^{1 to} R ²² .

Examples of the trivalent to tetravalent metal atom used for M ⁵ include the same metal atom as M ¹ described above.

Further, in the present invention, as the compound represented by the general formula (1), the compound further exemplified by the general formula (6) is mentioned as a preferable example.

[0174]

[Chemical 14]

[In the formula, R ^{81 to} R ¹⁰² are each independently
Hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, mercapto group,
Substituted or unsubstituted alkyl group, aralkyl group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group, arylthio group, alkenylthio group, monosubstituted amino group , Di-substituted amino group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, mono-substituted aminocarbonyl group, di-substituted aminocarbonyl group, acyloxy group, heteroaryl group, heteroaryloxy Represents a group or a heteroarylthio group, and each substituent of R ^{81 to} R ¹⁰² may together form a ring via an adjacent substituent and a linking group,
Further, each substituent of R ^{81 to} R ⁹¹ may be bonded to each substituent of R ^{92 to} R ¹⁰² via a linking group, and M ⁶
Represents a trivalent metal atom and one hydrogen atom, or a tetravalent metal atom. ]

In the compound represented by the general formula (6) of the present invention, specific examples of R ^{81 to} R ¹⁰² are: hydrogen atom; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; nitro group A cyano group; a hydroxyl group; an amino group; a carboxyl group; a mercapto group and the like.

A substituted or unsubstituted alkyl group, aralkyl group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group or arylthio group of R ^{81 to} R ¹⁰² , Alkenylthio group, monosubstituted amino group, disubstituted amino group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, monosubstituted aminocarbonyl group, disubstituted aminocarbonyl group, acyloxy Examples of the group, heteroaryl group, heteroaryloxy group or heteroarylthio group include R ¹ to
An alkyl group similar to R ¹⁶ , an aralkyl group, an aryl group,
Alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group, arylthio group, alkenylthio group, monosubstituted amino group, disubstituted amino group, acyl group,
Alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, mono-substituted aminocarbonyl group, di-substituted aminocarbonyl group, acyloxy group, heteroaryl group,
Examples thereof include a heteroaryloxy group and a heteroarylthio group.

Examples of the linking group when R ^{81 to} R ¹⁰² together form a ring via the linking group include the same linking groups as R ^{1 to} R ²² .

R ^{81 to} R ⁹¹ are bonded to each other via R ⁹² to R ⁹¹ via a linking group.
^Examples of the linking group at the time of bonding with ¹⁰² include R ^{1 to} R ²²
And a linking group similar to the above.

Examples of the trivalent to tetravalent metal atom used for M ⁶ include the same metal atom as M ¹ described above.

Further, in the present invention, as the compound represented by the general formula (1), the compound further exemplified by the general formula (7) is mentioned as a preferable example.

[0182]

[Chemical 15]

[In the formula, R ^{103 to} R ¹²⁰ are each independently
Hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, mercapto group,
Substituted or unsubstituted alkyl group, aralkyl group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group, arylthio group, alkenylthio group, monosubstituted amino group , Di-substituted amino group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, mono-substituted aminocarbonyl group, di-substituted aminocarbonyl group, acyloxy group, heteroaryl group, heteroaryloxy Represents a group or a heteroarylthio group, and each substituent of R ^{103 to} R ¹²⁰ may form a ring together through an adjacent substituent and a linking group,
Further, each substituent of R ^{103 to} R ¹¹¹ may be bonded to each substituent of R ^{112 to} R ¹²⁰ via a linking group, and M
⁷ represents a trivalent metal atom and one hydrogen atom, or a tetravalent metal atom. ]

In the compound represented by the general formula (7) of the present invention, specific examples of R ^{103 to} R ¹²⁰ include hydrogen atom; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; nitro group A cyano group; a hydroxyl group; an amino group; a carboxyl group; a mercapto group and the like.

A substituted or unsubstituted alkyl group, aralkyl group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group or arylthio group of R ^{103 to} R ¹²⁰ , Alkenylthio group, monosubstituted amino group, disubstituted amino group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, monosubstituted aminocarbonyl group, disubstituted aminocarbonyl group, acyloxy Examples of the group, heteroaryl group, heteroaryloxy group or heteroarylthio group include R ¹ to
An alkyl group similar to R ¹⁶ , an aralkyl group, an aryl group,
Alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group, arylthio group, alkenylthio group, monosubstituted amino group, disubstituted amino group, acyl group,
Alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, mono-substituted aminocarbonyl group, di-substituted aminocarbonyl group, acyloxy group, heteroaryl group,
Examples thereof include a heteroaryloxy group and a heteroarylthio group.

Examples of the linking group for R ^{103 to} R ¹²⁰ to form a ring together via the linking group include the same linking groups as R ^{1 to} R ²² .

R ^{103 to} R ¹¹¹ are bonded to each other via R ¹¹² to R ¹¹¹ via a linking group.
Examples of the linking group for bonding to R ¹²⁰ include R ^{1 to} R
The linking group similar to ²² is mentioned.

Examples of the trivalent to tetravalent metal atom used for M ⁷ include the same metal atom as M ¹ described above.

The compound represented by the general formula (1) used in the present invention is not limited, but for example, Chemical Physi
cs Letters, vol.215 (6), pp541-547 (1993), Inorg. C
hem., vol.36, pp5603-5608 (1997), Inorg. Chem., v
ol.39, pp1661-1667 (2000), Russ. J. Gen. Chem., vo
It is produced according to the method described in l.69 (1), pp142-144 (1999) and the like. Typically, it can be produced by the following reaction.

The azaporphyrin compounds represented by the general formulas (2) to (7) of the present invention are represented by the following formulas (14) and (1).
5) or only the compound represented by the formula (14), alcohols such as pentanol and hexanol, benzene, toluene, xylene, 1-chloronaphthalene, 1,2-dichlorobenzene, 1,2,4 -Organometallic salts such as acetylacetonate salts of trivalent or tetravalent metal atoms, acetates, trifluoroacetates or the like in aromatic solvents such as trichlorobenzene or hydrates thereof, halides of metal atoms, sulfates, In some cases, heat-react with inorganic metal salts such as nitrates, perchlorates, chlorates, hypochlorites or hydrates thereof, or disubstituted amide salts such as dimethylamide salts and diethylamide salts. Can be obtained at

[0191]

[Chemical 16]

[In the formula, R ^{121 to} R ¹³⁶ are R ^{1 of the} formula (2).
To R ¹⁶ each represent the same group, and the combination of X ⁵ , Y ⁵ , and Z ^{5 and} the combination of X ⁶ , Y ⁶ , and Z ⁶ are respectively the same as those of X ¹ , Y ¹ , and Z ¹ of the formula (2). Combination or X ² ,
It has the same meaning as the combination of Y ² and Z ² . ]

Alternatively, instead of the compound of the formula (14), a compound of the following formula (16) which is a lithium salt thereof, or a compound in which an oxygen-containing hydrocarbon compound such as dimethoxyethane is coordinated to the compound, Instead of the compound of the formula (15), a compound of the following formula (17), which is a lithium salt thereof, or a compound obtained by coordinating the compound with an oxygen-containing hydrocarbon compound such as dimethoxyethane, is reacted similarly. You can get it.

[0194]

[Chemical 17]

[In the formula, R¹³⁷~ R¹⁵², X⁷, Y⁷, Z
⁷Is R in the formula (14)¹²¹~ R¹²⁸, X^Five, Y ^Five, Z^FiveAnd that
Each represents the same group, R¹⁴⁵~ R¹⁵², X⁸, Y⁸, Z
⁸Is R in equation (15)¹²⁹~ R¹³⁶, X⁶, Y⁶, Z⁶And that
Each represents the same group. ]

Further, the compound of the following formula (18)
The compound of the formula (19) ).

[0197]

[Chemical 18]

[In the formula, R ^{153 to} R ¹⁸⁴ are R ^{1 of the} formula (2).
To R ¹⁶ respectively represent the same group, M ⁸ represents a trivalent metal atom, M ⁹ represents a tetravalent metal atom, and X ⁹ , Y ⁹ and Z ⁹
Combination of X ¹⁰ , Y ¹⁰ , Z ¹⁰ combination, X ¹¹ ,
The combination of Y ¹¹ and Z ^{11 and} the combination of X ¹² , Y ¹² and Z ¹² are respectively the combination of X ¹ , Y ¹ and Z ¹ of formula (2) or the combination of X ² , Y ² and Z ² . Each has the same meaning. ]

Further, using a compound of the following formula (20), using a silver compound such as silver trifluoroacetate as a reaction aid, benzene, toluene, xylene, 1-chloronaphthalene,
In an aromatic solvent such as 1,2-dichlorobenzene or 1,2,4-trichlorobenzene, the above formula (16) or the above formula (1
The compound of the following formula (21), which is the compound of the present invention, can be obtained by optionally reacting with the lithium compound of 7) by heating.

[0200]

[Chemical 19]

[In the formula, R¹⁸⁵~ R²⁰⁸Is R in the formula (2)¹
~ R¹⁶Represents the same group as^{1 0}And M¹¹Is 4
Represents a valent metal atom, Q¹, Q²Is fluorine atom, chlorine source
Represents a halogen atom such as a child, a bromine atom or an iodine atom, and X
¹³, Y¹³, Z¹³Combination of X ¹⁴, Y¹⁴, Z¹⁴Set of
Match and X¹⁵, Y¹⁵, Z¹⁵Combination of that
X of each type (2)¹, Y¹, Z¹Combination or X²,
Y², Z²Has the same meaning as each combination. ]

Further, among R ^{1 to} R ^{16 in} the formula (2) wherein any substituent is a hydrogen atom, for example, nitration, halogenation, formylation, amination, carboxylation, hydroxylation, acylation By a conventional synthetic method such as cationization, elimination reaction, etc., the selected hydrogen atom is substituted with an arbitrary substituent, and further, if necessary, a conventional synthetic method such as reduction, oxidation, isomerization, and transfer is used. It is also possible to obtain compounds of formula (2) to formula (7).

Specific examples of the azaporphyrin compounds represented by the general formulas (2) to (7) include, for example, compounds (1-1) to (1) having a substituent shown in Table 1.
-62) and the like. In addition, although the notation of the substituents and the like is shown in accordance with the formula (2), the formulas (3) to (7) are included in the formula (2), and the corresponding substituents and the like are replaced by others. Is self-evident.

[0204]

[Table 1]

[0205]

[Table 2]

[0206]

[Table 3]

[0207]

[Table 4]

[0208]

[Table 5]

[0209]

[Table 6]

[0210]

[Table 7]

[0211]

[Table 8]

[0212]

[Table 9]

The dye of the recording layer constituting the optical recording medium of the present invention is substantially composed of one or more azaporphyrin compounds, particularly compounds of formula (1) to formula (7). Yes, and 290 nm wavelength if desired
Absorption maximum at ~ 690nm, 300nm ~ 900n
You may mix with compounds other than the above whose refractive index in m is large. Specifically, cyanine compounds, squarylium compounds, naphthoquinone compounds, anthraquinone compounds, tetrapyrporphyrazine compounds, indophenol compounds, pyrylium compounds, thiopyrylium compounds, azulenium compounds, triphenylmethane compounds , Xanthene-based compounds, indacerene-based compounds,
Indigo compounds, thioindigo compounds, merocyanine compounds, thiazine compounds, acridine compounds,
There are oxazine-based compounds, dipyrromethene-based compounds, oxazole-based compounds, azaporphyrin-based compounds, porphyrin-based compounds, porphycene-based compounds, and the like, and a mixture of a plurality of compounds may be used. The mixing ratio of these compounds is about 0.1% by mass to 30% by mass.

When forming the recording layer, a quencher, a compound thermal decomposition accelerator, an ultraviolet absorber, an adhesive, an endothermic or endothermic decomposable compound may be added to the compound represented by the formula (1), if necessary. Alternatively, it is possible to mix an additive such as a polymer for improving the solubility, or to introduce a compound having such an effect into the compound represented by the formula (1) as a substituent.

Specific examples of the quencher include acetylacetonate type, bisdithiol type such as bisdithio-α-diketone type and bisphenyldithiol type, thiocateconal type, salicylaldehyde oxime type and thiobisphenolate type. Metal complexes are preferred. Further, amine type is also suitable.

The compound thermal decomposition accelerator is not particularly limited as long as the thermal decomposition of the compound can be confirmed by thermal loss analysis (TG analysis) and the like, and examples thereof include metal anti-knocking agents and metallocene compounds. , And metal compounds such as acetylacetonate-based metal complexes. Examples of the metal anti-knocking agent include tetraethyl lead, other lead compounds, simantrene [Mn (C ₅ H ₅ ) (C
O) ₃ ] and the like, and examples of the metallocene compound include iron biscyclopentadienyl complex (ferrocene), Ti, V, Mn, Cr, Co, N.
i, Mo, Ru, Rh, Zr, Lu, Ta, W, Os,
There are biscyclopentadienyl complexes such as Ir, Sc and Y. Among them, ferrocene, ruthenocene, osmosen,
Nickelocene, titanocene and their derivatives have a good effect of promoting thermal decomposition.

In addition to metallocene, other iron-based metal compounds, organic formate iron compounds such as iron formate, iron oxalate, iron laurate, iron naphthenate, iron stearate, iron acetate, acetylacetonate iron complex, Phenanthroline iron complex, bispyridine iron complex, ethylenediamine iron complex,
Chelating iron complexes such as ethylenediaminetetraacetic acid iron complex, diethylenetriamine iron complex, diethylene glycol dimethyl ether iron complex, diphosphino iron complex, and dimethylglyoximate iron complex, carbonyl iron complex, cyano iron complex, ammine iron complex, and other iron complexes, first chloride Examples thereof include iron halides such as iron, ferric chloride, ferrous bromide and ferric bromide, inorganic iron salts such as iron nitrate and iron sulfate, and iron oxide. The thermal decomposition accelerator used here is preferably one which is soluble in an organic solvent and has good wet heat resistance and light resistance.

Examples of the endothermic or endothermic decomposable compounds include the compounds described in JP-A No. 10-291366, and the compounds having a substituent described therein.

The above-mentioned various quenchers, compound thermal decomposition accelerators and endothermic or endothermic compounds may be used alone or in combination of two or more, as required.

Alternatively, a compound having a quencher ability, a compound thermal decomposition promoting ability, an ultraviolet absorbing ability, and an adhesive ability can be introduced as a substituent of the compound represented by the formula (1).

That is, a compound residue having a quencher ability, a compound thermal decomposition promoting ability, an ultraviolet absorbing ability, an adhesive ability, an endothermic ability or an endothermic resolution with respect to the azaporphyrin compound residue of the formula (1) of the present invention. Is at least one single bond,
A double bond or a triple bond may be chemically bonded to form one molecule. Preferably, each of the substituents R ^{1 to} R ²² of the azaporphyrin-based compound of the formula (2) is represented by the formula (22)-(L ⁿ )-(J ⁿ ) (22) [wherein L ⁿ is the formula (2). , A bond to the azaporphyrin compound, that is, a single bond, or the number of atoms selected by linking at least one kind selected from a methylene group, a methine group, an amino group, an imino group, an oxygen atom or a sulfur atom which may be substituted. Represents a chain of 1 to 20 atoms, J ⁿ is a quencher,
It represents a compound residue corresponding to R ^{1 to} R ²² having a compound thermal decomposition accelerator, an ultraviolet absorber, an adhesive ability, an endothermic ability or an endothermic resolution. ] Or a combination of the substituents represented by the formula (2), which are adjacent to each other, R ¹ and R ² , R ³ and R ⁴ , R
⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , R ¹³ and R
¹⁴ , R ¹⁵ and R ¹⁶ , R ² and R ¹⁷ , R ³ and R ¹⁷ , R ⁴ and R ¹⁸ ,
R ⁵ and R ¹⁸ , R ⁶ and R ¹⁹ , R ⁷ and R ¹⁹ , R ¹⁰ and R ²⁰ , R ¹¹
And R ²⁰ , R ¹² and R ²¹ , R ¹³ and R ²¹ , R ¹⁴ and R ²² , and R ¹⁵ and R ²² , the formula (23) − (L ^m1 ) − (J ^m ) − (L ^m2 ) − ( 23) [In the formula, L ^m1 and L ^m2 are adjacent to each other, and a binding portion to the azaporphyrin compound of the formula (2), that is, a single bond,
Or an optionally substituted methylene group, a methine group, an amino group, an imino group, an oxygen atom or a sulfur atom, which is an atom chain having 1 to 20 atoms selected and linked, and J ^m is a quencher , A compound thermal decomposition accelerator, an ultraviolet absorber, an adhesive ability, an endothermic ability or an endothermic resolution R ¹ ~
Represents a compound residue corresponding to R ²² . ] The substituent represented by this is mentioned.

Preferred examples of the atomic chain of L ⁿ , L ^m1 and L ^m2 include a single bond, —C (═O) —OCH ₂ — and —C (=
_{O) -OCH (CH 3) -} , - OCH 2 -, - OCH (C
_{H 3) -, - CH 2} OCH 2 -, - CH 2 OCH (CH 3)
_{-, - CH (CH 3)} OCH (CH 3) -, - O-C (=
O)-, -CH = CH-, -CH = N-, -C (= O)
-, -CH = CH-C (= O) O-, -C (C = O) C
_{H 2 CH 2 C (= O} ) -O- , and the like.

Preferred examples of J ⁿ and J ^m include metallocene residues such as ferrocene residue, cobaltocene residue, nickelocene residue, ruthenocene residue, osmocene residue and titanocene residue.

Examples of suitable skeletons of the formula (22) include the following metal complex residues.

[0225]

[Chemical 20]

(M 'is Fe, Ru, Co, Ni, Os
Or M "Z '₂(M "is Ti, Zr, Hf, Nb, M
o, V, Z'is CO, F, Cl, Br, I, above
R of the above ¹~ R¹⁶C1 which may have the same substituent as
-10 alkyl group, alkoxy group, aryl group, ari
Group, aralkyl group, aralkyloxy group
Represents). )

Further, examples of preferable skeleton of the formula (23) include the following metal complex residues.

[0228]

[Chemical 21]

(M 'is Fe, Ru, Co, Ni, Os
Or M "Z '₂(M "is Ti, Zr, Hf, Nb, M
o, V, Z'is CO, F, Cl, Br, I, above
R of the above ¹~ R¹⁶C1 which may have the same substituent as
-10 alkyl group, alkoxy group, aryl group, ari
Group, aralkyl group, aralkyloxy group
Represents). )

Further, if necessary, additional substances such as a binder, a leveling agent and an antifoaming agent may be added. Preferred binders include polyvinyl alcohol, polyvinylpyrrolidone, nitrocellulose, cellulose acetate, ketone resins, acrylic resins, polystyrene resins, urethane resins, polyvinyl butyral, polycarbonates, polyolefins and the like.

In order to improve the solvent resistance, reflectance, recording sensitivity, etc. of the substrate when the recording layer is formed on the substrate,
A layer made of an inorganic material or a polymer may be provided on the substrate.

Here, the content of the compound represented by the general formula (1) in the recording layer can be selected so that it can be recorded / reproduced, but it is usually 30% or more, preferably 60%. That is all. It is also preferable that it is substantially 100%.

The method for providing the recording layer is, for example, spin coating method, spraying method, casting method, slide method, curtain method, extrusion method, wire method, gravure method, spread method, roller coating method, knife method, dipping method. Examples of the coating method include a coating method, a sputtering method, a chemical vapor deposition method, a vacuum vapor deposition method, and the like, but the spin coating method is simple and preferable.

When a coating method such as a spin coating method is used, the compound represented by the general formula (1) is dissolved or dispersed in a solvent in an amount of 1 to 40% by mass, preferably 3 to 30% by mass. Although a coating solution is used, it is preferable to select a solvent that does not damage the substrate.
For example, alcohol solvents such as methanol, ethanol, isopropyl alcohol, octafluoropentanol, allyl alcohol, methyl cellosolve, ethyl cellosolve, tetrafluoropropanol, hexane,
Aliphatic or alicyclic hydrocarbon solvents such as heptane, octane, decane, cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane,
Aromatic hydrocarbon solvents such as toluene, xylene and benzene, halogenated hydrocarbon solvents such as carbon tetrachloride, chloroform, tetrachloroethane and dibromoethane,
Examples include ether solvents such as diethyl ether, dibutyl ether, diisopropyl ether and dioxane, ketone solvents such as acetone and 3-hydroxy-3-methyl-2-butanone, ester solvents such as ethyl acetate and methyl lactate, and water. To be These may be used alone or in combination of two or more.

If necessary, the compound of the recording layer may be dispersed in a polymer thin film or the like and used.

If a solvent that does not damage the substrate cannot be selected, sputtering, chemical vapor deposition, vacuum vapor deposition, etc. are effective.

The film thickness of the recording layer is 10 nm to 1000 nm.
However, it is preferably 20 nm to 300 nm. When the film thickness of the recording layer is smaller than 10 nm, recording may not be possible due to large thermal diffusion, distortion may occur in the recording signal, and the signal amplitude may become small. In addition, the film thickness is 1000n
If it is thicker than m, the reflectance may be lowered and the reproduction signal characteristics may be deteriorated.

Next, on the recording layer, preferably 50 nm-
A reflective layer having a thickness of 300 nm is formed. A reflection amplification layer or an adhesive layer can be provided between the recording layer and the reflection layer in order to increase the reflectance or improve the adhesion. The material of the reflective layer has a sufficiently high reflectance at the wavelength of the reproduction light, for example, Au, Al, Ag, Cu, Ti, Cr, Ni, P.
The metals of t, Ta and Pd can be used alone or as an alloy. Among these, Au, Ag, and Al have high reflectance and are suitable as materials for the reflective layer. When recording / reproducing with a blue laser, Al or Ag is preferable. Other than the above, the following may be included. For example, Mg, Se, Hf, V, Nb, Ru, W,
Mn, Re, Fe, Co, Rh, Ir, Zn, Cd, G
a, In, Si, Ge, Te, Pb, Po, Sn, Bi
Mention may be made of metals and semi-metals such as Also,
A material containing Ag or Al as a main component is preferable because a reflective layer having a high reflectance can be easily obtained. It is also possible to stack a low refractive index thin film and a high refractive index thin film alternately with a material other than metal to form a multilayer film and use it as a reflective layer.

As a method for forming the reflective layer, for example,
Examples of the method include a sputtering method, an ion plating method, a chemical vapor deposition method, a vacuum vapor deposition method and the like. A known inorganic or organic intermediate layer or adhesive layer may be provided on the substrate or under the reflective layer to improve reflectance, improve recording characteristics, improve reproduction light stability, improve adhesion, and the like. It can also be provided.

Further, the material of the protective layer formed on the reflective layer is not particularly limited as long as it protects the reflective layer from external force. Inorganic substances include SiO ₂ , Si ₃ N ₄ ,
MgF _2, AlN, SnO _2, etc. TiO ₂ and the like. Examples of the organic substance include thermoplastic resin, thermosetting resin, electron beam curable resin, and ultraviolet curable resin. It can be formed by dissolving a thermoplastic resin, a thermosetting resin, etc. in a suitable solvent to prepare a coating solution, coating the coating solution, and drying. The UV curable resin is prepared as it is or by dissolving it in an appropriate solvent to prepare a coating solution, and then applying this coating solution,
It can be formed by irradiating ultraviolet rays to cure. As the ultraviolet curable resin, for example, an acrylate resin such as urethane acrylate, epoxy acrylate, polyester acrylate can be used. These materials may be used alone or as a mixture, and may be used not only as one layer but also as a multilayer film.

As the method of forming the protective layer, a coating method such as a spin coating method or a casting method or a method such as a sputtering method or a chemical vapor deposition method is used as in the recording layer, and the spin coating method is preferable among them.

The thickness of the protective layer is generally 0.1 μm to 1
Although it is in the range of 00 μm, in the present invention, 3 μm
It is 30 μm, and more preferably 5 μm to 20 μm.

A label, a bar code or the like can be further printed on the protective layer.

A protective sheet or substrate can be attached to the outer surface of the reflective layer. Furthermore, the optical recording medium of the present invention capable of recording on both sides can be obtained by using a means such as bonding two optical recording media so that the outer surfaces of the reflective layers are inside each other.

On the mirror surface side of the substrate, an ultraviolet curable resin, an inorganic thin film or the like may be formed to protect the surface and prevent the adhesion of dust and the like.

When the optical recording medium as shown in FIG. 3 is manufactured, a reflective layer having a thickness of preferably 1 nm to 300 nm is formed on the substrate. A reflection amplification layer or an adhesive layer can be provided between the recording layer and the reflection layer in order to increase the reflectance or improve the adhesion. As the material of the reflective layer, a material having a sufficiently high reflectance at the wavelength of the reproduction light, for example, Al or A
It is possible to use the metals of g, Ni and Pt alone or as an alloy. Among these, Ag and Al have high reflectance and are suitable as materials for the reflective layer. Other than the above, the following may be included as necessary. For example, M
g, Se, Hf, V, Nb, Ru, W, Mn, Re, F
e, Co, Rh, Ir, Zn, Cd, Ga, In, S
i, Ge, Te, Pb, Po, Sn, Bi, Au, C
Mention may be made of metals and semi-metals such as u, Ti, Cr, Pd, Ta. A material containing Ag or Al as a main component and capable of easily obtaining a reflective layer having a high reflectance is suitable. It is also possible to stack a low refractive index thin film and a high refractive index thin film alternately with a material other than metal to form a multilayer film and use it as a reflective layer.

As a method of forming the reflective layer, for example,
Examples of the method include a sputtering method, an ion plating method, a chemical vapor deposition method, a vacuum vapor deposition method and the like. Further, a known inorganic or organic intermediate layer or adhesive layer may be provided on the substrate or below the reflective layer in order to improve the reflectance, the recording characteristics, and the adhesion.

Next, in forming the recording layer on the reflective layer, a layer made of an inorganic material or a polymer is formed on the reflective layer in order to improve solvent resistance, reflectance, recording sensitivity, etc. of the reflective layer. May be provided.

Here, the content of the compound represented by the general formula (1) in the recording layer can be selected to be any amount capable of recording / reproducing, but is usually 30% by mass or more, preferably 60% by mass. It is at least mass%. It is also preferable that the content is substantially 100% by mass.

The method for providing the recording layer is, for example, spin coating method, spraying method, casting method, slide method, curtain method, extrusion method, wire method, gravure method, spread method, roller coating method, knife method, dipping method. Examples of the coating method include a coating method, a sputtering method, a chemical vapor deposition method, and a vacuum vapor deposition method, and the spin coating method is simple and preferable.

When a coating method such as a spin coating method is used, the compound represented by the general formula (1) is dissolved or dispersed in a solvent in an amount of 1 to 40% by mass, preferably 3 to 30% by mass. Although a coating liquid is used, it is preferable to select a solvent that does not damage the reflective layer. For example, alcohol solvents such as methanol, ethanol, isopropyl alcohol, octafluoropentanol, allyl alcohol, methyl cellosolve, ethyl cellosolve, tetrafluoropropanol, hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane. Aliphatic or alicyclic hydrocarbon solvents such as, toluene, xylene, aromatic hydrocarbon solvents such as benzene, halogenated hydrocarbon solvents such as carbon tetrachloride, chloroform, tetrachloroethane, dibromoethane, diethyl ether, Ether-based solvents such as dibutyl ether, diisopropyl ether and dioxane, ketone-based solvents such as acetone and 3-hydroxy-3-methyl-2-butanone, ethyl acetate and lactic acid Ester solvents such as Le, and water. These may be used alone or in combination of two or more.

If necessary, the compound of the recording layer may be dispersed in a polymer thin film or the like and used.

If a solvent that does not damage the reflective layer cannot be selected, sputtering, chemical vapor deposition, vacuum vapor deposition, etc. are effective.

The thickness of the recording layer is usually 1 nm to 1000 n.
m, but preferably 5 nm to 300 nm. If the thickness of the recording layer is less than 1 nm
Distortion may occur in the recording signal and the signal amplitude may decrease. Further, when the film thickness is thicker than 1000 nm, the reflectance may be lowered and the reproduction signal characteristics may be deteriorated.

Further, the material of the protective layer formed on the recording layer is not particularly limited as long as it protects the recording layer from external influences such as external force and atmosphere. Inorganic substances include SiO ₂ , Si ₃ N ₄ , MgF ₂ , AlN and Sn.
Examples thereof include O ₂ and TiO ₂ . Further, as the organic substance, a thermoplastic resin, a thermosetting resin, an electron beam curable resin,
Examples thereof include ultraviolet curable resins. It can be formed by dissolving a thermoplastic resin, a thermosetting resin, etc. in a suitable solvent to prepare a coating solution, coating the coating solution, and drying. The UV-curable resin can be formed as it is or by dissolving it in a suitable solvent to prepare a coating solution, applying the coating solution, and then irradiating it with ultraviolet rays to cure it. As the ultraviolet curable resin, for example, an acrylate resin such as urethane acrylate, epoxy acrylate, polyester acrylate can be used. These materials may be used alone or as a mixture, and may be used not only as one layer but also as a multilayer film.

As the method for forming the protective layer, a coating method such as a spin coating method or a casting method or a method such as a sputtering method or a chemical vapor deposition method is used as in the recording layer, and the spin coating method is preferable among them.

The thickness of the protective layer is generally from 0.01 μm to
The range is 1000 μm, but depending on the case, 0.1 μm to
It can be 100 μm, and further, 1 μm to 20 μm.

A protective sheet can be attached to the outer surface of the substrate layer. Furthermore, the optical recording medium of the present invention capable of recording on both sides can be obtained by using a means such as bonding two optical recording media with the surfaces of the reflective layers facing each other inside.

On the side of the protective layer surface, an ultraviolet curable resin, an inorganic thin film or the like may be formed to protect the surface and prevent dust from adhering.

In the optical recording medium of the present invention, for the purpose of protecting the entire medium, for example, a case-type protection unit for protecting the disk is installed as seen in a floppy (registered trademark) disk or a magneto-optical disk. I don't mind. The material can be plastic or metal such as aluminum.

Basically, the material of the substrate should be transparent at the wavelengths of the recording light and the reproducing light. As a material of the supporting substrate, when a case where irradiation with a blue-violet laser is performed through the substrate 11 as shown in FIG. 4 is taken into consideration, for example, a polymer material such as acrylic resin, polyethylene resin, polycarbonate resin, polyolefin resin, or epoxy resin is used. Transparent materials such as inorganic materials such as glass and glass are used.
On the other hand, when the laser irradiation is performed from the side of the light transmission layer 15 'opposite to the substrate 11' as in the configuration shown in FIG. It can be selected from the materials. From the viewpoint of mechanical properties required for substrates and substrate productivity, materials that can be injection-molded or cast-molded such as acrylic resins, polycarbonate resins, and polyolefin resins are preferable. These substrate materials may be molded into a disc-shaped substrate by an injection molding method or the like.

If necessary, submicron-order guide grooves and / or prepits may be formed spirally or concentrically on the surface layer of these substrates. These guide grooves and prepits are preferably provided at the time of forming the substrate, and can be provided by injection molding using a stamper master or thermal transfer method using a photopolymer. A guide groove and / or a prepit may be formed in the light transmitting layer 15 ′ in FIG. 5, and the same method can be applied to the case where the guide groove and / or the prepit are formed. The pitch and the depth of the guide groove are preferably selected in the range of 0.25 to 0.80 μm as the pitch and 20 to 150 nm as the depth in the case of HD-DVD-R which performs higher density recording than DVD.

Generally, when used as an optical disk, it may have a disk shape with a thickness of about 1.2 mm and a diameter of about 80 to 120 mm, and may have a hole with a diameter of about 15 mm at the center.

Here, the wavelength in the present invention is 300 nm to 5 nm.
00 nm, 500-700 nm and 700-900 n
The laser of m is not particularly limited, but for example, a dye laser capable of wavelength selection in a wide range of visible light region or He-
Ne laser (633nm), nitrogen laser (337n)
m) or other gas laser, 445 nm wavelength helium-cadmium laser, 457 nm or 488 nm argon laser or other ion laser, wavelength 400 to 4
10 nm GaN laser, Cr-doped LiSn
Infrared laser with a wavelength of 860 nm and a laser oscillating its second harmonic 430 nm using AlF ₆ , infrared laser with a wavelength of 820 nm and its second harmonic 41
Lasers oscillating 0 nm, wavelengths 415, 425, 6
02, 612, 635, 647, 650, 660, 67
0, 680nm visible laser diode, 780nm,
Semiconductor lasers such as near infrared semiconductor lasers such as 830 nm, and their second harmonics 390 nm and 415 nm
Examples include lasers that oscillate. In the present invention, the above-mentioned semiconductor laser or the like can be appropriately selected according to the wavelength to which the recording layer for recording or reproducing is sensitive. High-density recording and reproduction can be performed at one wavelength or a plurality of wavelengths selected from the above semiconductor lasers.

[0265]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. The mass spectrometry (FD-MS) was measured using SX-102A manufactured by JEOL.

Synthesis Example 1 Synthesis of compound (1-1)

[0267]

[Chemical formula 22]

93.2 parts of the compound of the formula (a) was dissolved in 860 parts of dehydrated toluene and heated to reflux, 36 parts of tetrakis (diethylamino) zirconium was charged, and the mixture was heated to reflux for 4 hours. After cooling, the reaction mass was concentrated, and the target product was isolated by silica gel column chromatography using chloroform as a developing solvent. After concentrating the isolated solution, it was dried under reduced pressure at 120 ° C. to obtain a brown compound (1-1) having a metallic luster.
2.6 parts were obtained. Absorption maximum wavelength λmax in toluene solvent
(And Gram extinction coefficient εg) is 324 nm (7790
0), 545.5 nm (26400), 611 nm (3
1800). In addition, as mass spectrometry, FD-MS
As a result of measurement, m / z = 1163 was obtained.

Example 1 Of the compounds represented by the general formula (1), 0.2 g of the compound (1-1) shown in Table-1 was added to dimethylcyclohexane 10
It was dissolved in ml to prepare a dye solution. The board is made of polycarbonate resin and has continuous guide grooves (track pitch:
0.74 μm) outer diameter 120 mmφ, thickness 0.6
A disc-shaped one having a size of mm was used. A dye solution was spin-coated on this substrate at a rotation speed of 1500 min ⁻¹ and dried at 70 ° C. for 3 hours to form a recording layer. Silver was sputtered on the recording layer using a Balzers sputtering device (CDI-900) to form a reflective layer having a thickness of 100 nm.
Argon gas was used as the sputtering gas. Sputtering conditions are sputter power 2.5 kW and sputter gas pressure 1.3.
It was performed at 3 Pa (1.0 × 10 ^-2 Torr).

Further, on the reflective layer, an ultraviolet curable resin SD-
After spin-coating 1700 (manufactured by Dainippon Ink and Chemicals), it was irradiated with ultraviolet rays to form a protective layer having a thickness of 5 μm.
Further, after UV-curing resin SD-301 (manufactured by Dainippon Ink and Chemicals Incorporated) is spin-coated on the protective layer, a polycarbonate resin substrate similar to the above-mentioned substrate is placed thereon, and the substrate is irradiated with ultraviolet rays to bond the substrates to each other. Was produced.

The optical recording medium having the recording layer formed as described above was evaluated as follows.

Recording frequency of 9.7 by an evaluation machine equipped with a blue laser head having a wavelength of 403 nm and a numerical aperture of 0.65.
MHz, recording laser power 8.5 mW, linear velocity 9.0 m
The recording was performed with the / s and the shortest pit length of 0.46 μm.
Pits were well formed and recording was possible. After recording, when the reproduction was performed with the reproduction laser power of 0.6 mW at a linear velocity of 9.0 m / s, the pits could be read. Moreover, the C / N ratio was high, which was excellent. When the reproduction was repeated 1000 times or more, the pits could be read and the reproduction light stability was excellent.

Further, a light resistance test of applying 40,000 lux of Xe light was conducted. The pits could be read even after the test.

Further, a moist heat resistance test was carried out by leaving it in an atmosphere of humidity 85% RH and 80 ° C. The pit could be read after the test.

Example 2 Recording and reproduction were carried out in the same manner as in Example 1 except that the laser power was 6.5 mW on the optical recording medium produced according to Example 1. The pits were formed well and the pits could be read.

Example 3 Recording and reproduction were performed on the optical recording medium manufactured according to Example 1 in the same manner as in Example 1 except that the laser power was 7.5 mW. The pits were formed well and the pits could be read.

Example 4 In evaluating the optical recording medium manufactured according to Example 1, a linear velocity of 3.5 m / m was obtained by using an evaluation machine equipped with a semiconductor laser head having a wavelength of 660 nm corresponding to a thickness of 0.6 mm.
s, laser power 8 mW, shortest pit length 0.40 μm
It was recorded so that. The pits were well formed and recording was possible. After recording, when the reproduction was performed using the same evaluation device, the pits could be read. In addition, the reproduction light stability was excellent.

Example 5 Of the compounds represented by the general formula (1), the compound (1-1) shown in Table-1 was made of polycarbonate resin and had continuous guide grooves (track pitch: 0.74 μm). Diameter 1
A film having a thickness of 70 nm was formed on a disk-shaped substrate having a diameter of 20 mm and a thickness of 0.6 mm by a vacuum deposition method.

Silver was sputtered on this recording layer using a spattering apparatus (CDI-900) manufactured by Balzers Co., Ltd. to form a reflective layer having a thickness of 100 nm. Argon gas was used as the sputtering gas. The sputtering conditions are as follows: sputter power 2.5 kW, sputter gas pressure 1.33 Pa (1.0 × 1)
0 ^-2 Torr).

Furthermore, an ultraviolet curable resin SD is formed on the reflective layer.
-1700 (manufactured by Dainippon Ink and Chemicals, Inc.) was spin-coated and then irradiated with ultraviolet rays to form a protective layer having a thickness of 5 μm. Furthermore, on the protective layer, ultraviolet curable resin SD-301
After spin-coating (manufactured by Dainippon Ink and Chemicals, Inc.), a polycarbonate resin substrate having no guide groove similar to the above-mentioned substrate was placed, and the substrate was bonded by irradiating with ultraviolet rays to prepare an optical recording medium.

Next, recording and reproduction were performed in the same manner as in Example 1. The pits were formed well and the pits could be read.

Examples 6 to 65 Compounds (1-2) to (1-6 shown in Table 1 in the recording layer.
An optical recording medium was produced in the same manner as in Example 2 except that 1) was used, and recording and reproduction were performed in the same manner as in Example 1. The pits were formed well and the pits could be read.
In addition, the reproduction light stability was excellent.

Examples 66 to 125 Compounds (1-2) to (1-6 shown in Table 1 in the recording layer.
An optical recording medium was produced in the same manner as in Example 2 except that 1) was used, and recording and reproduction were performed in the same manner as in Example 4. The pits were formed well and the pits could be read. In addition, the reproduction light stability was excellent.

Example 126 An optical recording medium was prepared in the same manner as in Example 2 except that the compound (1-62) shown in Table 1 was used in the recording layer, and recording and reproduction were carried out in the same manner as in Example 1. went. It was possible to record by forming pits satisfactorily. In addition, the reproduction light stability was excellent.

Example 127 A disc-shaped substrate made of a polycarbonate resin and having continuous guide grooves (track pitch: 1.6 μm) with an outer diameter of 120 mmφ and a thickness of 1.2 mm was prepared, and Example 126 was formed on this substrate. The compound (1-6 shown in Table 1 prepared in 1.
2) A dye solution prepared by dissolving 0.2 g in 10 ml of dimethylcyclohexane was spin-coated at a rotation speed of 1000 to 1500 min ⁻¹ and dried at 70 ° C. for 3 hours to form a recording layer. Gold was sputtered on this recording layer using a Balzers sputtering device (CDI-900) to a thickness of 10
A 0 nm reflective layer was formed. Argon gas was used as the sputtering gas. Sputtering conditions are sputter power 2.5
kW, sputtering gas pressure 1.33 Pa (1.0 × 10 ^-2 T
orr).

Further, on the reflective layer, an ultraviolet curable resin SD-
After spin-coating 1700 (manufactured by Dainippon Ink and Chemicals), it was irradiated with ultraviolet rays to form a protective layer having a thickness of 6 μm.
Further, after UV-curing resin SD-301 (manufactured by Dainippon Ink and Chemicals Incorporated) is spin-coated on the protective layer, a polycarbonate resin substrate similar to the above-mentioned substrate is placed thereon, and the substrate is irradiated with ultraviolet rays to bond the substrates to each other. Was produced.

In evaluating the optical recording medium of the present example, a linear velocity of 14. was determined by using an evaluation machine equipped with a semiconductor laser head having a wavelength of 780 nm and a lens numerical aperture of 0.5 corresponding to a thickness of 1.2 mm. 4m / s, laser power 18
When recording was performed at up to 20 mW, pits were formed well and recording was possible. In addition, the reproduction light stability was excellent.

Example 128 Optical recording media obtained in Example 126 and Example 127 were bonded to each other with an adhesive so that the recording surface was on the outer side and the reflective layer was on the inner side. A recording medium was obtained.

Recording was performed in the same manner as in Example 126 on the side to which the optical recording medium obtained in Example 126 was attached.

Recording was performed in the same manner as in Example 127 on the side to which the optical recording medium obtained in Example 127 was attached.

Example 129 For the optical recording media obtained in Examples 1 and 127, the recording surface was on the outside and the reflective layer was on the inside.
Both were bonded with an adhesive to obtain an optical recording medium capable of recording on both sides.

Recording was performed in the same manner as in Example 1 on the side to which the optical recording medium obtained in Example 1 was attached. In addition, the unrecorded portion was recorded in the same manner as in Example 4 and could be recorded.

Further, on the side to which the optical recording medium obtained in Example 127 was attached, recording could be performed in the same manner as in Example 127.

Comparative Example 1 Instead of the compound (1-1), the compound represented by the formula (a)

[0295]

[Chemical formula 23]

An optical recording medium was prepared in the same manner as in Example 1 except that the compound of Example 1 was used, and recording and reproduction were carried out in the same manner as in Example 1. The C / N ratio was as low as 20 dB or less, and reproduction was difficult.

As described in Examples 1-129, the optical recording medium of the present invention is capable of recording / reproducing in any of the blue laser wavelength region, the red laser wavelength region and the near infrared laser wavelength region, Further, it is excellent in reproduction light stability, light resistance and wet heat resistance.

From this, the recording layer containing the compound having the structure defined in the present invention has a wavelength of 300 to 500 nm and / or 500 to 700 nm and / or 700 to
Signal recording is possible with a laser beam selected from 900 nm, and the optical recording medium of the present invention has a wavelength of 300 to 500.
nm and / or laser light selected from 500 to 700 nm and / or 700 to 900 nm can be used for an optical recording medium used for recording and reproduction.

[0299]

According to the present invention, by using the azaporphyrin compound of the present invention as a recording layer, wavelengths of 300 to 5 which are very noticeable as a high density optical recording medium.
A wavelength of 500 to 700 nm used for recording and reproduction with a 00 nm laser, particularly a blue-violet laser having a wavelength of 400 to 410 nm, and recording a moving image such as a movie for 2 hours or more.
Recording and playback with CD player, CD-
Wavelength 700-900 compatible with ROM player
It is possible to provide a write-once type optical recording medium capable of recording and reproducing at nm.

[Brief description of drawings]

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

FIG. 2 is a schematic diagram showing another configuration example of the optical recording medium of the present invention.

FIG. 3 is a schematic view showing still another configuration example of the optical recording medium of the present invention.

FIG. 4 is a schematic diagram showing another configuration example of the optical recording medium of the present invention.

FIG. 5 is a schematic view showing still another configuration example of the optical recording medium of the present invention.

FIG. 6 is a conceptual diagram illustrating a problem of the present invention.

[Explanation of symbols]

1: Substrate 2: Recording layer 3: Reflective layer 4: Protective layer 5: Adhesive layer 11: substrate 12: recording layer 13: reflective layer 14: protective layer 15: Dummy substrate layer 11 ': support substrate 12 ': recording layer 13 ': reflective layer 14 ': transparent protective layer 15 ': light transmitting layer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor U Tsukahara             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company (72) Inventor Yasunori Saito             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company (72) Inventor Masashi Koike             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company (72) Inventor Denmi Misawa             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company F-term (reference) 2H111 EA03 EA12 EA22 EA25 EA33                       EA48 FB42                 4C050 PA11                 5D029 JA04 JB28 JB47                 5D090 AA01 BB03 FF11 KK06

Claims (8)

[Claims] 1. An optical recording medium comprising at least one compound selected from an azaporphyrin compound in which a central metal is coordinated to two azaporphyrin rings and contained in a recording layer. 2. An optical recording medium having an organic dye layer as a recording layer on a substrate, wherein at least one azaporphyrin compound compound in which a central metal is coordinated to two azaporphyrin rings in the organic dye layer is used. The optical recording medium according to claim 1, wherein one or more compounds are selected and contained. 3. The optical recording medium according to claim 1, wherein the azaporphyrin compound is represented by the general formula (0). [Chemical 1] [In the formula, rings A, B, C, D, A ′, B ′, C ′ and D ′ each independently represent a pyrrole ring optionally having a substituent, and T ^{1 to} T ⁶ are each independently Represents a nitrogen atom or an optionally substituted methine group, and M represents a trivalent metal atom and one hydrogen atom, or a tetravalent metal atom. Each substituent of each ring of rings A, B, C, D is a substituent of each ring of rings A, B, C, D and / or rings A ′, B ′, C ′, D via a linking group. It may be bonded to each substituent of each ring of '. ] 4. The optical recording medium according to claim 1, wherein the azaporphyrin compound is represented by the general formula (1). [Chemical 2] [Wherein, E ^{1 to} E ¹⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxy group, a substituted or unsubstituted amino group , A substituted or unsubstituted mercapto group, a substituted carbonyl group or a substituted or unsubstituted heterocyclic group, wherein t ^{1 to} t ⁶ are each independently a nitrogen atom or any group represented by E ^{1 to} E ¹⁶ or Representing a methine group having an atom, E ^{1 to} E ¹⁶ and the respective substituents on the methine group are bonded together through the respective linking groups with the respective substituents of the same azaporphyrin ring or the facing azaporphyrin ring. Of course, M ¹ represents a trivalent metal atom and one hydrogen atom, or a tetravalent metal atom. ] 5. Wavelengths of 300 nm to 500 nm and / or 500 nm to 700 nm and / or 700 nm
5. The optical recording medium according to claim 1, which is capable of recording and reproducing with respect to a laser beam selected from the range of 900 nm. 6. A wavelength of 390 nm to 500 nm and / or 600 nm to 700 nm and / or 750 nm.
The optical recording medium according to claim 5, which is capable of recording and reproducing with respect to a laser beam selected from the range of 850 nm. 7. A wavelength of 400 nm to 410 nm and / or 630 nm to 690 nm and / or 770 nm.
The optical recording medium according to claim 6, which is capable of recording and reproducing with respect to a laser beam selected from the range of ˜840 nm. 8. An azaporphyrin compound represented by the following general formula (1). [Chemical 3] [Wherein, E ^{1 to} E ¹⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxy group, a substituted or unsubstituted amino group , A substituted or unsubstituted mercapto group, a substituted carbonyl group or a substituted or unsubstituted heterocyclic group, and t ^{1 to} t ⁶ are each independently a nitrogen atom or any group represented by E ^{1 to} E ¹⁶ or It represents a methine group having an atom, and any one or more of t ^{1 to} t ^{6 is} an optionally substituted methine group, and E ^{1 to} E ¹⁶
And each substituent on the methine group may be bonded together with each substituent on the same azaporphyrin ring or the facing azaporphyrin ring via a linking group, and M ¹ is 3
It represents a valent metal atom and one hydrogen atom, or a tetravalent metal atom. ]