JP2003182223A - Hydroporphyrin compound and its application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a write once read many type optical recording medium capable of excellently recording and reproducing by laser beams 390-500 nm and/or 500-900 nm in wavelength and a coloring matter for write once read many type recording. <P>SOLUTION: The optical recording medium contains at least one compound selected from hydroporphyrin compounds which can be converted into metal complexes in an organic coloring matter layer of a recording layer. <P>COPYRIGHT: (C)2003,JPO

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, particularly for recording a large-capacity write-once type optical recording medium capable of recording / reproducing information by a blue laser beam. The present invention relates to a hydroporphyrin compound useful as a dye. The present invention also relates to an optical recording medium containing the hydroporphyrin compound.

In addition, the present invention is particularly applicable to wavelengths of 400-41.
The present invention relates to an optical information recording medium having a recording layer capable of high-density recording and reproduction by 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 for using a phthalocyanine compound in a recording layer of a recording medium such as an optical disk or an optical card is disclosed in Japanese Patent Laid-Open No.
1-154888, 61-197280, 61-246091, 62-39286, 63-37991, 63-39388 and the like, these phthalocyanines are widely known. From the viewpoint of sensitivity, refractive index, recording characteristics, etc., it was insufficient for an optical recording medium. A compound obtained by improving it is described in JP-A-3-62878, but it has not been practically sufficient because of a problem in recording characteristics when writing with a laser beam. Further, JP-A-4-214388 and JP-A-5-238150 disclose phthalocyanine compounds having a fluorine atom introduced, but the introduction of a fluorine group improves the adhesion to the substrate resin. The sensitivity is low, and it is described in JP-A-5-247363.
A compound having a bromine atom introduced into the phthalocyanine ring cannot be said to have sufficient performance in high-speed, high-density recording. If the solubility decreases,
There is a problem that the solubility in the spin coating solvent is lowered when the recording medium is prepared.

Further, WO 98/14520 describes a compound obtained by modifying a phthalocyanine compound with a substituent such as a formyl group, but does not describe a metal compound.
The improvement in sensitivity was not sufficient with the bonding of organic groups.

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.
Ketochlorin compounds described in JP-A-3,
No. 144312, tetraazaporphyrin dye compounds, JP 2000-242968 A, metal chelate compounds, JP 2000-343823 A, corrole compounds, JP 2001-80217 A, hydroporphyrin compounds, JP 2001-8459 A
There is an optical recording medium using the (aza) porphyrin compound of JP-A No. 4 and the like. 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.

Further, by using a water-soluble resin material containing a ribosome containing a chlorin compound, flavin, nicotinamide adenine dinucleotide phosphate, and a water-soluble resin for dispersing the same as the recording layer, red light squeezed by a lens is used. Information is written by irradiating light including (600 to 700 nm), and ultraviolet light (320 to 360 nm) is written.
An optical recording medium capable of reading out information by irradiating light including a wavelength (nm) has been proposed (JP-A-60-
221794).

[0020]

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, 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 40
There has been an urgent need to develop an optical recording medium capable of high density recording / reproduction with a laser beam of 0 nm to 410 nm.

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

Furthermore, the optical recording medium described in JP-A No. 11-203729 capable of recording / reproducing in two wavelength regions of a blue laser wavelength region and a red laser wavelength region 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 39
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 430 nm and 630 nm to 690 nm, and storage stability of the recording portion. . In particular, JP-A-1
In the optical recording medium using the ketochlorin compound described in 0-101953, the wavelength is 400 nm to 410 nm.
Since the amount of light absorption in the area of is high, the reflectance decreases,
The reality is that recording and reproduction cannot be performed sufficiently.

On the other hand, in the optical recording medium described in JP-A-60-221794, the writing of information is performed with red light (600
It is indispensable to irradiate with the light including the light of ˜700 nm) and to read the information by irradiating with the light of the ultraviolet light (320 to 360 nm). In reality, it is impossible to perform high-density recording satisfactorily, such as reproduction, and to reproduce favorably with the existing DVD reproduction laser.

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 for writing and reading of recording.
Since a laser beam of up to 700 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. Especially for high-density optical recording media with more than 15 GB on one side, 3
Since the laser beam of 90 to 430 nm, and further 400 to 410 nm is used, the above condition control is more important as a recording material. (2) As described above, a large-capacity write-once type optical recording medium using the laser has been actively developed,
Although the development of dyes having particularly high light resistance and good high-speed recording characteristics is desired, the above-mentioned dye compounds are still available as recording materials capable of recording / reproducing with respect to laser light in both wavelength regions. The current situation is that sufficient characteristics have not been obtained and there is room for improvement. In addition, when a medium is manufactured by a coating method such as a spin coating method, which facilitates the formation of a recording film, one of the advantageous properties is that it has high solubility in a coating solvent. It is necessary to.

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 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. 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.

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

[0029]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention is: (1) An optical recording medium having an organic dye layer containing at least one hydroporphyrin compound as a recording layer on a substrate, wherein the hydroporphyrin compound is a metal complex. An optical recording medium, which may be formed into a ring, or the substituents on the pyrroline ring and / or the pyrrole ring of the compound may be bonded to each other via a linking group to form a ring. (2) The hydroporphyrin compound may have a hydrocarbon group which may have a hetero atom, a halogen atom or a hydroxyl group as a substituent, and further has a pyrroline ring and / or a pyrrole ring of the compound. The optical recording medium of (1), wherein the above substituents may be bonded to each other via a linking group to form a ring. (3) The optical recording medium of (2), wherein the hydroporphyrin compound is represented by the general formula (1).

[0030]

[Chemical 6]

[In the formula, each of rings A, B, C and D independently represents a pyrroline ring or a pyrrole ring which may have the above-mentioned substituent, and at least one of them represents a pyrroline ring; X, Y and Z each independently represent a nitrogen atom or a methine group which may have the above substituent, and M is 1
~ 2 hydrogen atoms, a metal atom or a metalloid atom which may have the above-mentioned substituent or a ligand, and an oxymetal atom. Each substituent of each ring of rings A, B, C and D may be bonded to each substituent of each ring of rings A, B, C and D via a linking group. (4) The optical recording medium of (3) in which the hydroporphyrin compound is represented by the general formula (2).

[0032]

[Chemical 7]

[Wherein R¹~ R¹⁴Each independently, water
Represents an elementary atom or the above substituent, R¹~ R¹⁴Each substituent of
Is a ring together through an adjacent substituent and linking group.
May be formed, Q¹~ Q^FourIndependently,
Child or C-R¹⁵~ CR¹⁸(R ¹⁵~ R¹⁸Is R¹~ R¹⁴
Represents one of the groups shown in 1))
Represents a methine group which may be R⁹And R^Ten, R¹¹And R¹²,
And R¹³And R¹⁴One or two of the combinations
May each form a single bond directly.
Ku, M¹May have two hydrogen atoms or a ligand 2 to
Tetravalent substituted or unsubstituted metal atom or metalloid source
Represents a child. ] (5) The hydroporphyrin compound is represented by the general formula (3)
The optical recording medium of (4) represented.

[0034]

[Chemical 8]

[Wherein R ^{19 to} R ³² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group,
Substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted aryloxy group A substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted aralkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted A heterocyclic thio group, a substituted or unsubstituted alkenylthio group, a substituted amino group, a substituted or unsubstituted acyloxy group, R ¹⁹
Each substituent of R ³² to R ³² is bonded to the adjacent substituent through a linking group,
They may be combined together to form a ring, and Q ^{5 to} Q ⁸ are each independently a nitrogen atom or C—R ^{33 to} C—R ³⁶ (R ³³ to
R ³⁶ represents an optionally substituted methine group represented by any one of R ^{19 to} R ³² ), and R ²¹ and R ²² , R ²³ and R ²⁴ , and R ²⁵ and R ^26. One or two of the above combinations may directly form a single bond, and M ² represents two hydrogen atoms, a divalent unsubstituted atom, a metal atom having a ligand, or a substituent. Represents a trivalent or tetravalent metal atom, a semimetal atom, or an oxymetal atom. (6) Recording and reproduction are possible with respect to a laser beam selected from a wavelength range of 390 nm to 500 nm and / or a wavelength range of 500 nm to 900 nm (1) to
The optical recording medium according to any one of (5). (7) The optical recording medium according to (6), which is capable of recording and reproducing with respect to a laser beam selected from a wavelength range of 390 nm to 430 nm and / or a wavelength range of 630 nm to 690 nm. (8) The optical recording medium according to (7), which is capable of recording and reproducing with respect to a laser beam selected from a wavelength range of 400 nm to 410 nm. (9) A hydroporphyrin compound represented by the general formula (2).

[0036]

[Chemical 9]

[In the formula, R ^{1 to} R ¹⁴ each independently represent a hydrogen atom, a hydrocarbon group which may have a hetero atom, a halogen atom or a hydroxyl group, and each substituent of R ^{1 to} R ¹⁴ May together form a ring via an adjacent substituent and a linking group, and Q ^{1 to} Q ⁴ are each independently,
Nitrogen atom or ^{C-R 15 ~C-R 18} (R 15 ~R 18 is R ¹
To R ¹⁴ ), which represents an optionally substituted methine group, represented by R ⁹ and R ¹⁰ , and R ¹¹ and R.
One or two combinations of ¹² , and R ¹³ and R ¹⁴ may directly form a single bond, and M ¹ may have two hydrogen atoms or a ligand. It represents a divalent to tetravalent substituted or unsubstituted metal atom or a semimetal atom. ] (10) The hydroporphyrin compound of (9) represented by the general formula (3).

[0038]

[Chemical 10]

[Wherein R ^{19 to} R ³² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group,
Substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted aryloxy group A substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted aralkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted A heterocyclic thio group, a substituted or unsubstituted alkenylthio group, a substituted amino group, a substituted or unsubstituted acyloxy group, R ¹⁹
Each substituent of R ³² to R ³² is bonded to the adjacent substituent through a linking group,
They may be combined together to form a ring, and Q ^{5 to} Q ⁸ are each independently a nitrogen atom or C—R ^{33 to} C—R ³⁶ (R ³³ to
R ³⁶ represents an optionally substituted methine group represented by any one of R ^{19 to} R ³² ), and R ²¹ and R ²² , R ²³ and R ²⁴ , and R ²⁵ and R ^26. One or two of the above combinations may directly form a single bond, and M ² represents two hydrogen atoms, a divalent unsubstituted atom, a metal atom having a ligand, or a substituent. Represents a trivalent or tetravalent metal atom, a semimetal atom, or an oxymetal atom. (11) The compound according to (9), wherein one or two of the combinations of R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , and R ¹³ and R ¹⁴ directly form a single bond. (12) The compound of (11), wherein one or two of Q ^{1 to} Q ⁴ are nitrogen atoms. (13) The compound according to (11), wherein two of the combinations of R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , and R ¹³ and R ¹⁴ directly form a single bond.

[0040]

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 a hydroporphyrin compound which may be metal-complexed, and particularly in the wavelength range of 400 nm to 410 nm. The present invention relates to a novel optical recording medium capable of recording and reproducing with a laser beam selected from

The optical recording medium according to the present invention refers to 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 disc, and has, for example, a guide groove on a support substrate, and a recording layer containing a reflection film and an organic dye as a main component on the guide groove. Although a medium for recording and reproducing a signal by irradiating a laser beam of 500 nm will be described, the optical recording medium of the present invention is not limited to such a shape and configuration, and a card shape, a sheet shape, etc. The present invention can be applied to various shapes, those having no reflective layer, and those applicable to recording and reproduction 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, an organic dye layer is provided as a recording layer on a substrate, and at least one hydroporphyrin compound which may be metal complexed is selected and contained as the organic dye. is there. And among them, the wavelength of 390 nm to 500 nm, and further the wavelength of 390
nm to 430 nm, especially 400 nm to 410 nm
Is an 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 above range, and having good reproducing light stability and high-quality signal characteristics. .

Examples of the hydroporphyrin compound referred to in the present invention include, for example, chlorin derivative (dihydroporphyrin derivative), bacteriochlorin derivative (tetrahydroporphyrin derivative), hexahydroporphyrin derivative, octahydroporphyrin derivative, azachlorin derivative (dihydroaza). Porphyrin derivatives), azabacteriochlorin compounds (tetrahydroazaporphyrin derivatives), hexahydroazaporphyrin derivatives, octahydroazaporphyrin derivatives and the like. Further, each of the pyrrole ring and the pyrroline ring contained in these ring structures may have a condensed ring. In addition, derivatives in which the hydro group (hydrogen atom) on the pyrroline ring is substituted with other substituents are also included in these derivatives.

The "hydrocarbon group which may have a hetero atom" as defined in the present invention means that in addition to the carbon atom and hydrogen atom constituting the hydrocarbon group, a hetero atom is used as a substituent or a main hydrocarbon group. It means that it has in the skeleton, and further means a hydrocarbon group bonded through a hetero atom (the hydrocarbon group may also have a substituent or a hetero atom in the main skeleton). . The case of having a hetero atom, for example, has a substituent containing a hetero atom such as a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an alkoxy group, an acyl group, an acyloxy group, or a heterocyclic group as a substituent. Two or more hydrogen atoms bonded to one carbon atom in a hydrocarbon group such as a hydrocarbon group or an acyl group are substituted by one oxygen atom, or a carbon atom in the main skeleton such as a heterocyclic group is hetero Substituents substituted by a hetero atom such as those substituted with atoms, hydrocarbon oxy groups, hydrocarbon thio groups, hydrocarbon amino groups and the like are shown. The "hydrocarbon group" herein means a linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group.

In the hydroporphyrin compound of the present invention, the substituents on the pyrroline ring and / or the pyrrole ring in the skeleton of the compound may be bonded to each other via a linking group to form a ring. , Especially the optical properties such as refractive index and extinction coefficient for blue laser light wavelength are optimal,
Good recording / playback can be performed.

The compound represented by the general formula (1) according to the present invention can arbitrarily select the absorption wavelength while maintaining the absorption coefficient by the selection of the substituent, and the organic dye layer as the recording layer is coated. When used as an organic dye, the solubility in an organic solvent, which is indispensable for production by the method, can be arbitrarily adjusted, and the optical constant required for the recording layer can be satisfied at the wavelength of the laser beam. It is a very useful compound.

Particularly, for recording in the blue laser wavelength region selected from the wavelength range of 400 nm to 410 nm, L, X, Y, Z in the general formula (1) (Q ^{1 to} Q ⁴ in the formula (2) are used. 1) or 2 are nitrogen atoms,
And one of the rings A to D is a pyrrole ring and the other is a pyrroline ring (in the formula (2), R ^{9 to} R ¹⁰ and R ^{11 1} to
(A combination of R ¹² and R ^{13 to} R ¹⁴ forms a single bond directly), and two of rings A to D are pyrrole rings and the other is a pyrroline ring. (In formula (2),
Two of the above-mentioned combinations are preferably used because the azabacteriochlorin compound which directly forms a single bond has good storage stability in the medium. Also, L, X, Y, Z (Q ¹ to
Q ⁴ ) is an optionally substituted methine group, two of rings A to D are pyrrole rings, and the other is a pyrroline ring (in formula (2), two of the above combinations are , Each of which directly forms a single bond)
A bacteriochlorin compound is preferably used. Further, as the hydrocarbon group which may have a hetero atom bonded to the pyrrole ring or the pyrroline ring represented by rings A, B, C and D, one having 1 to 16 carbon atoms is preferable because of excellent recording.

The present invention will be described in more detail below.

Regarding the compound represented by the general formula (1) described in the present invention, the pyrrole ring or the pyrroline ring which may have a substituent represented by rings A, B, C and D,
Specific examples of the substituent capable of substituting with the hydrogen atom include a halogen atom, a hydroxyl group, and a hydrocarbon group which may have a hetero atom.

Specific examples of the optionally substituted methine group represented by L, X, Y and Z of the hydroporphyrin skeleton of the general formula (1) are represented by the formula (α). , Formula (β), formula (γ), formula (δ)

[0054]

[Chemical 11]

[In the formula, G ¹ , G ² , G ³ and G ⁴ are represented by the formula (2)
Has the same meaning as each group shown in R ^{15 to} R ¹⁸ . ] The methine group etc. which may be substituted which are shown by these are mentioned.

Further, in the above-mentioned substituents which are substituted on the pyrrole ring and the pyrroline ring, the substituents on the pyrrole ring or the pyrroline ring may be linked to each other via a linking group. Examples thereof include ring formation by group condensation or aromatic condensation, or formation of a heterocycle in which the linking group contains a hetero atom or a hetero atom such as a metal complex residue.

In the formula (1), M represents two hydrogen atoms, a divalent to tetravalent substituted or unsubstituted metal atom which may have a ligand, or a metalloid atom.

In the present invention, the compound represented by the general formula (1) is preferably a compound represented by the general formula (2).

[0059]

[Chemical 12]

[Wherein, R ^{1 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a hydrocarbon group which may have a hetero atom, and each of the substituents R ^{1 to} R ¹⁸ May together form a ring via an adjacent substituent and a linking group, and Q ^{1 to} Q ⁴ are each independently a nitrogen atom or C—R ^{15 to} C—R ¹⁸ (R ^{15 to} R). ¹⁸ is R ¹ ~
Represented by indicating one of the groups shown in R ^14), represents a methine group which may be substituted, R ⁹ and R ^10, R ¹¹ and R ^12, and of the combination of R ¹³ and R ^14, 1 Or two combinations each may directly form a single bond, M ¹ is 2 hydrogen atoms, a divalent to tetravalent substituted or unsubstituted metal atom which may have a ligand, or Represents a metalloid atom. ]

Examples of the halogen atom of R ^{1 to} R ¹⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Preferable specific examples of the hydrocarbon group which may have a hetero atom represented by R ^{1 to} R ¹⁴ include an alkyl group, an aralkyl group, an aryl group, a heteroaryl group, an alkenyl group, Substituted or unsubstituted hydrocarbon group such as heterocyclic group; substituted or unsubstituted hydrocarbon oxy group such as alkoxy group, aralkyloxy group, aryloxy group, heteroaryloxy group, alkenyloxy group, acyloxy group; alkylthio group , Substituted or unsubstituted hydrocarbon thio groups such as aralkylthio groups, arylthio groups, heteroarylthio groups, alkenylthio groups; substituted or unsubstituted alkyl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted aryl Group, substituted or unsubstituted alkenyl group, substituted or unsubstituted heterocyclic group, etc., which may have a hetero atom Hydrocarbon amino group such as mono- or disubstituted amino group hydrogen group; and the like.

Specific examples of the optionally substituted methine group represented by Q ^{1 to} Q ⁴ of the hydroporphyrin skeleton of the formula (2) are L of the formula (1),
The same methine groups as X, Y and Z can be mentioned.

Further, in the above-mentioned substituents which are substituted on the pyrrole ring and the pyrroline ring, each substituent on the pyrrole ring and the pyrroline ring may be preferably linked via a linking group. Includes the formation of a ring by aliphatic condensation or aromatic condensation, or the formation of a heterocycle in which the linking group contains a hetero atom or a hetero atom such as a metal complex residue.

As M ¹ in the formula (2), a divalent or tetravalent substituted or unsubstituted metal atom which may have a ligand or a semimetal atom is a preferable divalent non-valent metal atom. Examples thereof include a metal atom having a substituent or a ligand, a trivalent or tetravalent metal atom having a substituent or a metalloid atom, and an oxymetal atom.

In the present invention, the compound represented by the general formula (1) is preferably a compound represented by the general formula (3).

[0067]

[Chemical 13]

[Wherein, R ^{19 to} R ³² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group,
Substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted aryloxy group A substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted aralkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted A heterocyclic thio group, a substituted or unsubstituted alkenylthio group, a substituted amino group, a substituted or unsubstituted acyloxy group, R ¹⁹
Each substituent of R ³² to R ³² is bonded to the adjacent substituent through a linking group,
They may be combined together to form a ring, and Q ^{5 to} Q ⁸ are each independently a nitrogen atom or C—R ^{33 to} C—R ³⁶ (R ³³ to
R ³⁶ represents an optionally substituted methine group represented by any one of R ^{19 to} R ³² ), and R ²¹ and R ²² , R ²³ and R ²⁴ , and R ²⁵ and R ^26. One or two of the above combinations may directly form a single bond, and M ² represents two hydrogen atoms, a divalent unsubstituted atom, a metal atom having a ligand, or a substituent. Represents a trivalent or tetravalent metal atom, a semimetal atom, or an oxymetal atom. ]

The halogen atom for R ^{19 to} R ³² is R ¹
The same halogen atom as the halogen atom for R ¹⁴ to R ¹⁴ can be mentioned.

The substituted or unsubstituted alkyl group represented by R ^{19 to} R ³² 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;

4 to 10 carbon atoms 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 methylsulfonaminomethyl group, methylsulfonaminoethyl group, ethylsulfonaminoethyl group, propylsulfonaminoethyl group, octylsulfonaminoethyl group;

Methylsulfonylmethyl group, ethylsulfonylmethyl group, butylsulfonylmethyl group, methylsulfonylethyl group, ethylsulfonylethyl group, butylsulfonylethyl group, 2-ethylhexylsulfonylethyl group, 2,2,3,3-tetrafluoro An alkyl group having 2 to 10 carbon atoms substituted with an alkylsulfonyl group such as a propylsulfonylmethyl group or a 2,2,3,3-tetrachloropropylsulfonylmethyl group;

Benzenesulfonylmethyl group, benzenesulfonylethyl group, benzenesulfonylpropyl group, benzenesulfonylbutyl group, toluenesulfonylmethyl group, toluenesulfonylethyl group, toluenesulfonylpropyl group, toluenesulfonylbutyl group, xylenesulfonylmethyl group, xylenesulfonyl group 7 to 1 carbon atoms substituted with an arylsulfonyl group such as ethyl group, xylenesulfonylpropyl group, xylenesulfonylbutyl group
An alkyl group of 2;

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) titanocenemethyl 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;

Cobaltcenecarbonyloxymethyl 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 ^{19 to} R ³² 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 ^{19 to} R ³² 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 heterocyclic group represented by R ^{19 to} R ³² are heterocyclic groups which may have the same substituents as the above-mentioned alkyl groups, 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, benzotriazole-
1-yl group, purinyl group, quinolinyl group, isoquinolinyl group, coumarinyl group, cinnolinyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group, phenanthronylyl group, phenothiazinyl group, flavonyl group, phthalimidyl group, naphthylimidyl group An unsubstituted heteroaryl group such as a 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,
Alkylthio groups such as methoxymethylthio group, ethoxyethylthio group, ethoxyethylthio group, trifluoromethylthio group; aralkylthio groups such as benzylthio group, phenethylthio group; phenylthio group, tolylthio group, naphthylthio group, xylylthio group, mesylthio group, Arylthio groups such as chlorophenylthio group and methoxyphenylthio group; Dialkylamino groups such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group; acetyl group, propionyl group, butanoyl group, ferrocenecarbonyl group, cobaltocenecarbonyl group Group, acyl group such as nickelocenecarbonyl group; methoxycarbonyl group, ethoxycarbonyl group, ferrocenemethoxycarbonyl group, 1-methylferrocene-1′-ylmethoxycarbonyl group, cobal Tocenylmethoxycarbonyl group,
Alkoxycarbonyl groups such as nickelocenylmethoxycarbonyl group; aralkyloxycarbonyl groups such as benzyloxycarbonyl group, phenethyloxycarbonyl group; phenoxycarbonyl group, tolyloxycarbonyl group, naphthoxycarbonyl group, xylyloxycarbonyl group, mesyloxy Aryloxycarbonyl group such as carbonyl group, chlorophenoxycarbonyl group and methoxyphenoxycarbonyl group; vinyloxycarbonyl group,
Alkyloxycarbonyl 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, octylaminocarbonyl group, nonylaminocarbonyl group, 3,5,5-trimethylhexylaminocarbonyl group, 2 A monoalkylaminocarbonyl group having 2 to 10 carbon atoms such as an ethylhexylaminocarbonyl group, a dimethylaminocarbonyl group, a diethylaminocarbonyl group,
Dipropylaminocarbonyl group, dibutylaminocarbonyl group, dipentylaminocarbonyl group, dihexylaminocarbonyl group, diheptylaminocarbonyl group, dioctylaminocarbonyl group, piperidinocarbonyl group, morpholinocarbonyl group, 4-methylpiperazinocarbonyl group An alkylaminocarbonyl group such as a 4-alkylpiperazinocarbonyl group having 3 to 20 carbon atoms such as a dialkylaminocarbonyl group;

Furanyl group, pyrrolyl group, 3-pyrrolino group, pyrrolidino group, 1,3-oxolanyl group, pyrazolyl group, 2-pyrazolinyl group, pyrazolidinyl 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, 4H-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, phenothiazinyl group, flavonyl group, etc. A heterocyclic group;

A heteroaryl group substituted with a substituent such as 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 alkenyl group for R ^{19 to} R ³² are alkenyl groups which may have the same substituents as the above-mentioned alkyl groups, and are 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- Examples thereof include alkenyl groups having 2 to 20 carbon atoms such as methylsulfone vinyl group, styryl group, 4-phenyl-2-butenyl group and phytyl group.

Examples of the substituted or unsubstituted alkoxy group of R ^{19 to} R ³² 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-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
An alkoxy group having 2 to 10 carbon atoms, which is substituted with an alkylamino group such as a-(n-butylamino) ethoxy group, a 3- (n-hexylamino) propoxy group, a 4- (cyclohexylamino) butyloxy group;

Methylaminomethoxymethoxy group, methylaminoethoxyethoxy group, methylaminoethoxypropoxy group, ethylaminoethoxypropoxy group, 4-
3 to 1 carbon atoms substituted with an alkylaminoalkoxy group such as (2′-isobutylaminopropoxy) butoxy group
An alkoxy group of 0;

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 of R ^{19 to} R ³² 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 for R ^{19 to} R ³² are 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 heterocyclic oxy group for R ^{19 to} R ³² include a heterocyclic oxy group which may have a substituent similar to the above-mentioned alkyl group, 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, pyri Dazinyloxy group, pyrimidinyloxy group, pyrazinyloxy group, piperazinyloxy group, triazinyloxy group, benzofuranyloxy group, indolyloxy group, thionaphthenyloxy group, benzimidazolyloxy group, benzothiazoli Group, benzotriazol-2-yloxy group, benzotriazole-
1-yloxy group, purinyloxy group, quinolinyloxy group, isoquinolinyloxy group, coumarinyloxy group,
Cinnolinyloxy group, quinoxalinyloxy group, dibenzofuranyloxy group, carbazolyloxy group, phenanthronylyloxy group, phenothiazinyloxy group, flavonyloxy group, phthalimidyloxy group, naphthylimi An unsubstituted heteroaryloxy group such as a diloxy 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,
Alkylthio groups such as methoxymethylthio group, ethoxyethylthio group, ethoxyethylthio group, trifluoromethylthio group; aralkylthio groups such as benzylthio group, phenethylthio group; phenylthio group, tolylthio group, naphthylthio group, xylylthio group, mesylthio group, Arylthio groups such as chlorophenylthio group and methoxyphenylthio group; Dialkylamino groups such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group; acetyl group, propionyl group, butanoyl group, ferrocenecarbonyl group, cobaltocenecarbonyl group Groups, acyl groups such as nickelocenecarbonyl groups;

Alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, ferrocenemethoxycarbonyl group, 1-methylferrocene-1'-ylmethoxycarbonyl group, cobaltcenylmethoxycarbonyl group, nickelocenylmethoxycarbonyl group; benzyloxy Aralkyloxycarbonyl group such as carbonyl group, phenethyloxycarbonyl group; phenoxycarbonyl group, tolyloxycarbonyl group, naphthoxycarbonyl group, xylyloxycarbonyl group, mesyloxycarbonyl group, chlorophenoxycarbonyl group, methoxyphenoxycarbonyl group, etc. Aryloxycarbonyl group;
Alkenyloxycarbonyl groups such as vinyloxycarbonyl group, allyloxycarbonyl group, butenyloxycarbonyl group, butadienyloxycarbonyl group, cyclopentadienyloxy group, pentenyloxycarbonyl group, octenyloxycarbonyl group; methylaminocarbonyl Group, ethylaminocarbonyl group, propylaminocarbonyl group, butylaminocarbonyl group, pentylaminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group, octylaminocarbonyl group, nonylaminocarbonyl group, 3,5,5-trimethylhexyl group C2-C10 monoalkylaminocarbonyl groups such as aminocarbonyl groups and 2-ethylhexylaminocarbonyl groups, dimethylaminocarbonyl groups, and diethylaminocarbo groups. Group, dipropylaminocarbonyl group, dibutylaminocarbonyl group, dipentylaminocarbonyl group, dihexylaminocarbonyl group, diheptylaminocarbonyl group, dioctylaminocarbonyl group, piperidinocarbonyl group, morpholinocarbonyl group, 4-methylpiperazyl group Alkylcarbonyl group such as dicarbonylaminocarbonyl group having 3 to 20 carbon atoms such as nocarbonyl group and 4-ethylpiperazinocarbonyl group;

Furanyl group, pyrrolyl group, 3-pyrrolino group, pyrrolidino group, 1,3-oxolanyl group, pyrazolyl group, 2-pyrazolinyl group, pyrazolidinyl 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, 4H-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, phenothiazinyl group, flavonyl group, etc. A heterocyclic group;

Examples of the heteroaryloxy group include 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 alkenyloxy group for R ^{19 to} R ³² 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 Carbon such as oxy group, 2-cyano-2-methylcarboxyl vinyloxy group, 2-cyano-2-methylsulfone vinyloxy group, styryloxy group, 4-phenyl-2-butenyloxy group, cinnamylalkoxy group and phytyloxy group The alkenyloxy group of several 2-20 is mentioned.

Examples of the substituted or unsubstituted alkylthio group represented by R ^{19 to} R ³² 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 of R ^{19 to} R ³² are aralkylthio groups which may have the same substituents as the above-mentioned alkyl groups, 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 ^{19 to} R ³² 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 heterocyclic thio group for R ^{19 to} R ³² include a heterocyclic thio group which may have a substituent similar to the above-mentioned alkyl group, 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, benzothiazolylthio group, benzotriazol-2-ylthio group, benzotriazol-1-ylthio group, purinylthio group, quinolinylthio group, isoquinolinylthio group, coumarinylthio group, cinnolinylthio group Unsubstituted heteroaryl such as quinoxalinylthio group, dibenzofuranylthio group, carbazolylthio group, phenanthronylylthio group, phenothiazinylthio group, flavonylthio group, phthalimidylthio group and naphthylimidylthio group Oh 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,
Alkylthio groups such as methoxymethylthio group, ethoxyethylthio group, ethoxyethylthio group, trifluoromethylthio group; aralkylthio groups such as benzylthio group, phenethylthio group; phenylthio group, tolylthio group, naphthylthio group, xylylthio group, mesylthio group, Arylthio groups such as chlorophenylthio group and methoxyphenylthio group; Dialkylamino groups such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group; acetyl group, propionyl group, butanoyl group, ferrocenecarbonyl group, cobaltocenecarbonyl group Groups, acyl groups such as nickelocenecarbonyl groups;

Alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, ferrocenemethoxycarbonyl group, 1-methylferrocene-1'-ylmethoxycarbonyl group, cobaltcenylmethoxycarbonyl group, nickelocenylmethoxycarbonyl group; benzyloxy Aralkyloxycarbonyl groups such as carbonyl group and phenethyloxycarbonyl group; phenoxycarbonyl group, tolyloxycarbonyl group, naphthoxycarbonyl group, xylyloxycarbonyl group, mesyloxycarbonyl group, chlorophenoxycarbonyl group, methoxyphenoxycarbonyl group, etc. Aryloxycarbonyl group;
Alkenyloxycarbonyl groups such as vinyloxycarbonyl group, allyloxycarbonyl group, butenyloxycarbonyl group, butadienyloxycarbonyl group, cyclopentadienyloxy group, pentenyloxycarbonyl group, octenyloxycarbonyl group; methylaminocarbonyl Group, ethylaminocarbonyl group, propylaminocarbonyl group, butylaminocarbonyl group, pentylaminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group, octylaminocarbonyl group, nonylaminocarbonyl group, 3,5,5-trimethylhexyl group C2-C10 monoalkylaminocarbonyl groups such as aminocarbonyl groups and 2-ethylhexylaminocarbonyl groups, dimethylaminocarbonyl groups, and diethylaminocarbo groups. Group, dipropylaminocarbonyl group, dibutylaminocarbonyl group, dipentylaminocarbonyl group, dihexylaminocarbonyl group, diheptylaminocarbonyl group, dioctylaminocarbonyl group, piperidinocarbonyl group, morpholinocarbonyl group, 4-methylpiperazyl group Alkylcarbonyl group such as dicarbonylaminocarbonyl group having 3 to 20 carbon atoms such as nocarbonyl group and 4-ethylpiperazinocarbonyl group;

Furanyl group, pyrrolyl group, 3-pyrrolino group, pyrrolidino group, 1,3-oxolanyl group, pyrazolyl group, 2-pyrazolinyl group, pyrazolidinyl 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, 4H-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, phenothiazinyl group, flavonyl group, etc. A heterocyclic group;

A heteroarylthio group substituted by a substituent such as 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 alkenylthio group for R ^{19 to} R ³² 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 an alkenylthio group having 2 to 20 carbon atoms such as a hexanedienylthio group, a cyclopentadienylthio group, a styrylthio group, a cyclohexenylthio group, a decenylthio group and a phytylthio group.

Examples of the substituted amino group of R ^{19 to} R ³² include:
It is a mono-substituted amino group or a di-substituted amino group which may have the same substituents as the above-mentioned alkyl groups, preferably a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group. Group, hexylamino group, heptylamino group, octylamino group, (2-
Ethylhexyl) amino group, cyclohexylamino group,
A monoalkylamino group having 1 to 10 carbon atoms such as (3,5,5-trimethylhexyl) amino group, nonylamino group and 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
A mono-substituted amino group such as an acylamino group having 1 to 16 carbon atoms such as a methylferrocene-1′-carbonylamino group, a cobaltocenecarbonylamino group or a nickelocenecarbonylamino group;

Dimethylamino group, diethylamino 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-
A dialkylamino group having 2 to 16 carbon atoms such as a (2-cyanoethyl) amino group and 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. A disubstituted amino group such as;

Examples of the substituted or unsubstituted acyloxy group of R ^{19 to} R ³² 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 Zoyloxy 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 substituents R ^{33 to} R ³⁶ of the optionally substituted methine group represented by Q ^{5 to} Q ⁸ are R ^{19 to} R ^32.
The same substituents as can be mentioned. Q ^{5 to} Q ⁸ are preferably unsubstituted methine groups, fluorine atoms, chlorine atoms,
Examples thereof include halogen atoms such as bromine atom and iodine atom; substituted or unsubstituted alkyl groups; substituted or unsubstituted aralkyl groups; substituted or unsubstituted aryl groups; and substituted methine groups substituted with an acyloxy group and the like.

R¹⁹~ R³²Via the adjacent substituent and linking group
And as a connecting group when forming a ring together
Is a nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, metal atom
Heteroatoms such as children and metalloid atoms and carbon atoms as appropriate
A group which is selected and combined, and a preferable linking group
By way of example, -O-, -S- or may be substituted.
Methylene group, methine group, ethynylene group, phenylene group,
Amino group, imino group, metal atom, etc.
The desired ring can be obtained by combining. By linking group
The ring formed by the
A ring having a shape or a three-dimensional shape can be used. Of connected skeletons
As a preferred example, -CH₂-CH₂-CH ₂-CH₂-,
-CH₂(NO₂) -CH₂-CH₂-CH₂-, -CH
(CH₃) -CH₂-CH₂-CH₂-, -CH (Cl)-
CH₂-CH₂An aliphatic fused ring such as-,

-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 C
_{H 2 CH (CH 3) -} (OCH 3)) = C (Cl) -C
(Cl) = C (OCH ₂ CH ₂ CH (CH ₃ )-(OC
_{H 3)) -, - C} (OCH 2 CH 2 CH (CH 3) 2) = C
(Cl) -C (Cl) = C (OCH 2 CH 2 CH (C
_{H 3) 2) -, -} CH = C (CH 3) -C (CH 3) = CH
-, -C (Cl) = CH-CH = CH-, -C {OCH
[CH (CH _{3) 2] 2} = CH-CH = CH} -, - C
{OCH [CH (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) = C
H-CH = CH -, - 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- aromatic such fused _{ring; -O-CH 2 -CH 2 -O} -, - O-CH (CH
₃₎ -CH (CH ₃₎ -O-, etc. chain linked heterocycle or,

[0153]

[Chemical 14]

(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 ¹⁹~ R³²C1 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 ^{19 to} R ³² are each connected to the adjacent substituent through a linking group, a suitable combination of links is R ¹⁹
And R ²⁰ , R ²¹ and R ²² , R ²¹ and R ²⁷ , R ²² and R ²⁷ , R ²² and R ²⁸ , R ²³ and R ²⁴ , R ²³ and R ³⁰ , R ²⁴ and R ²⁹ , R ²⁴ and R ^24.
30 , R ²⁵ and R ²⁶ , R ²⁵ and R ³² , R ²⁶ and R ³¹ , R ³¹ and R ³²
Etc.

Examples of the divalent to tetravalent metal atom or metalloid atom represented by M ² include groups IIA to VIIA and VIII of the periodic table,
Mention may be made of metal atoms as well as metalloid atoms of groups IB to VIIB.

Specific examples of the divalent metal atom include C
u, Zn, Fe, Co, Ni, Ru, Rh, Pd, P
t, Mn, Sn, Mg, Pb, Hg, Cd, Ba, T
i-, Be-, Ca-, Re-, Os-, etc., divalent unsubstituted metal atoms, or substituted or unsubstituted 5-membered ring nitrogen-containing aromatic compounds as ligands, 6-membered ring nitrogen-containing aromatic compounds, condensed ring-containing Examples thereof include heterocyclic compounds such as nitrogen compounds, divalent metal atoms coordinated with carbon monoxide, alcohols and the like.

Examples of the substituted or unsubstituted 5-membered ring nitrogen-containing aromatic compound coordinated to a divalent metal atom include pyrrole, 1-methylpyrrole, 3-methylpyrrole, 2,
5-dimethylpyrrole, pyrazole, N-methylpyrazole, 3,5-dimethylpyrazole, imidazole, N
-Methylimidazole, 2-methylimidazole, 4-
Methyl imidazole, 1,2-dimethyl imidazole,
Oxazole, thiazole, 4-methylthiazole,
2,4-dimethylthiazole, 1,2,3-oxadiazole, 1,2,3-triazole, 1,2,4-triazole, 1,3,4-thiadiazole, 2,5-dimethyl-1,3 , 4-thiadiazole and the like.

Examples of the substituted or unsubstituted 6-membered ring nitrogen-containing aromatic compound coordinated to a divalent metal atom include pyridine, 2-methylpyridine, 3-methylpyridine and 4-methylpyridine.
Methylpyridine, 2,3-dimethylpyridine, 2,4-
Dimethylpyridine, 2,5-dimethylpyridine, 2,6
-Dimethylpyridine, 3,4-dimethylpyridine, 3,
5-dimethylpyridine, 2-chloropyridine, 3-chloropyridine, 2-methoxypyridine, pyridazine, 3-
Examples thereof include methylpyridazine, pyrimidine, 4-methylpyrimidine, 2-chloropyrimidine, pyrazine, 2-methylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2-methoxypyrazine, and s-triazine.

Examples of the substituted or unsubstituted fused ring-containing nitrogen compound coordinated to a divalent metal atom include indole and
N-methylindole, 2-methylindole, 3-methylindole, 5-methylindole, 1,2-dimethylindole, 2,3-dimethylindole, 4-chloroindole, 5-chloroindole, 6-chloroindole, 4 -Methoxyindole, 5-methoxyindole, 6-methoxyindole, benzimidazole, 2-methylbenzimidazole, 5-methylbenzimidazole, 5,6-dimethylbenzimidazole,
5-chlorobenzimidazole, benzothiazole, 2
-Methylbenzothiazole, 2,5-dimethylbenzothiazole, 2-chlorobenzothiazole, purine, quinoline, 2-methylquinoline, 3-methylquinoline, 4-
Methylquinoline, 6-methylquinoline, 7-methylquinoline, 8-methylquinoline, 2,4-dimethylquinoline, 2,6-dimethylquinoline, 2-chloroquinoline,
6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, isoquinoline, 1-methylquinoline, quinoxaline, 2-methylquinoxaline, 2,3-dimethylquinoxaline, carbazole, N-methylcarbazole, acridine, 9-methylacridine, Examples include phenothiazine.

Suitable specific examples of the divalent metal atom include Cu, Ni, Co, Rh, Zn, Fe, Cu (pyridine) ₂ , Zn (pyridine) ₂ , Co (pyridine) ₂ , and F.
Examples thereof include an unsubstituted or dicoordinated divalent metal atom such as e (N-methylimidazole) and Co (N-methylimidazole).

The trivalent metal atom or metalloid atom having a substituent represented by M ² is Sc, Ti, V or C.
r, Mn, Mo, Ag, U, Fe, Co, Ni, Cu,
Y, Nb, Ru, Rh, La, Ta, Ir, Au, I
n, Tl, Bi, Ce, Pr, Nd, Pm, Sm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, L
u, B, As, Sb, or other trivalent non-substituted metal atom or non-substituted semimetal atom may be substituted with a hydroxyl group, an amino group, or a halogen atom or a substituent represented by R ^{1 to} R ¹⁴ described above. An alkyl group which may have, an aryl group,
Heteroaryl group, alkoxy group, aryloxy group,
Heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, the same halogen atom as the substituted amino group, an alkyl group which may have a substituent, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, Heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, substituted amino group, or a trivalent metal atom or semimetal atom selected from and bonded to a silyloxy group substituted with an alkyl group or an aryl group, or a substituent The same halogen atom as the above-mentioned substituent, optionally substituted alkyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio Group, a substituted trivalent amino group selected from substituted amino groups A heterocyclic compound such as a 5-membered ring nitrogen-containing aromatic compound, a 6-membered ring nitrogen-containing aromatic compound, a condensed ring nitrogen-containing compound, etc., which is substituted or unsubstituted as a ligand to a group atom or a semimetal atom, carbon monoxide, 3 coordinated with alcohol
Examples include valent metal atoms.

Examples of the silyloxy group substituted with an alkyl group or an aryl group include a trialkylsilyloxy group such as a trimethylsilyloxy group and a triethylsilyl group, a triarylsilyloxy group such as a triphenylsilyloxy group and a dimethylphenylsilyloxy group. Examples thereof include alkylarylsilyloxy groups and the like.

Preferable specific examples of the trivalent metal atom include Al-F, Al-Cl, Al-Br, Al-I and G.
a-F, Ga-Cl, Ga-Br, Ga-I, In-
F, In-Cl, In-Br, In-I, Ti-F, T
i-Cl, Ti-Br, Ti-I, Al-C 6 H 5, Al
_{-C 6 H 4 (CH 3)} , In-C 6 H 5, In-C 6 H 4 (C
_{H 3), Mn (OH)} , Mn (OC 6 H 5), Mn [OS
i (CH _{3) 3],} Fe-Cl, Fe-Cl ( bis (N-
And methyl-imidazole)), Fe- (imidazolyloxy), Ru-Cl, and other mono-substituted trivalent metal atoms.

Specific preferred examples of the trivalent semimetal atom include BF, B-OCH ₃ , B-C ₆ H ₅ and B-C ₆ H _4.
(CH ₃ ), B (OH), B (OC ₆ H ₅ ), B [OSi
(CH ₃ ) ₃ ] and other mono-substituted trivalent semimetal atoms.

M²A tetravalent metal having a substituent represented by
As the atom or metalloid atom, Ti, Cr, Sn, Z
Tetravalent unsubstituted metal atom such as r, Ge, Mn, Si, etc.
Is an unsubstituted semimetal atom, a hydroxyl group as a substituent,
Amino group, or R mentioned above ¹~ R¹⁴Indicated by
Group atom, optionally substituted alkyl group, aryl
Group, heteroaryl group, alkoxy group, aryloxy
Group, heteroaryloxy group, alkylthio group, aryl
Similar to ruthio group, heteroarylthio group, and substituted amino group
Halogen atom, an alkyl group which may have a substituent,
Reel group, heteroaryl group, alkoxy group, aryl
Oxy group, heteroaryloxy group, alkylthio group,
Arylthio group, heteroarylthio group, substituted amino
Groups, or silyl groups substituted with alkyl or aryl groups
Tetravalent metal atom or half-gold selected from xyl group and bonded
Substituted or unsubstituted 5-membered ring containing nitrogen as a ligand
Elementary aromatic compounds, 6-membered nitrogen-containing aromatic compounds, condensed ring-nitrogen containing compounds
Heterocyclic compounds such as elementary compounds, carbon monoxide, alcohols, etc.
And a tetravalent metal atom which may be coordinated.

As preferable specific examples of the tetravalent metal atom,
Is TiF₂, TiCl₂, TiBr ₂, TiI₂, CrF
₂, CrCl₂, CrBr₂, CrI₂, SnF₂, SnC
l₂, SnBr₂, SnI₂, ZrF₂, ZrCl₂, Zr
Br₂, ZrI₂, GeF₂, GeCl₂, GeBr₂, G
eI₂, MnF₂, MnCl₂, MnBr₂, MnI₂, T
i (OH)₂, Cr (OH)₂, Sn (OH)₂, Zr
(OH)₂, Ge (OH)₂, Mn (OH)₂, TiA₂,
CrA₂, SnA₂, ZrA₂, GeA₂, MnA₂, Ti
(OA)₂, Cr (OA)₂, Sn (OA)₂, Zr (O
A)₂, Ge (OA) ₂, Mn (OA)₂, Ti (S
A)₂, Cr (SA)₂, Sn (SA)₂, Zr (S
A)₂, Ge (SA)₂, Mn (SA)₂, Ti (NH
A)₂, Cr (NHA)₂, Sn (NHA)₂, Zr (N
HA)₂, Ge (NHA)₂, Mn (NHA)₂, Ti
(NA2)₂, Cr (NA₂)₂, Sn (NA₂)₂, Zr
(NA₂)₂, Ge (NA₂)₂, Mn (NA₂)₂[A is
R mentioned above¹⁹~ R³²An alkyl group represented by, an aryl group,
Substituted or unsubstituted alkyl similar to the heteroaryl group
A group, an aryl group and a heteroaryl group are shown. ], Etc.
Alternative tetravalent metal atoms are mentioned.

Preferred specific examples of the tetravalent semimetal atom include SiF ₂ , SiCl ₂ , SiBr ₂ , SiI ₂ and Si.
(OH) ₂ , SiA ₂ , Si (OA) ₂ , Si (SA) ₂ ,
Si (NHA) ₂ , Si (NA ₂ ) ₂ [A means the above-mentioned A. ] Disubstituted tetravalent semimetal atoms such as

Specific examples of the oxymetal atom represented by M ² include VO, MnO, TiO, OsO _{2 and the} like.

As M ² , preferably Cu, Ni or C
o, Rh, Zn, Fe, MnCl, CoCl, FeC
l, Fe (N-methylimidazolyloxy), Fe-C
l (bis (N-methylimidazole)), Cu (pyridine) ₂ , Zn (pyridine) ₂ , Co (pyridine) ₂ , Fe
(N- methylimidazole), Co (N- _{methylimidazole) 2, VO, TiO, TiA} 2, SiA 2, Sn
A ₂ , RuA ₂ , RhA ₂ , GeA ₂ , Si (OA) ₂ , S
n (OA) ₂ , Ge (OA) ₂ , Si (SA) ₂ , Sn
(SA) ₂ , Ge (SA) ₂ [A means A described above. ] Is mentioned.

The compound represented by the general formula (1) used in the present invention is not limited, for example, J. Amer. Chem.
Soc., Vol.91, pp7485-7489 (1969), Tetrahedron Lett
ers, vol.33 (15), pp1985-1988 (1992), Tetrahedron Le
tters, vol.34 (40), pp6369-6370 (1993), Liebigs An
n., pp1509-1514 (1995), Heterocycles, vol.39 (2), pp
439-443 (1994), J. Photochem. Photobiol, vol.23 (2-
3), pp239-243 (1994), CIBA Foundation Symposia, vol1
46, pp17 (1989), J. Chem. Soc., Pp3461-3469 (1957),
It is produced according to the method described in J. Chem. Soc., Pp733 (1957) and the like. Typically, it can be produced by the following reaction.

Regarding the hydroporphyrin compound represented by the general formula (3) of the present invention, the compound represented by the following formula (4) is prepared by adding an iron salt such as iron (III) chloride and an acetate such as sodium acetate. Under heat, if necessary, under heating in a solvent such as acetic acid to synthesize an iron complex chloride represented by the following formula (5), metal alcohol such as isoamyl alcohol is used as a solvent, sodium metal, metal potassium, etc. Alkali metal is added and the reaction is heated if necessary, and the reaction mass is neutralized with an acid, and then an iron (II) sulfate hydrochloric acid solution is added, followed by extraction with an organic solvent such as toluene or benzene and an aqueous phosphoric acid solution. The (aza) chlorin compound of the present invention represented by the following formula (6) can be obtained by washing and optionally performing metal complexation with a metal salt such as acetylacetonate metal salt and acetic acid metal salt. Kill.

[0173]

[Chemical 15]

[In the formula, R³⁷~ R⁴⁴, Q⁹~ Q¹², M³Is
R in formula (3)¹⁹~ R²⁶, Q^Five~ Q⁸, M ²Respectively the same as
Represents the meaning of. ]

Alternatively, the compound of the formula (4) is reacted with an alkali metal such as metal sodium or potassium in an alcohol such as isoamyl alcohol as a solvent, and if necessary, heated to react with an acid to give a reaction mass. After harmonizing
Add iron (II) sulphate hydrochloric acid solution, extract and wash with organic solvents such as toluene and benzene and aqueous ammonia, or heat with toluene sulfonyl hydrazide and potassium carbonate in a solvent such as pyridine. Then
After neutralizing the reaction mass with an acid, extract and wash with an organic solvent such as toluene and benzene and ammonia water, and if necessary, metal complex with a metal salt such as acetylacetonate metal salt and acetic acid metal salt. Thus, the (aza) bacteriochlorin compound of the present invention represented by the following formula (7) can be obtained.

[0176]

[Chemical 16]

[Wherein R ^{45 to} R ⁵² , Q ^{13 to} Q ¹⁶ , M
⁴ has the same meaning as R ^{19 to} R ²⁶ , Q ^{5 to} Q ⁸ and M ² of the formula (3), respectively. ]

Further, by reacting the compound of formula (4) with an excess of osmium oxide such as osmium tetroxide, the present invention represented by formula (8) or formula (9) which is a corresponding product. The (aza) chlorin compound or (aza) bacteriochlorin compound can be obtained.

[0179]

[Chemical 17]

[Wherein R ^{53 to} R ⁶⁰ , Q ^{17 to} Q ²⁰ , M
⁵ has the same meaning as R ^{19 to} R ²⁶ , Q ^{5 to} Q ⁸ and M ² of the formula (3), respectively. ]

With respect to R ^{19 to} R ³² of the formula (3) wherein any group is a hydrogen atom, for example, hydrocarbonation, nitration, halogenation, formylation, amination, hydroxylation, acylation, The selected hydrogen atom is replaced with an arbitrary substituent by a conventional synthetic method such as elimination reaction and mercapto-formation, and further, a standard synthetic method such as reduction, oxidation, isomerization, and rearrangement is used as necessary. It is also possible to obtain a compound of formula (3) in which a hydrogen atom is substituted.

Regarding R ^{19 to} R ^{32 in} the formula (3) wherein any group is a hydroxyl group, for example, hydrocarbonation, halogenation, amination, acylation, elimination reaction,
By a conventional synthetic method such as mercapto conversion, the selected hydroxyl group is substituted with an arbitrary substituent, and further, by using a conventional synthetic method such as reduction, oxidation, isomerization and transfer, a hydroxyl group can be obtained. It is also possible to obtain a compound of formula (3) in which

Further, among R ^{19 to} R ^{32 in} the formula (3), those in which any group is a halogen atom can be prepared by conventional methods such as hydrocarbonation, amination, hydroxylation, elimination reaction and mercapto formation. According to the synthetic method, the selected halogen atom is substituted with an arbitrary substituent, and further, if necessary, reduction,
A compound of formula (3) substituted with a halogen atom can also be obtained by using a conventional synthetic method such as oxidation, isomerization, and transfer.

Specific examples of the hydroporphyrin compound represented by the general formula (2) include compounds (1-1) to (1-11) having a substituent described below.

The notation of substituents and the like is shown in accordance with the formula (2), but the formula (6) to the formula (9) are represented by the formula (2).
, And the replacement of the corresponding substituents is obvious.

[0186]

[Chemical 18]

[0187]

[Chemical 19]

The dye of the recording layer constituting the optical recording medium of the present invention is substantially composed of one or more hydroporphyrin compounds, particularly compounds of the formulas (1) to (3). And, if desired, a wavelength of 290n
Absorption maximum at m-690nm, 300nm-900
It may be mixed with a compound having a large refractive index in nm other than the above. Specifically, cyanine compounds, squarylium compounds, naphthoquinone compounds, anthraquinone compounds, tetrapyrporphyrazine compounds, indophenol compounds, pyrylium compounds, thiopyrylium compounds, azulenium compounds, triphenylmethane compounds , Xanthene compounds, indasulen compounds, indigo compounds, thioindigo compounds, merocyanine compounds, thiazine compounds, acridine compounds, oxazine compounds, dipyrromethene compounds, oxazole compounds, porphyrin compounds, porphycene compounds, etc. However, it may be a mixture of a plurality of compounds. The mixing ratio of these compounds is 0.1% by mass to 3%.
It is about 0 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, as iron-based metal compounds, organic acid iron compounds such as iron formate, iron oxalate, iron laurate, iron naphthenate, iron stearate, and iron acetate, acetylacetonato 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 compounds described in JP-A No. 10-291366, compounds having a substituent described in the publication, and the like.

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

Alternatively, it is possible to introduce a compound having a quencher ability, a compound thermal decomposition promoting ability, an ultraviolet absorbing ability, and an adhesive ability 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 hydroporphyrin compound residue of the formula (1) of the present invention. May be chemically bonded to each other through at least one single bond, double bond or triple bond to form one molecule. Preferably, each substituted R ^{1 to} R ¹⁸ of the hydroporphyrin compound of formula (2) is represented by formula (10)

-(Lⁿ)-(Jⁿ) (10) [In the formula, LⁿIs a hydroporphyrin compound of formula (2)
To, ie a single bond, or may be substituted
Methylene group, methine group, amino group, imino group, oxygen source
At least one selected from a child or a sulfur atom
Represents an atomic chain of 1 to 20 atoms, JⁿQuencher
ー, compound thermal decomposition accelerator, ultraviolet absorber, adhesive ability, heat absorption
R with ability or endothermic resolution¹~ R¹⁸Compound corresponding to
Represents a residue. ] Or a substituent of formula (2)
R that is a combination of adjacent substituents ¹And R², R³When
R^Four, R^FiveAnd R⁶, R⁷And R⁸, R⁹And R^Ten, R¹¹And R¹², R
¹³And R¹⁴, R³And R⁹, R³And R^Ten, R^FourAnd R⁹, R^FourWhen
R^Ten, R⁶And R¹¹, R^FiveAnd R¹², R⁶And R¹¹, R⁶And R¹²,
R⁷And R¹³, R⁷And R¹⁴, R⁸And R¹³, R⁸And R¹⁴About
Then, the formula (11)

-(L ^m1 )-(J ^m )-(L ^m2 )-(11) [wherein, L ^m1 and L ^m2 are adjacent to each other, and a binding site to the hydroporphyrin-based compound of the formula (2), That is, a single bond, or a methylene group which may be substituted, a methine group,
An amino chain, an imino group, an atom chain having 1 to 20 atoms selected by connecting at least one kind from an oxygen atom or a sulfur atom, and J ^m is a quencher, a compound thermal decomposition accelerator, an ultraviolet absorber, an adhesive ability R having endothermic ability or endothermic resolution
¹ represents a compound residue corresponding to R ¹⁴ . ] 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, —OCH ₂ —, —OCH (CH ₃ ) —,
_{-CH 2 OCH 2 -, - CH} 2 OCH (CH 3) -, - CH
_{(CH 3) OCH (CH 3} ) -, - CH = CH -, - CH
= N-, -CH = CH-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 (10) include the following metal complex residues.

[0202]

[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 ¹⁹~ R³²C1 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 (11) include the following metal complex residues.

[0205]

[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 ¹⁹~ R³²C1 which may have the same substituent as
-10 alkyl group, alkoxy group, aryl group, ari
Group, aralkyl group, aralkyloxy group
Represents). )

Further, if necessary, an additive substance 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.

When a recording layer is formed on a substrate, in order to improve solvent resistance, reflectance, recording sensitivity, etc. of 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 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. 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 and a casting method and a method such as a sputtering method and a chemical vapor deposition method are used as in the recording layer, and the spin coating method is preferable among them.

The film 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.

Further, a label, a bar code or the like can be 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 dust from adhering.

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, in order to improve solvent resistance, reflectance, recording sensitivity, etc. of the reflective layer, a layer made of an inorganic material or a polymer is formed on 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 so that it can be recorded and reproduced, 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, 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 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 desired, 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 film 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.

Furthermore, 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 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 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 may 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 protective layer surface side, 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 base material should be transparent at the wavelengths of recording light and 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 spirally or concentrically formed 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 of 390 nm to 5 referred to in the present invention is used.
The lasers of 00 nm and 500 to 900 nm are not particularly limited, but for example, a dye laser capable of wavelength selection in a wide range of visible light region and a He-Ne laser (633n).
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.

[0242]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto.

Example 1 Among the compounds represented by the general formula (1), the exemplified compound (1
-1) 0.2 g was dissolved in 10 ml of 2,2,3,3-tetrafluoropropanol to prepare a dye solution. As the substrate, a disc-shaped substrate made of a polycarbonate resin having a continuous guide groove (track pitch: 0.74 μm) with an outer diameter of 120 mmφ and a thickness of 0.6 mm was used. A dye solution was spin-coated on this substrate at a rotation speed of 1500 min ⁻¹ and dried 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 sputtering power 2.5 kW and sputtering gas pressure 1.33 Pa.
(1.0 × 10 ^-2 Torr).

Furthermore, an ultraviolet curable resin "S
D-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, an ultraviolet curable resin "SD-30" is provided on the protective layer.
1 "(manufactured by Dainippon Ink and Chemicals, Inc.) was spin-coated, a polycarbonate resin substrate similar to the above-mentioned substrate was placed thereon, and the substrate was bonded by irradiating with ultraviolet rays to prepare an optical recording medium.

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

Recording frequency was 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 at a high C / N ratio. After recording, with the same evaluation device, reproduction laser power 0.6m
When reproduction was performed at W at a linear velocity of 9.0 m / s, the pits could be read. Moreover, although the reproduction was repeated, the pits could be read.

The wavelength 660 corresponding to the thickness of 0.6 mm
When a reproducing was performed at a linear velocity of 3.5 m / s using an evaluation machine equipped with a red semiconductor laser head of nm, the pits could be read. The reproduction was repeated, but the pit could be read.

Example 2 Instead of the exemplified compound (1-1), the exemplified compound (1-
Recording was performed in the same manner as in Example 1 except that 2) was used.
The pits were formed well and the pits could be read. Moreover, although the reproduction was repeated, the pits could be read.

Example 3 Among the compounds represented by the general formula (1), the exemplified compound (1
-3) is made of polycarbonate resin and has an outer diameter of 120 mm with continuous guide grooves (track pitch: 0.74 μm)
A film having a thickness of 70 nm was formed by a vacuum vapor deposition method on a disk-shaped substrate having a diameter of φ and a thickness of 0.6 mm.

Silver was sputtered on the recording layer by using a sputtering 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, the ultraviolet curable resin "S" is formed on the reflective layer.
D-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, an ultraviolet curable resin "SD-30" is provided on the protective layer.
1 "(manufactured by Dainippon Ink and Chemicals, Inc.) was spin-coated, a polycarbonate resin substrate having no guide groove similar to the above-mentioned substrate was placed thereon, and the substrate was bonded by irradiating with ultraviolet rays to prepare an optical recording medium.

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

Recording frequency was 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 at a high C / N ratio. After recording, with the same evaluation device, reproduction laser power 0.6m
When reproduction was performed at W at a linear velocity of 9.0 m / s, the pits could be read. Moreover, although the reproduction was repeated, the pits could be read.

Examples 4 to 11 Instead of the exemplified compound (1-3), the exemplified compound (1-
Recording was performed in the same manner as in Example 3 except that 4) to (1-11) were used. The pits were formed well and the pits could be read. Moreover, although the reproduction was repeated, the pits could be read.

Example 12 In recording / reproduction of the optical recording medium obtained by recording in Example 1, a linear velocity of 9.0 m / s was obtained using an evaluation machine equipped with a blue laser head having a wavelength of 403 nm and a numerical aperture of 0.65. Instead of recording at, wavelength 660n corresponding to 0.6mm thickness
Recording was performed at a linear velocity of 3.5 m / s by using an evaluation machine equipped with a red semiconductor laser head of m.

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

[0257]

[Chemical formula 22] An optical recording medium was prepared in the same manner as in Example 1 except that the chlorophyll (a) compound shown in was used, and recording and reproduction were carried out in the same manner as in Example 1. The C / N ratio was low and a good reproduced signal could not be obtained.

As described in Examples 1 to 12, the optical recording medium of the present invention is capable of high-density recording with a blue laser, and can be repeatedly reproduced with a blue laser or a red laser, and has excellent reproduction light. Shows stability.

From this fact, the recording layer containing the compound having the structure defined in the present invention is capable of signal recording by the laser beam selected from the wavelengths of 390 to 500 nm and / or 500 to 900 nm, and the optical recording medium of the present invention is used. The recording medium has a wavelength of 390 to 500 nm and / or a wavelength of 500 to 900.
A laser beam selected from nm can be used for an optical recording medium used for recording and reproduction.

[0260]

According to the present invention, by using the hydroporphyrin compound of the present invention as a recording layer, wavelengths of 390 to 390, which have received a great deal of attention as a high density optical recording medium.
Wavelength 500-700n used for recording and reproduction with 500nm laser, especially 400-410nm wavelength blue-violet laser, and recording of movies such as movies for 2 hours or more.
It is possible to provide a write-once type optical recording medium capable of recording and reproducing at m.

[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 Denmi Misawa             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company (72) Inventor Masakatsu Nakatsuka             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company F term (reference) 2H111 EA03 EA22 EA25 EA31 FB42                 4C050 PA02 PA06 PA20                 5D029 JA04 JB47                 5D090 AA01 BB03 DD02 KK06 LL01

Claims (13)

[Claims] 1. An optical recording medium having, as a recording layer on a substrate, an organic dye layer containing at least one kind of hydroporphyrin compound, wherein the hydroporphyrin compound is metal-complexed. The optical recording medium is characterized in that the substituents on the pyrroline ring and / or the pyrrole ring of the compound may be bonded to each other via a linking group to form a ring. 2. The hydroporphyrin compound may have a hydrocarbon group which may have a hetero atom, a halogen atom or a hydroxyl group as a substituent,
The optical recording medium according to claim 1, wherein the substituents on the pyrroline ring and / or the pyrrole ring of the compound may be bonded to each other via a linking group to form a ring. 3. The optical recording medium according to claim 2, wherein the hydroporphyrin compound is represented by the general formula (1). [Chemical 1] [In the formula, each of the rings A, B, C, and D independently represents a pyrroline ring or a pyrrole ring which may have the substituent, and at least one represents a pyrroline ring, and L,
X, Y and Z each independently represent a nitrogen atom or a methine group which may have the above substituent, and M may have 1 to 2 hydrogen atoms, the above substituent or a ligand. Represents a good metal atom, a metalloid atom, or an oxymetal atom. Each substituent of each ring of rings A, B, C and D may be bonded to each substituent of each ring of rings A, B, C and D via a linking group. ] 4. A hydroporphyrin compound is represented by the general formula
The optical recording medium according to claim 3, which is represented by (2). [Chemical 2] [In the formula, R¹~ R¹⁴Are each independently a hydrogen atom, or
R represents the substituent,¹~ R¹⁴Each substituent of
Even if they form a ring together through a substituent and a linking group,
Well, Q¹~ Q^FourAre each independently a nitrogen atom or C-
R¹⁵~ CR¹⁸(R ¹⁵~ R¹⁸Is R¹~ R¹⁴Any shown in
An optionally substituted methyl group represented by
R group⁹And R^Ten, R¹¹And R¹², And R¹³And R
¹⁴One or two of the combinations
May each directly form a single bond, and M¹Is 2
A hydrogen atom, a divalent to tetravalent substituent which may have a ligand, or
Represents an unsubstituted metal atom or a metalloid atom. ] 5. The optical recording medium according to claim 4, wherein the hydroporphyrin compound is represented by the general formula (3). [Chemical 3] [In the formula, R ^{19 to} R ³² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted A substituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aralkyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, Substituted or unsubstituted alkenyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aralkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkenyl thio, substituted amino group, a substituted or an unsubstituted acyloxy group, location each substituent of R ¹⁹ to R ³² is adjacent Through the group and the connecting group may form a ring together respectively, the Q ⁵ to Q ⁸ are each independently a nitrogen atom or ^{C-R 33 ~C-R 36} (R 33 ~R 36 is R ¹⁹ ~ R
³² shows represented by representing) one of the groups represents a methine group which may be substituted, R ²¹ and R ^22, R ²³ and R ^24,
And one or two of the combinations of R ²⁵ and R ²⁶
Each of the two combinations may directly form a single bond, and M ² represents two hydrogen atoms, a divalent non-substituted or ligand-containing metal atom, and a substituent-containing trivalent or tetravalent metal atom. Alternatively, it represents a semimetal atom or an oxymetal atom. ] 6. The optical recording medium according to claim 1, which is capable of recording and reproducing with respect to a laser beam selected from a wavelength range of 390 nm to 500 nm and / or a wavelength range of 500 nm to 900 nm. . 7. The optical recording medium according to claim 6, which is capable of recording and reproducing with respect to a laser beam selected from a wavelength range of 390 nm to 430 nm and / or a wavelength range of 630 nm to 690 nm. 8. The optical recording medium according to claim 7, which is capable of recording and reproducing with respect to a laser beam selected from a wavelength range of 400 nm to 410 nm. 9. A hydroporphyrin compound represented by the general formula (2). [Chemical 4] [In the formula, R ^{1 to} R ¹⁴ each independently represent a hydrogen atom, a hydrocarbon group which may have a hetero atom, a halogen atom or a hydroxyl group, and the respective substituents of R ^{1 to} R ¹⁴ are adjacent to each other. through a substituent and a linking group, they may form a ring together respectively, Q ¹ to Q ⁴ are each independently a nitrogen atom or ^{C-R 15 ~C-R 18} (R 15 ~R 18 is R ^{1 to} R ¹⁴ ) which represents an optionally substituted methine group represented by R ^{1 and} R ¹⁴ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , and R
Of the combinations of ¹³ and R ¹⁴ , one or two combinations may directly form a single bond, and M ¹
Represents two hydrogen atoms, a divalent to tetravalent substituted or unsubstituted metal atom which may have a ligand, or a metalloid atom. ] 10. The hydroporphyrin compound according to claim 9, which is represented by the general formula (3). [Chemical 5] [In the formula, R ^{19 to} R ³² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted A substituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aralkyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, Substituted or unsubstituted alkenyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aralkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkenyl thio, substituted amino group, a substituted or an unsubstituted acyloxy group, location each substituent of R ¹⁹ to R ³² is adjacent Through the group and the connecting group may form a ring together respectively, the Q ⁵ to Q ⁸ are each independently a nitrogen atom or ^{C-R 33 ~C-R 36} (R 33 ~R 36 is R ¹⁹ ~ R
³² shows represented by representing) one of the groups represents a methine group which may be substituted, R ²¹ and R ^22, R ²³ and R ^24,
And one or two of the combinations of R ²⁵ and R ²⁶
Each of the two combinations may directly form a single bond, and M ² is two hydrogen atoms, a divalent non-substituted or ligand-containing metal atom, and a substituent-containing trivalent or tetravalent metal atom. Alternatively, it represents a semimetal atom or an oxymetal atom. ] 11. The compound according to claim 9, wherein one or two of the combinations of R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , and R ¹³ and R ¹⁴ directly form a single bond. 12. The compound according to claim 11, wherein one or two of Q ^{1 to} Q ⁴ are nitrogen atoms. 13. The compound according to claim 11, wherein two of the combinations of R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , and R ¹³ and R ¹⁴ each form a direct single bond.