JP2005302272A - Optical information recording medium and its recording and reproducing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical information recording medium capable of obtaining signals having uniform and excellent contrast in the entire region of a recording region and to provide a recording and reproducing method using the optical information recording medium. <P>SOLUTION: The optical information recording medium having a substrate in which a recessed guide groove is formed and at least a reflection layer, a recording layer containing an organic dye and a surface protective layer which are successively layered on the substrate is characterized in that the reflection layer has a recessed part corresponding to the recessed guide groove in the substrate, the sectional shape of the recessed part in a direction crossing a track is a nearly reversely trapezoidal shape having an upper bottom longer than the lower bottom and a push-pull signal of the optical information recording medium is 0.25 to 0.60. The reflection layer preferably contains aluminum or an aluminum alloy. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a heat mode write-once type optical information recording medium (hereinafter also referred to as “optical recording medium” or “information recording medium”) capable of at least one of recording and reproducing information, and the The present invention relates to a recording / reproducing method using an optical information recording medium.

  2. Description of the Related Art Conventionally, a write-once type optical information recording medium (a write-once type optical disc, so-called CD-R) capable of recording information only once with a laser beam is known. In a typical structure, a recording layer containing an organic dye, a reflective layer, and a surface protective layer are laminated in this order on a transparent disk-shaped substrate. Information recording on this CD-R is performed by irradiating a laser beam in the near-infrared region (usually a laser beam having a wavelength of around 780 nm), and the irradiated portion of the recording layer absorbs the light and is localized. When the temperature rises, information is recorded by changing the optical characteristics of the portion due to physical or chemical changes (for example, generation of pits). On the other hand, reading (reproduction) of information is also performed by irradiating the CD-R with laser light having the same wavelength as the recording laser light, and the optical characteristics of the recording layer are changed (recording portion). This is done by detecting the difference in reflectance from the non-recorded part (unrecorded part).

  In recent years, an optical information recording medium having a higher recording density has been demanded. In response to such a demand, an optical disc called a recordable digital versatile disc (so-called DVD-R) has been proposed (see Non-Patent Document 1). This DVD-R is a transparent disk-shaped substrate having a narrow groove width (0.74 to 0.8 μm) in which the guide groove (pre-groove) for tracking the laser beam to be irradiated is less than half of the CD-R. Two discs with a recording layer containing at least an organic dye, a reflective layer, and a surface protective layer stacked in this order on top of each other, with the recording layer inside, or a disk-shaped protection with the same shape as this disc It has a structure in which the substrate is bonded with the recording layer inside. Recording and reproduction of information on this DVD-R is performed by irradiating visible laser light (usually laser light having a wavelength in the range of 630 nm to 680 nm), and recording with higher density than CD-R is possible. Is possible.

  Recently, networks such as the Internet and high-definition TV are rapidly spreading. Also, HDTV (High Definition Television) has started to be broadcast. Under such circumstances, a large-capacity recording medium capable of recording image information inexpensively and simply is required. The DVD-R plays a role as a large-capacity recording medium at present, but there is an increasing demand for larger capacity and higher density, and the development of a recording medium that can meet these requirements has been developed. is necessary. For this reason, development of a larger capacity recording medium capable of performing high-density recording with light having a shorter wavelength than that of the DVD-R is underway.

  Therefore, in an optical information recording medium having at least a reflective layer and a recording layer containing an organic dye on a substrate, information is recorded and reproduced by irradiating a laser beam having a wavelength of 530 nm or less from the recording layer side toward the reflective layer side. A number of recording / reproducing methods have been proposed (see Patent Documents 1 to 15). In these methods, a recording layer containing an organic dye such as a porphyrin compound, an azo dye, a metal azo dye, a quinophthalone dye, a trimethine cyanine dye, a dicyanovinylphenyl skeleton dye, a coumarin compound, or a naphthalocyanine compound is provided. Information is recorded and reproduced by irradiating the optical disc with blue (wavelength 430 nm, 488 nm) or blue-green (wavelength 515 nm) laser light.

By the way, the recordable type and the erasable optical information recording medium are generally prepits for information such as a track groove for recording, erasing, and reproducing information, an address for data management, and a format for a synchronization signal. (Hereinafter, information preliminarily formed on the substrate including these track grooves and prepits may be referred to as “preformat”).
As a method for forming a recording layer in the optical information recording medium, for example, a method using a vapor deposition method such as vapor deposition or sputtering, or a wet coating method is known. Among these, the wet coating method is a method attracting attention because it can reduce the cost of forming the recording layer. However, when the recording layer is provided on the substrate on which the preformat has been formed by the wet coating method, it is difficult to form the coating film uniformly because the coating liquid is accumulated in the concave portions of the substrate. For example, when a recording layer containing an organic dye is provided by a wet coating method, the thickness of the recording layer differs between the substrate surface and the substrate recess, and as a result, the reflectance differs between the substrate surface and the substrate recess. There is.

  At present, in the optical disc described in the above-mentioned prior art, further improvement of the reflectance is studied by using silver (Ag) for the reflective layer. However, when silver (Ag) is used for the reflective layer, Since (Ag) is expensive, the cost becomes high, which is a big problem when mass-producing such an optical disc. In addition, depending on the formation conditions, there is a problem that the reflective layer made of silver (Ag) has low resistance to corrosion.

  Therefore, an inexpensive and high-capacity optical information recording medium capable of obtaining a signal having a uniform and excellent contrast over the entire recording area has not yet been obtained, and the prompt provision thereof is desired. It is.

JP-A-4-74690 JP-A-7-304256 JP-A-7-304257 JP-A-8-127174 Japanese Patent Laid-Open No. 11-53758 JP-A-11-334204 JP 11-334205 A Japanese Patent Laid-Open No. 11-334206 JP 11-334207 A JP 2000-43423 A JP 2000-108513 A JP 2000-113504 A JP 2000-149320 A JP 2000-158818 A JP 2000-228028 A "Nikkei New Media" separate volume "DVD", published in 1995

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention provides an optical information recording medium capable of obtaining a signal having a uniform and excellent contrast over the entire recording area and achieving a higher recording density, and a recording / reproducing method using the optical information recording medium. The purpose is to do.

Means for solving the problems are as follows. That is,
<1> An optical information recording medium in which a substrate on which a concave guide groove is formed, and at least a reflective layer, a recording layer containing an organic dye, and a surface protective layer are laminated on the substrate in this order. The layer has a recess corresponding to the concave guide groove in the substrate, the cross-sectional shape in the direction crossing the track of the recess is a substantially inverted trapezoid whose upper base is longer than the lower base, and the push in the optical information recording medium An optical information recording medium having a push-pull signal of 0.25 to 0.60. In the optical information recording medium according to <1>, the cross-sectional shape in the direction in which the reflective layer crosses the track of the concave portion corresponding to the concave guide groove in the substrate has a substantially inverted trapezoidal shape in which the upper base is longer than the lower base. Thus, the generation of a distorted signal waveform can be suppressed. That is, in the conventional CD-R and DVD-R, the reflective layer is formed by laminating the reflective layer on the dye layer laminated on the substrate. As a result, the push-pull signal was uneven. On the other hand, in the present invention, since the reflective layer is formed on the substrate, it can be formed in a substantially inverted trapezoidal shape. As a result, the generation of a distorted signal waveform is suppressed, a signal with excellent contrast can be obtained, and the non-uniformity of the contrast of the reproduction signal in the central portion and the peripheral portion of the recording area of the optical information recording medium is suppressed. be able to.

<2> The optical information recording medium according to <1>, wherein at least one of recording and reproduction is performed by irradiating a laser beam having an oscillation wavelength of 500 nm or less from the surface protective layer side.
<3> The cross-sectional shape of the interface between the substrate and the reflective layer in the direction crossing the track of the recess in the reflective layer is a substantially inverted trapezoid, and the length (CL) of the upper base of the substantially inverted trapezoid is 90 to 200 nm. The optical information recording medium according to any one of <1> to <2>.
<4> The cross-sectional shape of the interface between the substrate and the reflective layer in a direction crossing the track of the recess in the reflective layer is a substantially inverted trapezoid, and the length (BL) of the bottom of the substantially inverted trapezoid is 25 nm or more. The optical information recording medium according to any one of <1> to <3>.
<5> The length (BL) of the bottom of the substantially inverted trapezoidal shape satisfies the relationship of the following formula, BL ≧ TP / 13 (where TP represents a track pitch (nm)): An optical information recording medium.
<6> The cross-sectional shape of the interface between the reflective layer and the recording layer in the direction across the track of the concave portion in the reflective layer is a substantially inverted trapezoid, and the length (UL) of the bottom of the substantially inverted trapezoid is 10 nm or more. The optical information recording medium according to any one of <1> to <5>.
<7> The length (UL) of the bottom of the substantially inverted trapezoidal shape satisfies the relationship of the following formula, UL ≧ TP / 32 (where TP represents the track pitch (nm)): An optical information recording medium.
<8> In any one of <1> to <7>, an angle θ between a surface connecting the upper base and the lower base in the trapezoidal portion of the concave portion of the reflective layer, and the upper base and the lower base is 60 ° or less. This is an optical information recording medium.
In the optical information recording medium according to any one of <3> to <8>, a reflectance difference obtained by a film thickness difference between a convex portion and a concave portion of a reflective layer when the preformat is scanned with a light beam. The difference in reflectance obtained as a result of the comprehensive action of the phase difference obtained by the step between the concave portion and the convex portion and the diffraction of light on the concave slope is obtained as much as possible and stably obtained. .

  <9> The optical information recording medium according to any one of <1> to <8>, wherein the reflective layer contains either aluminum or an aluminum alloy. In the optical information recording medium according to <9>, the reflective layer contains either aluminum or an aluminum alloy, and the cost can be reduced by selecting a cross-sectional shape of the reflective layer that provides good contrast. , Has excellent recording characteristics.

<10> The optical information recording medium according to any one of <1> to <9>, wherein the reflective layer has a thickness of 20 to 200 nm.
<11> The optical information recording medium according to any one of <1> to <10>, wherein the reflectance of the organic dye in the recording layer is 8% or more at a wavelength of light used for at least one of recording and reproduction. is there.

ただし、前記構造式中、中心金属Ｍは、Ｃｕ、ＶＯ、Ｎｉ、Ｈ、Ｚｎ、Ｐｄ、Ｃｄ、Ｃｏ、及びＦｅから選択されるいずれかを表す。Ｒは、有機置換基を表す。
＜１４＞ 中心金属Ｍは、ＶＯ、Ｚｎ、Ｐｄ、及びＣｏから選択されるいずれかを表し、Ｒは、Ｃ_６Ｈ_５−（ＣＦ_３）_２Ｃ−Ｏ−を表す前記＜１３＞に記載の光情報記録媒体である。
＜１５＞ 中心金属Ｍは、Ｃｕ、ＶＯ、Ｎｉ、Ｈ、Ｚｎ、Ｐｄ、Ｃｄ、Ｃｏ、及びＦｅから選択されるいずれかを表し、Ｒは、下記構造式から選択されるいずれかを表す前記＜１３＞に記載の光情報記録媒体である。

＜１６＞ 中心金属Ｍは、下記構造式で表される置換基であり、Ｒは、−ＯＣＨ_２ＣＦ_２ＣＦ_２Ｈである前記＜１３＞に記載の光情報記録媒体である。

ただし、前記構造式中、Ｃｐは、Ｆｅ（Ｃ_５Ｈ_５）_２を表す。
＜１７＞ 中心金属Ｍは、Ｃｕを表し、Ｒは、−ＳＯ_２Ｃ_４Ｈ_９を表す前記＜１３＞に記載の光情報記録媒体である。 <12> The optical information recording medium according to any one of <1> to <11>, wherein the organic dye is a phthalocyanine dye.
<13> The optical information recording medium according to <12>, wherein the phthalocyanine dye is a compound represented by the following structural formula.

However, in the structural formula, the central metal M represents one selected from Cu, VO, Ni, H, Zn, Pd, Cd, Co, and Fe. R represents an organic substituent.
<14> The central metal M represents any one selected from VO, Zn, Pd, and Co, and R represents C ₆ H ₅ — (CF ₃ ) ₂ C—O—. This is an optical information recording medium.
<15> The central metal M represents any one selected from Cu, VO, Ni, H, Zn, Pd, Cd, Co, and Fe, and R represents any one selected from the following structural formulas <13> The optical information recording medium according to <13>.

<16> The optical information recording medium according to <13>, wherein the central metal M is a substituent represented by the following structural formula, and R is —OCH ₂ CF ₂ CF ₂ H.

In Structural Formula, Cp represents _{Fe (C 5 H 5) 2} .
<17> The optical information recording medium according to <13>, wherein the central metal M represents Cu and R represents —SO ₂ C ₄ H ₉ .

<18> The optical information recording medium according to any one of <1> to <11>, wherein the organic dye is an azo dye.
<19> The optical information recording medium according to <18>, wherein the azo dye is represented by the following structural formula.

ただし、前記一般式（Ｉ）及び（ＩＩ）中、Ａは置換基を有していてもよい芳香環を表し、ＢはＯＨ以外の置換基を有していてもよい芳香環を表す。ｎは１〜３の整数、ｍは２〜６の整数を表す。Ｌは置換されてもよい２価の連結基または単結合を表す。ＶはＬ以外に置換基を有していてもよい芳香環を表す。

ただし、前記一般式（ＩＩＩ）及び（ＩＶ）中、Ｒ^１及びＲ^２は互いに同一であっても異なっていてもよい置換基を表し、ｐ及びｑは０乃至３の整数を表す。ｍは２〜６の整数を表す。Ｌは置換されてもよい２価の連結基または単結合を表す。ＶはＬ以外に置換基を有していてもよい芳香環を表す。

ただし、前記一般式（Ｖ）中、Ｒ^１及びＲ^２は互いに同一であっても異なっていてもよい置換基を表し、ｐ及びｑは０乃至３の整数を表す。ｍは２または３の整数を表す。Ｖは置換基を有していてもよい芳香環を表す。 <20> The optical information recording medium according to any one of <1> to <11>, wherein the organic dye is represented by at least one of the following structural formulas (I) to (V).

However, in said general formula (I) and (II), A represents the aromatic ring which may have a substituent, and B represents the aromatic ring which may have substituents other than OH. n represents an integer of 1 to 3, and m represents an integer of 2 to 6. L represents a divalent linking group or a single bond which may be substituted. V represents an aromatic ring which may have a substituent other than L.

However, in said general formula (III) and (IV), R < ¹ > and R < ² > represents the substituent which may mutually be same or different, p and q represent the integer of 0-3. m represents an integer of 2 to 6. L represents a divalent linking group or a single bond which may be substituted. V represents an aromatic ring which may have a substituent other than L.

However, in said general formula (V), R < ¹ > and R < ² > represents the substituent which may mutually be same or different, p and q represent the integer of 0 thru | or 3. m represents an integer of 2 or 3. V represents an aromatic ring which may have a substituent.

<21> The light according to any one of <1> to <20>, wherein the track pitch on the substrate is 200 to 400 nm, the groove depth of the guide groove is 10 to 150 nm, and the half width of the guide groove is 50 to 250 nm. An information recording medium.
<22> The optical information recording medium according to any one of <1> to <21>, wherein the transmittance of the surface protective layer is 80% or more with respect to laser light used for at least one of recording and reproduction. is there.

  <23> At least one of information recording and reproduction by irradiating laser light having an oscillation wavelength of 500 nm or less from the surface protective layer side in the optical information recording medium according to any one of <1> to <22>. The recording / reproducing method is characterized in that In the recording / reproducing method according to <23>, laser light having an oscillation wavelength of 500 nm or less is irradiated from the surface protective layer side in the optical information recording medium of the present invention. As a result, a signal having a uniform and excellent contrast in the entire recording area can be obtained, and a higher recording density can be achieved. Here, the contrast means the relationship between the concave guide groove which is a dark part with little reflection of laser light and the land which is a bright part with much reflection of the laser light, and excellent contrast is Means good tracking.

  According to the present invention, various problems in the prior art can be solved, and the reflective layer contains either aluminum or an aluminum alloy, and the cost can be reduced by selecting the cross-sectional shape of the reflective layer that provides good contrast. An optical information recording medium having excellent recording characteristics can be provided.

(Optical information recording medium)
In the optical information recording medium of the present invention, a substrate on which a concave guide groove (groove) is formed, and at least a reflective layer, a recording layer containing an organic dye, and a surface protective layer are laminated on the substrate in this order. It has a barrier layer, an adhesive layer, and other layers as required.
In this case, the optical information recording medium performs at least one of recording and reproduction by irradiating a laser beam having an oscillation wavelength of 500 nm or less from the surface protective layer side.

The optical information recording medium needs to have a push-pull signal of 0.25 to 0.60, preferably 0.5 to 0.6. If the push-pull signal is less than 0.25, the ratio between the signal obtained from the groove and the signal obtained from the land is small, so that the position is not accurately known and tracking cannot be performed. If it exceeds 0.60, the voltage value that can be detected by the detector will be exceeded, and a clean sine wave cannot be obtained, so tracking may not be applied.
In this case, the push-pull signal is obtained by, for example, using the optical disc evaluation machine (DDU1000, Pulstec Industrial Co., Ltd.) as the signal of the peak 11 and valley 12 of the signal crossing the track in a state where the optical information recording medium is focused. And can be calculated from the following formula, push-pull signal = (l1−l2) / (l1 + l2).

The reflective layer has a concave portion corresponding to a concave guide groove (pre-groove) in the substrate, and a cross-sectional shape in a direction crossing the track of the concave portion is a substantially inverted trapezoid whose upper base is longer than the lower base.
Here, FIG. 1 and FIG. 2 are schematic cross-sectional views in the track crossing direction of the optical information recording medium according to one embodiment of the present invention. In FIG. 1, 1 is an optical information recording medium, 2 is a substrate, and a concave preformat, for example, a tracking track 7 is formed on the surface thereof. A reflective layer 3 is formed on the surface of the substrate 2 on which the preformat is formed by sputtering or vapor deposition, a recording layer 4 is formed on the reflective layer by wet coating, and a barrier layer 5 and an adhesive layer are further formed. 6, the surface protective layer 8 is laminated in this order.

  FIG. 2 is an enlarged partial cross-sectional view of the optical information recording medium of FIG. As shown in FIG. 2, the concave reflective layer 3 of the optical information recording medium 1 has a trapezoidal cross-sectional shape in the cross-track direction, and the trapezoidal portion is the length (BL) of the bottom base of the substrate / reflective layer interface. The length of the upper base of the substrate / reflective layer interface (CL), and the lower base (UL) of the trapezoidal portion of the reflective layer / recording layer interface is a so-called substantially inverted base in which the length of the lower base is shorter than the upper base. Shape. Such a substantially inverted trapezoidal shape suppresses the generation of a distorted signal waveform. As a result, an excellent contrast signal can be obtained, and the central and peripheral portions of the recording area of the optical information recording medium can be obtained. Thus, it is possible to suppress non-uniformity of the contrast of the reproduction signal.

  The shape of the preformat concave portion is the angle (θ) of the slope of the trapezoidal portion, the depth (d) of the concave portion, that is, the depth (d1) of the substrate / reflective layer interface and the depth of the reflective layer / recording film interface ( d2) and further defined by the length (UL) of the lower base, the length (BL) of the lower base, and the length (CL) of the upper base. These control the contrast of the preformat reproduction signal. That is, for example, the reproduction light beam of the reflection layer formed on the slope of the trapezoidal part diffracts the reproduction light when traversing the preformat recess. Therefore, the angle (θ) defines the degree of diffraction.

  Furthermore, the ratio of the width UL of the rectangular portion to the width BL of the recess defines the ratio of the region where the reflective layer has the lowest reflectance in the preformat recess, and this ratio is also the preformat. This affects the contrast of the reproduction signal.

  Therefore, the angle (θ), depth (d), and width (UL, BL, CL) of the concave portions are the film thickness differences between the convex portions and the concave portions of the reflective layer when the preformat is scanned with a light beam. The difference in reflectance obtained by the above and the phase difference obtained by the step between the concave portion and the convex portion, and the reflectance change obtained as a result of the comprehensive action of factors such as light diffraction on the concave slope, are as large as possible. Is preferably set to a value that can be obtained stably. For example, the widths BL, UL, and CL of the preformat recesses preferably satisfy the following conditions in order to obtain a high-quality optical information recording medium.

The cross-sectional shape of the interface between the substrate and the reflective layer in the direction crossing the track of the recess in the reflective layer is a substantially inverted trapezoidal shape, and the length (CL) of the upper base of the generally inverted trapezoidal shape is preferably 90 to 200 nm. 140 to 180 nm is more preferable.
The cross-sectional shape of the interface between the substrate and the reflective layer in the direction across the track of the recess in the reflective layer is a substantially inverted trapezoidal shape, and the length (BL) of the bottom of the substantially inverted trapezoidal shape is preferably 25 nm or more, 85 to 150 nm is more preferable.
The length (BL) of the bottom of the substantially inverted trapezoidal shape preferably satisfies the relationship of the following formula, BL ≧ TP / 13 (where TP represents a track pitch (nm), preferably 200 to 400 nm). BL ≧ TP / 3.7 is more preferable.
The cross-sectional shape of the interface between the reflective layer and the recording layer in the direction crossing the concave track in the reflective layer is a substantially inverted trapezoid, and the length (UL) of the bottom of the substantially inverted trapezoid is preferably 10 nm or more. 85 to 120 nm is more preferable.
The length (UL) of the bottom of the substantially inverted trapezoidal shape preferably satisfies the relationship of the following formula, UL ≧ TP / 32 (where TP represents a track pitch (nm), preferably 200 to 400 nm). UL ≧ TP / 3.7 is more preferable.

In addition, the width (CL) of the preformat recess differs depending on the configuration of the recording / reproducing system, for example, the configuration of the tracking system, etc. It is preferable that the relationship of the following formula 1 is satisfied with the spot diameter (φ) of the recording / reproducing light beam.
<Formula 1>
0.23 <(CL / spot diameter (φ)) <0.52
For example, when the spot diameter (φ) of the light beam on the optical information recording medium is 400 ± 15 nm, the width (CL) of the preformat recess is preferably 88.55 to 215.8 nm, more preferably 100 to 200 nm. 140-180 nm is still more preferable.

The angle (θ) between the surface connecting the upper base and the lower base of the trapezoidal portion of the concave portion of the reflective layer and the upper and lower bases (the angle (θ) formed between the slope of the trapezoidal portion and the surface of the substrate) is 60 ° or less, preferably 15 to 60 °, more preferably 30 to 60 °, and particularly preferably 40 to 60 °. When the preformat is scanned with a light beam by setting the angle (θ) within the above range, the reflection layer has the lowest reflectivity, although it cannot be defined unconditionally due to interference with the recording layer. The film thickness shown can be formed stably, and the shape of the reflective layer formed on the slope of the trapezoidal part can sharply reduce the reflectance of the light beam from the preformat. It can be a shape. As a result, high contrast can be secured stably, and this is advantageous when the track is pulled. The angle (θ) formed in FIG. 2 is the angle (θ ₂ ) between the surface connecting the upper base and the lower base and the line connecting the contact points of the upper base, and the surface connecting the upper base and the lower base. It means the angle (θ ₁ ) made with the line connecting the contact point with the bottom.

  Further, depending on the angle (θ) of the hypotenuse of the trapezoidal portion, for example, when the angle (θ) is 15 to 60 °, the depth (d) is 5 to 80 nm, and further the angle (θ) is 30 to 60. When the angle is 20 to 60 nm, especially when the angle (θ) is 40 to 60 ° and 40 to 60 nm, and the angle (θ) is within the above range, the contrast can be improved.

Here, FIG. 1 is a schematic sectional view showing an example of the optical information recording medium of the present invention. In this optical information recording medium, a concave preformat, for example, a tracking track 7 is formed on the surface of a transparent substrate 2. A reflective layer 3, a recording layer 4, a barrier layer 5, and an adhesive layer 6 are provided on the substrate 2, and finally a surface protective layer 8 is bonded.
Hereinafter, each layer will be specifically described.

-Board-
There is no restriction | limiting in particular as said board | substrate 2, According to the objective, it can select suitably, For example, Glass; Acrylic resin, such as a polycarbonate and a polymethylmethacrylate; Vinyl chloride type, such as a polyvinyl chloride and a vinyl chloride copolymer Resin; Epoxy resin; Amorphous polyolefin; Polyester; Transparent resin material such as polymethylpentene and amorphous polyolefin (preferably a glass transition temperature (Tg) of 100 to 200 ° C.), metal such as aluminum; These may be used in combination. In addition, these are formed into a desired shape, and a desired preformat pattern such as address information is transferred to one side thereof, or the address information and the like are desired on one side of a transparent ceramic plate such as glass formed in a desired shape. Any transparent substrate belonging to publicly known ones such as those in close contact with a transparent resin layer to which the preformat pattern is transferred can be used.
Among these, polycarbonate and amorphous polyolefin are preferable from the viewpoint of moisture resistance, dimensional stability and price, and polycarbonate is particularly preferable.
There is no restriction | limiting in particular in the thickness of the said board | substrate, According to the objective, it can select suitably, 0.8-1.4 mm is preferable.

  The substrate is formed in a disk shape having a center hole at the center. In addition, the said board | substrate can be shape | molded by well-known methods, such as injection molding or extrusion molding.

The preformat pattern includes at least a beam guide for causing a reproducing laser beam to follow a recording track. For this purpose, a concave or convex embossed pit method, or a wobble method that modulates the width of the groove or land according to information is possible. As the wobble method, a method of meandering one or both side surfaces of the inner peripheral side or the outer peripheral side of the groove portion can be adopted.
In FIG. 1 and FIG. 2, the beam guide portion is constituted by a guide groove formed concentrically or concentrically with the center hole, and prepits such as address pits and clock pits are formed along the guide grooves. Is formed.
When the prepits are formed on the guide grooves, the guide grooves and the prepits are formed at different depths so that they can be discriminated optically. When prepits are formed between adjacent guide grooves, they can be formed to the same depth.

The pregroove is preferably formed directly on the substrate when a resin material such as polycarbonate resin is injection molded or extruded. The pregroove may be formed by providing a pregroove layer. As a material for the pregroove layer, for example, a mixture of at least one monomer (or oligomer) of monoester, diester, triester and tetraester of acrylic acid and a photopolymerization initiator can be used.
The pre-groove layer is formed by, for example, applying a mixed solution of the above acrylate ester and a polymerization initiator on a precisely made master (stamper), and further, mounting a substrate on the coating solution layer. After being placed, the coating layer is cured by irradiating ultraviolet rays through the substrate or the mother die to fix the substrate and the coating layer. Subsequently, it can obtain by peeling a board | substrate from a mother mold.
There is no restriction | limiting in particular in the layer thickness of the said pre-groove layer, According to the objective, it can select suitably, 0.01-100 micrometers is preferable and 0.05-50 micrometers is more preferable.

  In order to achieve a higher recording density, the substrate 2 is preferably a substrate on which a pre-groove having a narrower track pitch is formed compared to a CD-R or DVD-R. The track pitch of the pregroove of the substrate is preferably 200 to 400 nm, and more preferably 250 to 350 nm. Further, the groove depth of the guide groove is preferably 10 to 150 nm, more preferably 20 to 100 nm, and still more preferably 30 to 80 nm. Moreover, 50-250 nm is preferable and the half width of a guide groove has more preferable 100-200 nm.

-Reflective layer-
There is no restriction | limiting in particular as a material used for the said reflection layer 3, According to the objective, it can select suitably, For example, metals, such as aluminum, silver, copper, or an alloy which has these as a main component can be used. . Conventional reflective layers generally use silver, gold, or alloys based on these alloys, but in the present invention, they are less expensive than silver (Ag) or gold (Au). It is preferable to use aluminum or an aluminum alloy.
The reflective layer made of aluminum or an aluminum alloy preferably has a reflectance with respect to laser light of 50% or more, more preferably 60% or more, and still more preferably 80% or more.

As the aluminum or aluminum alloy used in the reflective layer, pure aluminum having a purity of 99.0% or more used as industrial aluminum, or an alloy containing aluminum as a main component and containing a trace amount of foreign elements is preferable. From this viewpoint, pure aluminum is preferable.
The trace amount of foreign elements contained in the aluminum alloy preferably contains one or more elements selected from those described in the periodic table of elements in the range of 0.1 to 10% by mass. Examples of the different elements contained in the aluminum alloy include silicon (Si), iron (Fe), copper (Cu), manganese (Mn), magnesium (Mg), chromium (Cr), zinc (Zn), zirconium ( Zr), titanium (Ti), vanadium (V), nickel (Ni), bismuth (Bi), silver (Ag), gold (Au), platinum (Pt), and the like. Among these, 1% by mass or less of Si, Mg, Ag, Au, Pt, Cu and the like that do not reduce the reflectance are preferable. Further, as reflective layer materials, Fe, Ti, Zr, Ta, Cr, Mo, W, Ni, Rh, Pd, Pt, Cu, Ag, Au, Zn, In, Si, Ge, Te, Sn, Bi, Sb and It is preferable to contain at least one element selected from Tl, or an oxide, nitride, carbide, or sulfide thereof. Specific examples of the oxide include ZnS, SiO, SiN, AlN, ZnO—SiO ₂ , SiC, ZnO ₂ , and the like.

  The aluminum and aluminum alloy can be formed as a reflective layer on the substrate by vapor deposition, sputtering, or ion plating. Among these, the reflective layer is preferably formed by sputtering.

Hereinafter, a method for forming the reflective layer of the optical information recording medium of the present invention using sputtering will be described in detail.
Argon (Ar) is preferably used as the discharge gas used for the sputtering. The sputtering conditions are preferably an Ar flow rate of 1 to 50 sccm, a power of 0.5 to 10 kW, and a film formation time of 0.1 to 30 seconds, and an Ar flow rate of 3 to 20 sccm, a power of 1 to 7 kW, and a film formation time of 0.5. The range of ˜15 seconds is more preferable, and the range of Ar flow rate 4 to 10 sccm, power 2 to 6 kW, and film formation time 1 to 5 seconds is more preferable. As for the sputtering conditions, at least one of Ar flow rate, power, and film formation time is preferably in the above range, more preferably two or more are in the above range, and all the conditions are in the above range. It is particularly preferred. By forming the reflective layer under such sputtering conditions, the reflectance and corrosion resistance can be further improved, and an optical information recording medium having excellent recording characteristics can be obtained.
The film forming rate of the reflective layer is preferably 6 to 95 nm / s, more preferably 7 to 90 nm / s, and still more preferably 8 to 80 nm / s. When the film formation rate is less than 6 nm / s, oxygen easily enters during sputtering, and the reflectivity may decrease due to oxidation, and the corrosion resistance of the reflective layer may decrease, exceeding 95 nm / s. If the temperature rises, the substrate may be warped.
It is also possible to apply a technique for increasing the reflectivity of the reflective layer by changing the degree of vacuum in the vacuum chamber (for example, about 10 to 5 torr) to form a film having a different density or crystallization state. it can.

  There is no restriction | limiting in particular in the layer thickness of the said reflection layer, Although it can select suitably according to the objective, 20-200 nm is preferable, 30-180 nm is more preferable, 35-160 nm is still more preferable. If the layer thickness is less than 20 nm, there may be a problem that a desired reflectance cannot be obtained, a problem that the reflectance decreases during storage, and a problem that the recording amplitude cannot be sufficiently obtained. On the other hand, if the layer thickness exceeds 200 nm, the surface shape may be rough, and the reflectance may decrease.

-Recording layer-
The recording layer 4 is preferably selected from a material and a film thickness so that the reflectance at the recording / reproducing laser beam wavelength is 4% or more, particularly 8% or more. If the reflectance is less than 4%, a problem may occur in tracking or the like, and good recording may be difficult. Here, the reflectance means an absolute reflectance measured by using a UV-2500 (PC) SGLP manufactured by Shimadzu Corporation, for example, by forming a recording layer on a quartz substrate by a spin coat method. .

  The recording layer contains at least an organic dye, a resin capable of dispersing the organic dye, a binder, a browning inhibitor, and further contains other components as necessary.

  The organic dye is not particularly limited and may be appropriately selected depending on the intended purpose. The dye handbook (Kodansha, published on March 20, 1986, first edition, editor: Nobu Okawara, et al.) Nos. 547 to 550 Examples include materials exhibiting absorption in the wavelength range of 381 to 435 nm and derivatives thereof, such as polymethine dyes, anthraquinone dyes, dioxidin dyes, triphenodithiazine dyes, phenanthrene dyes, and cyanine dyes. Dye, dicarbocyanine dye, phthalocyanine dye, naphthalocyanine dye, merocyanine dye, pyrylium dye, porphyrin dye, xanthene dye, triphenylmethane dye, azulene dye, metal-containing azo dye, azo dye , Azo dyes, squarylium dyes, polyene dyes, base stills Dyes, formazan chelate dyes, croconium dyes, indigoid dyes, methine dyes, sulfide dyes, methanedithiolate dyes, or derivatives thereof, among these, cyanine dyes or derivatives thereof Dicarbocyanine dyes or derivatives thereof, phthalocyanine dyes or derivatives thereof, naphthalocyanine dyes or derivatives thereof, azo dyes or derivatives thereof are particularly preferably used. A dye material to which various quenchers such as an aminium dye are added can also be used.

Examples of the phthalocyanine dye or derivatives thereof include the following metal phthalocyanine dyes (hereinafter sometimes referred to as “MPc”). In addition, since the same code | symbol used in many formulas represents the same substituent, it decided to describe only once.
MPc-Rn (R = alkyl group, cycloalkyl group, oxaalkyl group), MPc- (XR) n (X = O, S, Se, Te), MPc- (Ar) n (Ar = aryl group), MPc - (YAr) n (Y = O, S, Se), MPc- (SO 3 M) n (M = H, metal _{ions), MPc- (SO 2 NR 1} R 2) n (R 1, R 2 = H, an alkyl group, an aryl group), MPc- (COOM) n ( M = metal _{ion), MPc- (COZ) n (} Z = R, OR, NR 1 R 2), MPc- (NR 1 R 2) n , MPc- (NR ₁ -COR ₂ ) n, MPc- (SiNR ₁ R ₂ R ₃ ) n (R ₃ = alkyl group, aryl group), MPc- (NO ₂ ) n, MPc-Fn, and the like.

  Examples of the central metal M of the dye include Li, Na, K, Be, Mg, Ca, Ba, Al, Ga, In, Ti, Si, Ge, Sn, Pb, As, Sb, Sc, Y, and La. , Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, Pa, U, Np, Am, Ti, Zr, Hf, V, VO, Nb , Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Ir, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, and the like.

Among these, those represented by the following structural formula are preferable.

  In the structural formula, the central metal M is preferably Cu, VO, Ni, H, Zn, Pd, Cd, Co, or Fe. Examples of R include those shown in Tables 1 to 7 below. However, M of the compound shown in Table 7 has an organic substituent as described in the table. In Tables 1 to 7, (1/4) means that one of four Rs is a substituent, and similarly (2/4) (3/4) (4/4) means that 2 to 4 are the substituents. In addition, (1/3) means that one of the four Rs is hydrogen and one of the remaining three Rs is a substituent, and similarly (2/3) ) Means that two are the substituents. Moreover, what does not have the above display means that all four R are the substituents.

Among these, the following phthalocyanines, among the above phthalocyanines, have a high degree of modulation and can achieve good recording.
The central metal M is any one of VO, Zn, Pd, and Co, and four Rs are C ₆ H ₅ — (CF ₃ ) ₂ C—O—.
The central metal M is any one of Cu, VO, Ni, H, Zn, Pd, Cd, Co, and Fe, and four Rs are represented by any one selected from the following structural formula.

中心金属Ｍが下記構造式で表れる置換基であり、４個のＲが−ＯＣＨ_２ＣＦ_２ＣＦ_２Ｈである。

The central metal M is a substituent represented by the following structural formula, and four Rs are —OCH ₂ CF ₂ CF ₂ H.

ただし、前記構造式中、Ｃｐは、Ｆｅ（Ｃ_５Ｈ_５）_２を表す。

In Structural Formula, Cp represents _{Fe (C 5 H 5) 2} .

The central metal is M and four Rs are —SO ₂ C ₄ H ₉ .
The central metal M is any one of VO, Zn, Pd, and Co, and four Rs are represented by the following structural formula.

  In addition, porphyrin dyes represented by the following formulas also have a high degree of modulation and can achieve good recording. The film thickness is preferably 10 to 100 nm, and if it is thinner than 10 nm, the absorptance decreases, which is a problem. Further, when the film thickness exceeds 100 nm, good recording may not be achieved.

ただし、各式中、Ｘ_１〜Ｘ_２はそれぞれ独立に窒素原子又はＣＨ基を示し、Ｒ１からＲ８はそれぞれ独立に、水素原子、ハロゲン原子、炭素数１〜１２の置換又は無置換のアルキル基、炭素数６〜２０の置換又は無置換のアリール基、水酸基、置換又は無置換のアルコキシ基、置換又は無置換のアリールオキシ基、アミノ基又はアルキルアミノ基、ニトロ基、シアノ基、カルボキシ基、置換又は無置換のカルボン酸エステル基、置換及び無置換のカルボン酸アミド基、アルキルチオ基、アリールチオ基、スルホン酸基、置換又は無置換のスルホン酸エステル基、置換又は無置換のスルホンアミド基、置換又は無置換のシリル基及びシロキシ基から選択される。また中心金属Ｍは、遷移金属を示し、電荷を有してカチオン塩構造をとっても良い。

However, in each formula, X < ₁ > -X < ₂ > shows a nitrogen atom or CH group each independently, R <1> -R <8> is each independently a hydrogen atom, a halogen atom, a C1-C12 substituted or unsubstituted alkyl group. A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, an amino group or an alkylamino group, a nitro group, a cyano group, a carboxy group, Substituted or unsubstituted carboxylic acid ester group, substituted and unsubstituted carboxylic acid amide group, alkylthio group, arylthio group, sulfonic acid group, substituted or unsubstituted sulfonic acid ester group, substituted or unsubstituted sulfonamido group, substituted Or, it is selected from an unsubstituted silyl group and a siloxy group. The central metal M represents a transition metal and may have a charge and a cation salt structure.

  In particular, when at least one compound represented by the following general formula (1) is contained, an excellent effect is exhibited. Then, recording / reproduction can be performed with respect to a recording laser wavelength and a reproduction laser wavelength selected from wavelengths of 300 nm to 500 nm and / or 500 nm to 700 nm. Above all, to obtain a good C / N ratio for a recording laser wavelength and a reproducing laser wavelength selected from a wavelength range of 400 nm to 500 nm and / or 600 nm to 700 nm, and further from a wavelength range of 339 nm to 435 nm and / or 635 nm to 670 nm. In addition, the write-once type optical recording medium is capable of providing high-quality signal characteristics with good reproduction light stability.

ただし、前記一般式（１）中、環Ａ、Ｂ、Ｃ、Ｄはそれぞれ独立に置換基を有していてもよいピロール環骨格を表し、Ｘ、Ｙ、Ｚはそれぞれ独立に置換基を有していてもよいメチン基又は窒素原子を表し、Ｘ、Ｙ、Ｚのうち少なくとも１つが置換基を有していてもよいメチン基である。Ｍは、２個の水素原子、置換基又は配位子を有していてもよい２〜４価の金属原子又は半金属原子、オキシ金属原子の何れかを表す。

However, in the general formula (1), rings A, B, C, and D each independently represent a pyrrole ring skeleton that may have a substituent, and X, Y, and Z each independently have a substituent. Represents a methine group or a nitrogen atom which may be present, and at least one of X, Y and Z is a methine group which may have a substituent. M represents any of two hydrogen atoms, a substituent or a ligand, a divalent to tetravalent metal atom, a metalloid atom or an oxymetal atom which may have a ligand.

In the compound represented by the general formula (1), the absorption wavelength can be arbitrarily selected while maintaining the extinction coefficient by selecting a substituent. Therefore, the optical constant necessary for the recording layer is satisfied at the wavelength of the laser beam. It is a very useful organic dye that can be made.
Specific examples of the substituent of the pyrrole ring A, B, C, D that may have a substituent in the general formula (1) include, for example, a halogen atom, a nitro group, a cyano group, a hydroxyl group, Amino group, carboxyl group, sulfonic acid group, substituted or unsubstituted alkyl group, aralkyl group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group, arylthio Group, alkenylthio group, monosubstituted amino group, disubstituted amino group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, monosubstituted aminocarbonyl group, disubstituted aminocarbonyl group, And acyloxy group or heteroaryl group .

  In addition, specific examples of the substituents of the methine groups X, Y, and Z that may have a substituent located at the meso position of the azaporphyrin skeleton of the general formula (1) are the formula (14) and the formula, respectively. (15), an optionally substituted methine group represented by formula (16), and the like.

ただし、式中、Ｇ^１、Ｇ^２、Ｇ^３は水素原子、ハロゲン原子、シアノ基、置換又は無置換の「アルキル基、アラルキル基、アリール基」の何れかを示す。

In the formula, G ¹ , G ² , and G ^{3 each} represent a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted “alkyl group, aralkyl group, aryl group”.

In addition, the substituent on the pyrrole ring and the substituent on the methine group represented by X, Y, and Z are each substituents on the pyrrole ring or a substituent on the pyrrole ring via a linking group. It may be linked with a substituent on an adjacent methine group, specifically, ring formation by aliphatic condensation or aromatic condensation, or a hetero atom such as a hetero atom or a metal complex residue as a linking group For example, formation of a heterocyclic ring is exemplified.
Further, specific examples of M in the general formula (1) include a divalent unsubstituted or ligand-containing metal atom, a substituted trivalent or tetravalent metal atom or semimetal atom, and an oxymetal atom. Etc.

ただし、式中、Ｒ^１〜Ｒ^８はそれぞれ独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシル基、アミノ基、カルボキシル基、スルホン酸基、置換又は無置換の「アルキル基、アラルキル基、アリール基、アルケニル基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、アルケニルオキシ基、アルキルチオ基、アラルキルチオ基、アリールチオ基、アルケニルチオ基」、モノ置換アミノ基、ジ置換アミノ基、置換又は無置換の「アシル基、アルコキシカルボニル基、アラルキルオキシカルボニル基、アリールオキシカルボニル基、アルケニルオキシカルボニル基」、モノ置換アミノカルボニル基、ジ置換アミノカルボニル基、置換又は無置換の「アシルオキシ基、ヘテロアリール基」の何れかを表し、Ｌ^１は窒素原子又はＣ−Ｒ^９（Ｒ^９は水素原子、ハロゲン原子、シアノ基、置換又は無置換の「アルキル基、アラルキル基、アリール基」の何れかを表す）で示される置換されていてもよいメチン基を表し、Ｌ^２は窒素原子又はＣ−Ｒ^１０（Ｒ^１０は水素原子、ハロゲン原子、シアノ基、置換又は無置換の「アルキル基、アラルキル基、アリール基」の何れかを表す）で示される置換されていてもよいメチン基を表し、Ｌ^３は、窒素原子又はＣ−Ｒ^１１（Ｒ^１１は水素原子、ハロゲン原子、シアノ基、置換又は無置換の「アルキル基、アラルキル基、アリール基」の何れかを表す）で示される置換されていてもよいメチン基を表し、Ｌ^１〜Ｌ^３のうち、少なくとも１つはメチン基を表し、Ｒ^１〜Ｒ^１１の各置換基は連結基を介して、隣接する置換基と共に環を形成してもよく、Ｍ^１は２個の水素原子、２価の無置換又は配位子を有する金属原子、置換基を有する３価又は４価の金属原子又は半金属原子、オキシ金属原子の何れかを表す。 Preferable examples of the compound represented by the general formula (1) include compounds represented by the following general formulas (2) to (8).

However, in the formula, R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, a substituted or unsubstituted “alkyl group, aralkyl” Group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group, arylthio group, alkenylthio group ", mono-substituted amino group, di-substituted amino group, substituted or Unsubstituted “acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group”, monosubstituted aminocarbonyl group, disubstituted aminocarbonyl group, substituted or unsubstituted “acyloxy group, heteroaryl” Any one of “group”, and L ¹ is a nitrogen atom Or a substituted methine represented by C—R ⁹ (wherein R ⁹ represents any one of a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted “alkyl group, aralkyl group, aryl group”) L ² represents a nitrogen atom or C—R ¹⁰ (R ¹⁰ represents a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted “alkyl group, aralkyl group, aryl group”). L ³ represents a nitrogen atom or C—R ¹¹ (R ¹¹ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted “alkyl group, aralkyl group, aryl group”. A methine group which is optionally substituted, and at least one of L ^{1 to} L ³ represents a methine group, and each substituent of R ^{1 to} R ¹¹ is a linking group. Through the adjacent May form a ring together with the substituent, M ¹ is two hydrogen atoms, a metal atom having a divalent unsubstituted or ligand, trivalent or tetravalent metal atom or metalloid atom having a substituent group Represents any of oxymetal atoms.

ただし、式中、Ｒ^１２〜Ｒ^１９はそれぞれ独立に、前記一般式（２）のＲ^１〜Ｒ^８と同一の基を表し、Ｒ^２０、Ｒ^２１はそれぞれ独立に、前記一般式（２）のＲ^９〜Ｒ^１１と同一の基を表し、Ｒ^１２〜Ｒ^２１の各置換基は連結基を介して、隣接する置換基と共に環を形成してもよく、Ｍ^２は前記一般式（２）のＭ^１と同一の物質を表す。これらの中でも、Ｒ^２０、Ｒ^２１が置換又は無置換のフェニル基のものが好ましい。

However, in the formula, R ^{12 to} R ¹⁹ each independently represent the same group as R ^{1 to} R ^{8 in} the general formula (2), and R ²⁰ and R ²¹ each independently represent the general formula (2). represent the same groups as ^R 9 ^{to R 11, and} each substituent group of R 12 ^{to R 21} via a linking group, may form a ring together with adjacent substituents, ^{M 2} is the formula (2 It represents the same material as ^{M 1} in). Among these, R ²⁰ and R ²¹ are preferably substituted or unsubstituted phenyl groups.

ただし、式中、Ｒ^２２〜Ｒ^２９はそれぞれ独立に、前記一般式（２）のＲ^１〜Ｒ^８と同一の基を表し、Ｒ^３０〜Ｒ^３２はそれぞれ独立に、前記一般式（２）のＲ^９〜Ｒ^１１と同一の基を表し、Ｒ^２２〜Ｒ^３２の各置換基は連結基を介して、隣接する置換基と共に環を形成してもよく、Ｍ^３は前記一般式（２）のＭ^１と同一の物質を表す。これらの中でも、Ｒ^３０〜Ｒ^３２が置換又は無置換のフェニル基も好ましく用いられる。

However, in the formula, R ^{22 to} R ²⁹ each independently represent the same group as R ^{1 to} R ^{8 in} the general formula (2), and R ^{30 to} R ³² each independently represent the general formula (2). represents the ^R 9 ^{to R 11} the same ^groups, each substituent group of R 22 ^{to R 32} via a linking group, may form a ring together with adjacent substituents, ^{M 3} is the formula (2 It represents the same material as ^{M 1} in). Among these, a phenyl group in which R ^{30 to} R ³² are substituted or unsubstituted is also preferably used.

ただし、式中、Ｒ^３３〜Ｒ^４４はそれぞれ独立に、水素原子、ハロゲン原子、ヒドロキシル基、置換又は無置換の「アルキル基、アリール基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、アルケニルオキシ基、アルキルチオ基、アリールチオ基、又はヘテロアリール基」の何れかを表し、Ｒ^３３とＲ^３４、Ｒ^３５とＲ^３６は、連結基を介して、それぞれ置換基を有していてもよい脂肪族環を形成してもよく、Ｘ^１、Ｙ^１、Ｚ^１はそれぞれ独立にメチン基又は窒素原子を表し、Ｘ^１、Ｙ^１、Ｚ^１のうち少なくとも２つが窒素原子であり、Ｍ^４は前記一般式（２）のＭ^１と同一の物質を表す。

However, in the formula, R ^{33 to} R ⁴⁴ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted “alkyl group, aryl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group” , An alkylthio group, an arylthio group, or a heteroaryl group ”, R ³³ and R ³⁴ , R ³⁵ and R ³⁶ are each an aliphatic ring optionally having a substituent via a linking group. X ¹ , Y ¹ , and Z ¹ each independently represent a methine group or a nitrogen atom, and at least two of X ¹ , Y ¹ , and Z ¹ are nitrogen atoms, and M ⁴ represents the above general formula It represents the same substance as M ^{1 in} formula (2).

ただし、式中、Ｒ^４５〜Ｒ^５６はそれぞれ独立に、前記一般式（５）のＲ^３３〜Ｒ^４４と同一の基を表し、Ｒ^４５とＲ^４６、Ｒ^４７とＲ^４８は、連結基を介して、それぞれ置換基を有していてもよい脂肪族環を形成してもよく、Ｍ^５は前記一般式（２）のＭ^１と同一の物質を表す。

However, in the formula, R ^{45 to} R ⁵⁶ each independently represent the same group as R ^{33 to} R ^{44 in} the general formula (5), and R ⁴⁵ and R ⁴⁶ , R ⁴⁷ and R ⁴⁸ represent a linking group. Each may form an aliphatic ring which may have a substituent, and M ⁵ represents the same substance as M ^{1 in the} general formula (2).

ただし、式中、Ｒ^５７〜Ｒ^６８はそれぞれ独立に、前記一般式（５）のＲ^３３〜Ｒ^４４と同一の基を表し、Ｒ^５７とＲ^５８、Ｒ^５９とＲ^６０は連結基を介して、それぞれ置換基を有していてもよい脂肪族環を形成してもよく、Ｍ^６は前記一般式（２）のＭ^１と同一の物質を表す。

However, in the formula, R ^{57 to} R ⁶⁸ each independently represent the same group as R ^{33 to} R ^{44 in} the general formula (5), and R ⁵⁷ and R ⁵⁸ , R ⁵⁹ and R ⁶⁰ are connected via a linking group. Each of them may form an aliphatic ring which may have a substituent, and M ⁶ represents the same substance as M ^{1 in the} general formula (2).

ただし、式中、Ｒ^６９〜Ｒ^８０はそれぞれ独立に、前記一般式（５）のＲ^３３〜Ｒ^４４と同一の基を表し、Ｒ^６９とＲ^７０、Ｒ^７１とＲ^７２は連結基を介して、それぞれ置換基を有していてもよい脂肪族環を形成してもよく、Ｍ７は前記一般式（２）のＭ１と同一の物質を表す。

However, in the formula, R ^{69 to} R ⁸⁰ each independently represent the same group as R ^{33 to} R ^{44 in} the general formula (5), and R ⁶⁹ and R ⁷⁰ , and R ⁷¹ and R ⁷² are connected via a linking group. Each of them may form an aliphatic ring which may have a substituent, and M7 represents the same substance as M1 in the general formula (2).

  It is represented by the following general formula (11), which is produced by reacting maleonitrile represented by the following general formula (9), acetophenone represented by the following general formula (10), a metal halide and / or a metal derivative. A mixture of azaporphyrin compounds (herein, a mixture is a mixture of structural isomers produced by the combination of raw materials, maleonitrile and acetophenone).

ただし、式中、Ｒ^８１〜Ｒ^８６はそれぞれ独立に、前記一般式（５）のＲ^３３〜Ｒ^４４と同一の基を表し、Ｒ^８１とＲ^８２は連結基を介して、置換基を有していてもよい脂肪族環を形成してもよく、Ｑはハロゲン原子又はシアノ基を表す。

However, in the formula, R ^{81 to} R ⁸⁶ each independently represent the same group as R ^{33 to} R ^{44 in} the general formula (5), and R ⁸¹ and R ⁸² have a substituent via a linking group. An aliphatic ring which may be substituted, and Q represents a halogen atom or a cyano group.

In the azaporphyrin compound represented by the general formula (2), specific examples in the case where R ^{1 to} R ⁸ are halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Specific examples of the case where R ^{1 to} R ⁸ are substituted or unsubstituted alkyl groups include the following groups (a) to (e).

(1) methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-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-dimethylbutyl 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-trimethyl Butyl 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-dimethyl Pentyl 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 , 5,7-tetraethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, n-tetrade Sil 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-cyclohexyl-2,2-dimethylpropyl group and the like, an unsubstituted linear, branched or cyclic alkyl group having 1 to 15 carbon atoms.

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

(3) Hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 2-hydroxy-3-methoxypropyl group, 2-hydroxy-3-chloropropyl group, 2-hydroxy-3 -Substituted with hydroxyl groups such as ethoxypropyl group, 3-butoxy-2-hydroxypropyl group, 2-hydroxy-3-cyclohexyloxypropyl group, 2-hydroxypropyl group, 2-hydroxybutyl group, 4-hydroxydecalyl group Alkyl group having 1 to 10 carbon atoms.

(4) 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.

(5) Hydroxymethoxymethoxymethyl group, hydroxyethoxyethoxyethyl group, [2 ′-(2′-hydroxy-1′-methylethoxy) -1′-methylethoxy] ethoxyethyl group, [2 ′-(2′- Hydroxyalkoxyalkoxy such as fluoro-1′-hydroxyethoxy) -1′-methylethoxy] ethoxyethyl group, [2 ′-(2′-chloro-1′-hydroxyethoxy) -1′-methylethoxy] ethoxyethyl group A C3-C10 alkyl group substituted with a group.

(6) 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, a 3-butoxy-2-cyanopropyl group, a 2-cyano-3-cyclohexylpropyl group, a 2-cyanopropyl group, a 2-cyanobutyl group or the like substituted with a cyano group.

(7) 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) ) Carbon substituted with an alkoxy group such as ethyl group or (3,3,3-trichloropropoxy) ethyl group An alkyl group of 2 to 15.

(8) 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 ′ -Alkoxyalkoxy groups such as -ethoxy-1'-methylethoxy) -1-methylethyl group, (3,3,3-trifluoropropoxy) ethoxyethyl group, (3,3,3-trichloropropoxy) ethoxyethyl group; A substituted alkyl group having 3 to 15 carbon atoms;

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

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

(11) Formyloxymethyl group, acetoxyethyl group, propionyloxyethyl group, butanoyloxyethyl group, valeryloxyethyl group, (2-ethylhexanoyloxy) ethyl group, (3,5,5-trimethylhexanoyl) Carbon number substituted with acyloxy groups such as (oxy) ethyl group, (3,5,5-trimethylhexanoyloxy) hexyl group, (3-fluorobutyryloxy) ethyl group, (3-chlorobutyryloxy) ethyl group 2 to 15 alkyl groups.

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

(13) Acetoxymethoxymethoxymethyl group, acetoxyethoxyethoxyethyl group, propionyloxyethoxyethoxyethyl group, valeryloxyethoxyethoxyethyl group, (2-ethylhexanoyloxy) ethoxyethoxyethyl group, (3, 5, 5- C5-C15 alkyl group substituted by acyloxyalkoxyalkoxy groups such as trimethylhexanoyloxy) ethoxyethoxyethyl group, (2-fluoropropionyloxy) ethoxyethoxyethyl group, (2-chloropropionyloxy) ethoxyethoxyethyl group .

(14) Methoxycarbonylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylethyl group, butoxycarbonylethyl group, (p-ethylcyclohexyloxycarbonyl) cyclohexyl group, (2,2,3 , 3-tetrafluoropropoxycarbonyl) methyl group, (2,2,3,3-tetrachloropropoxycarbonyl) methyl group and other alkylcarbonyl groups substituted with an alkoxycarbonyl group.

(15) C 8-15 substituted with an aryloxycarbonyl group such as a phenoxycarbonylmethyl group, phenoxycarbonylethyl group, (4-t-butylphenoxycarbonyl) ethyl group, naphthyloxycarbonylmethyl group, biphenyloxycarbonylethyl group Alkyl group.

(16) 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, or a (4-cyclohexyloxybenzyloxycarbonyl) methyl group.

(17) 4 to 10 carbon atoms substituted with an alkenyloxycarbonyl group such as vinyloxycarbonylmethyl group, vinyloxycarbonylethyl group, allyloxycarbonylmethyl group, cyclopentadienyloxycarbonylmethyl group, octenoxycarbonylmethyl group Alkyl group.

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

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

(20) 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- Silaminoethyl 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-butylamino Propyl group, di-n-hexylaminopropyl group, di-n-octylaminopropyl group, di-n-decylaminopropyl group, N-isoamyl-N-methylaminopropyl group, piperidinopropyl group, di (methoxy) Methyl) aminopropyl group, di (methoxyethyl) amino Nopropyl group, di (ethoxymethyl) aminopropyl group, di (ethoxyethyl) aminopropyl group, di (propoxyethyl) aminopropyl group, di (butoxyethyl) aminopropyl group, bis (2-cyclohexyloxyethyl) aminopropyl group Dimethylaminobutyl 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) amino Butyl group, bis (2-cyclohexyloxy-ethyl) alkyl group having 3 to 20 carbon atoms dialkylamino group is substituted, such as aminobutyl group.

(21) Substitution with acylamino groups such as acetylaminomethyl group, acetylaminoethyl group, propionylaminoethyl group, butanoylaminoethyl group, cyclohexanecarbonylaminoethyl group, p-methylcyclohexanecarbonylaminoethyl group, succiniminoethyl group An alkyl group having 3 to 10 carbon atoms.

(22) An alkyl group having 2 to 10 carbon atoms substituted with an alkylsulfonamino group such as a methylsulfonaminomethyl group, a methylsulfonaminoethyl group, an ethylsulfonaminoethyl group, a propylsulfonaminoethyl group, or an octylsulfonaminoethyl group.

(23) 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;

(24) Benzenesulfonylmethyl group, benzenesulfonylethyl group, benzenesulfonylpropyl group, benzenesulfonylbutyl group, toluenesulfonylmethyl group, toluenesulfonylethyl group, toluenesulfonylpropyl group, toluenesulfonylbutyl group, xylenesulfonylmethyl group, xylenesulfonyl An alkyl group having 7 to 12 carbon atoms substituted with an arylsulfonyl group such as an ethyl group, a xylenesulfonylpropyl group, or a xylenesulfonylbutyl group;

(25) thiadiazolinomethyl group, pyrrolinomethyl group, pyrrolidinomethyl group, pyrazolidinomethyl group, imidazolidinomethyl group, oxazolyl group, triazolinomethyl group, morpholinomethyl group, indolinomethyl group, benzimidazolino An alkyl group having 2 to 13 carbon atoms substituted with a heterocyclic group such as a methyl group or a carbazolinomethyl group;

(26) 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, ferrocenylneopentyl 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.

(27) cobaltcenylmethyl group, cobaltcenylethyl group, cobaltcenyl-n-propyl group, cobaltcenyl-iso-propyl group, cobaltcenyl-n-butyl group, cobaltcenyl-iso-butyl group, cobaltcenyl-sec-butyl group, Cobaltcenyl-t-butyl group, cobaltcenyl-n-pentyl group, cobaltcenyl-iso-pentyl group, cobaltcenyl-2-methylbutyl group, cobaltcenyl-1-methylbutyl group, cobaltcenylneopentyl group, cobaltcenyl-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, cobaltcenyl-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, cobaltcenyl-2-methylhexyl Base , Cobaltcenyl-3-methylhexyl group, cobaltcenyl-4-methylhexyl group, cobaltcenyl-5-methylhexyl group, cobaltcenyl-2,4-dimethylpentyl group, cobaltcenyl-n-octyl group, cobaltcenyl-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.

(28) a nickelocenylmethyl group, a nickelocenylethyl group, a nickelocenyl-n-propyl group, a nickelocenyl-iso-propyl group, a nickelocenyl-n-butyl group, a nickelocenyl-iso-butyl group, a 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 Base , 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.

(29) Dichlorotitanocenylmethyl group, trichlorotitanium cyclopentadienylmethyl group, bis (trifluoromethanesulfonate) titanocenemethyl group, dichlorozirconocenylmethyl group, dimethylzirconocenylmethyl group, diethoxyzirconocenylmethyl 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 (cyclopentadienyl) ruthenium methyl group, bis (cyclopentadienyl) vanadium methyl group, or bis (cyclopentadienyl) dichlorovanadium methyl group.

(30) Ferrocenylmethoxymethyl group, ferrocenylmethoxyethyl group, ferrocenylmethoxypropyl group, ferrocenylmethoxybutyl group, ferrocenylmethoxypentyl group, ferrocenylmethoxyhexyl group, ferrocenylmethoxyheptyl Group, ferrocenylmethoxyoctyl group, ferrocenylmethoxynonyl group, ferrocenylmethoxydecyl group, ferrocenylethoxymethyl group, ferrocenylethoxyethyl group, ferrocenylethoxypropyl group, ferrocenylethoxybutyl group , Ferrocenylethoxypentyl group, ferrocenylethoxyhexyl group, ferrocenylethoxyheptyl group, ferrocenylethoxyoctyl group, ferrocenylethoxynonyl group, ferrocenylethoxydecyl group, ferrocenylpropoxymethyl group, Fe Cenylpropoxyethyl group, ferrocenylpropoxypropyl group, ferrocenylpropoxybutyl group, ferrocenylpropoxypentyl group, ferrocenylpropoxyhexyl group, ferrocenylpropoxyheptyl group, ferrocenylpropoxyoctyl group, ferrocele Nylpropoxynonyl group, ferrocenylpropoxydecyl group, ferrocenylbutoxymethyl group, ferrocenylbutoxyethyl group, ferrocenylbutoxypropyl group, ferrocenylbutoxybutyl group, ferrocenylbutoxypentyl group, ferrocenyl Butoxyhexyl, Ferrocenylbutoxyheptyl, Ferrocenylbutoxyoctyl, Ferrocenylbutoxynonyl, Ferrocenylbutoxydecyl, Ferrocenyldecyloxymethyl, Ferrocenyldecyloxyethyl Group, ferrocenyldecyloxypropyl group, ferrocenyldecyloxybutyl group, ferrocenyldecyloxypentyl group, ferrocenyldecyloxyhexyl group, ferrocenyldecyloxyheptyl group, ferrocenyldecyloxyoctyl group, Ferrocenyldecyloxynonyl group, ferrocenyldecyloxydecyl group.

(31) Cobaltcenylmethoxymethyl group, cobaltcenylmethoxyethyl group, cobaltcenylmethoxypropyl group, cobaltcenylmethoxybutyl group, cobaltcenylmethoxypentyl group, cobaltcenylmethoxyhexyl group, cobaltcenylmethoxyheptyl Group, cobaltcenylmethoxyoctyl group, cobaltcenylmethoxynonyl group, cobaltcenylmethoxydecyl group, cobaltcenylethoxymethyl group, cobaltcenylethoxyethyl group, cobaltcenylethoxypropyl group, cobaltcenylethoxybutyl group , Cobaltcenylethoxypentyl group, cobaltcenylethoxyhexyl group, cobaltcenylethoxyheptyl group, cobaltcenylethoxyoctyl group, cobaltcenylethoxynonyl group, cobaltcenylethoxydecyl , Cobaltcenylpropoxymethyl group, cobaltcenylpropoxyethyl group, cobaltcenylpropoxypropyl group, cobaltcenylpropoxybutyl group, cobaltcenylpropoxypentyl group, cobaltcenylpropoxyhexyl group, cobaltcenylpropoxyheptyl group, Cobaltcenylpropoxyoctyl group, cobaltcenylpropoxynonyl group, cobaltcenylpropoxydecyl group, cobaltcenylbutoxymethyl group, cobaltcenylbutoxyethyl group, cobaltcenylbutoxypropyl group, cobaltcenylbutoxybutyl group, cobalt Cenylbutoxypentyl group, cobaltcenylbutoxyhexyl group, cobaltcenylbutoxyheptyl group, cobaltcenylbutoxyoctyl group, cobaltcenylbutoxynonyl group, cobaltcenylbutyl group Toxidecyl group, cobalt senyl decyloxymethyl group, cobalt senyl decyloxy ethyl group, cobalt senyl decyloxy propyl group, cobalt senyl decyloxy butyl group, cobalt senyl decyloxy pentyl group, cobalt senyl decyloxy hexyl group , Cobalt senyl decyloxy heptyl group, cobalt senyl decyloxy octyl group, cobalt senyl decyloxy nonyl group, cobalt senyl decyloxy decyl group.

(32) nickelocenyl methoxymethyl group, nickelocenyl methoxyethyl group, nickelocenyl methoxypropyl group, nickelocenyl methoxybutyl group, nickelocenyl methoxypentyl group, nickelocenyl methoxyhexyl group, nickelocenyl methoxyheptyl 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 , 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, Nicke Locenylbutoxypentyl group, nickelocenylbutoxyhexyl group, nickelocenylbutoxyheptyl group, nickelocenylbutoxyoctyl group, nickelocenylbutoxynonyl group, nickelocenylbyl Toxidecyl group, Nickelocenyldecyloxymethyl group, Nickelocenyldecyloxyethyl group, Nickelocenyldecyloxypropyl group, Nickelocenyldecyloxybutyl group, Nickelocenyldecyloxypentyl group, Nickelocenyldecyloxyhexyl group A nickelocenyldecyloxyheptyl group, a nickelocenyldecyloxyoctyl group, a nickelocenyldecyloxynonyl group, a nickelocenyldecyloxydecyl group.

(33) Dichlorotitanosenylmethoxymethyl group, trichlorotitanium cyclopentadienylmethoxyethyl group, bis (trifluoromethanesulfonate) titanocenemethoxypropyl group, dichlorozirconocenylmethoxybutyl group, dimethylzirconocenylmethoxypentyl group, di Ethoxyzirconocenylmethoxymethyl group, bis (cyclopentadienyl) chromium methoxyhexyl group, bis (cyclopentadienyl) dichlorohafnium methoxymethyl group, bis (cyclopentadienyl) dichloroniobium methoxyoctyl group, bis (cyclopenta Dienyl) ruthenium methoxymethyl group, bis (cyclopentadienyl) vanadium methoxymethyl group, bis (cyclopentadienyl) dichlorovanadium methoxyethyl group, osmocenyl methoxy Alkyl group prime 12-30 substituted with metallocenylphosphines alkenyl alkyl group such as ethyl.

(34) Ferrocenecarbonyloxymethyl group, ferrocenecarbonyloxyethyl group, ferrocenecarbonyloxypropyl group, ferrocenecarbonyloxybutyl group, ferrocenecarbonyloxypentyl group, ferrocenecarbonyloxyhexyl group, ferrocenecarbonyloxyheptyl group, ferrocenecarbonyloxyoctyl group , Ferrocenecarbonyloxynonyl group, ferrocenecarbonyloxydecyl group.

(35) Cobaltcenecarbonyloxymethyl group, cobaltcenecarbonyloxyethyl group, cobaltcenecarbonyloxypropyl group, cobaltcenecarbonyloxybutyl group, cobaltcenecarbonyloxypentyl group, cobaltcenecarbonyloxyhexyl group, cobaltcenecarbonyloxyheptyl group Group, cobaltcenecarbonyloxyoctyl group, cobaltcenecarbonyloxynonyl group, cobaltcenecarbonyloxydecyl group.

(36) Nickelocenecarbonyloxymethyl group, Nickelocenecarbonyloxyethyl group, Nickelocenecarbonyloxypropyl group, Nickelocenecarbonyloxybutyl group, Nickelocenecarbonyloxypentyl group, Nickelocenecarbonyloxyhexyl group, Nickelocenecarbonyloxyheptyl group Group, nickelocenecarbonyloxyoctyl group, nickelocenecarbonyloxynonyl group, nickelocenecarbonyloxydecyl group.

(37) Dichlorotitanosenylcarbonyloxymethyl group, trichlorotitanium cyclopentadienylcarbonyloxyethyl group, bis (trifluoromethanesulfonate) titanocenecarbonyloxymethoxypropyl group, dichlorozirconocenecarbonyloxybutyl group, dimethylzirconocenecarbonyloxypentyl group , Diethoxyzirconocenecarbonyloxymethyl group, bis (cyclopentadienyl) chrome carbonyloxyhexyl group, bis (cyclopentadienyl) dichlorohafniumcarbonyloxymethyl group, bis (cyclopentadienyl) dichloroniobylcarbonyloxyoctyl group, Bis (cyclopentadienyl) ruthenium carbonyloxymethyl group, bis (cyclopentadienyl) vanadium carbonyloxime Group, bis (cyclopentadienyl) dichloro vanadium carbonyloxy ethyl group, bis (cyclopentadienyl) alkyl group having a carbon number of 12 to 30 was replaced with metallocenylphosphines alkenyl carbonyl group such as osmium carbonyloxy ethyl group.

In addition, specific examples in the case where R ^{1 to} R ⁸ are substituted or unsubstituted aralkyloxy groups include aralkyloxy groups having the same substituents as in the case of the alkyl group described above, and benzyl is preferable. Oxy group, nitrobenzyloxy group, cyanobenzyloxy group, hydroxybenzyloxy group, methylbenzyloxy group, trifluoromethylbenzyloxy group, naphthylmethoxy group, nitronaphthylmethoxy group, cyanonaphthylmethoxy group, hydroxynaphthylmethoxy group, methyl And an aralkyloxy group having 7 to 15 carbon atoms such as a naphthylmethoxy group, a trifluoromethylnaphthylmethoxy group, and a fluoren-9-ylethoxy group.

Further, specific examples in the case where R ^{1 to} R ⁸ are substituted or unsubstituted aryloxy groups include aryloxy groups having the same substituents as in the case of the alkyl groups described above, and preferably 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 And an aryloxy group having 6 to 18 carbon atoms, such as a nickelocenyloxy group, an octamethylferrocenyloxy group, an octamethylcobalcenyloxy group, and an octamethylnickelocenyloxy group.

In addition, specific examples in the case where R ^{1 to} R ⁸ are substituted or unsubstituted alkenyloxy groups include alkenyloxy groups having the same substituents as those in the above-described alkyl group, and vinyloxy is preferable. Group, 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-dicyanovinyloxy group, 2-cyano-2-methylcarboxylvinyloxy group, 2-cyano-2-methylsulfonvinyloxy group, styryloxy group, 4 -Alkyl having 2 to 10 carbon atoms such as phenyl-2-butenyloxy group and cinnamylalkoxy group Is a Niruokishi group.

In addition, specific examples in the case where R ^{1 to} R ⁸ are substituted or unsubstituted alkylthio groups include alkylthio groups having the same substituents as in the case of the alkyl groups described above, preferably methylthio groups, Ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, neopentylthio group, 2- It is an alkylthio group having 1 to 10 carbon atoms such as methylbutylthio group, methylcarboxylethylthio group, 2-ethylhexylthio group, 3,5,5-trimethylhexylthio group, and decalylthio group.

In addition, specific examples in the case where R ^{1 to} R ⁸ are substituted or unsubstituted aralkylthio groups include aralkylthio groups having the same substituents as in the case of the alkyl groups described above, and benzylthio is preferable. Group, nitrobenzylthio group, cyanobenzylthio group, hydroxybenzylthio group, methylbenzylthio group, trifluoromethylbenzylthio group, naphthylmethylthio group, nitronaphthylmethylthio group, cyanonaphthylmethylthio group, hydroxynaphthylmethylthio group, methylnaphthyl And an aralkylthio group having 7 to 12 carbon atoms such as a methylthio group, a trifluoromethylnaphthylmethylthio group, and a fluoren-9-ylethylthio group.

In addition, specific examples in the case where R ^{1 to} R ⁸ are substituted or unsubstituted arylthio groups include arylthio groups having the same substituents as in the case of the alkyl groups described above. Preferred are phenylthio groups, 4-methylphenylthio group, 2-methoxyphenylthio group, 4-t-butylphenylthio group, naphthylthio group, ferrocenylthio group, cobaltcenylthio group, nickelocenylthio group, octamethylferrocenylthio group, octamethylcobalt An arylthio group having 6 to 10 carbon atoms such as a senylthio group and an octamethylnickelocenylthio group;

Further, specific examples in the case where R ^{1 to} R ⁸ are substituted or unsubstituted alkenylthio groups include alkenylthio groups having the same substituents as in the case of the alkyl groups described above, preferably vinylthio Group, allylthio group, butenylthio group, hexanedienylthio group, cyclopentadienylthio group, styrylthio group, cyclohexenylthio group, alkenylthio group such as decenylthio group.

Further, as a specific example of R ¹ to R ⁸ is a mono-substituted amino group, include mono-substituted amino group having a case similar to the substituent of the alkyl group described above, preferred are the following (1 ) To (5).
(1) methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, (2-ethylhexyl) amino group, cyclohexylamino group, (3, 5,5-trimethylhexyl) monoalkylamino groups having 1 to 10 carbon atoms such as amino group, nonylamino group, decylamino group and the like.

(2) benzylamino group, phenethylamino group, (3-phenylpropyl) amino group, (4-ethylbenzyl) amino group, (4-isopropylbenzyl) amino group, (4-methylbenzyl) amino group, (4- Monoethyl having 7 to 10 carbon atoms such as (ethylbenzyl) amino group, (4-allylbenzyl) amino group, [4- (2-cyanoethyl) benzyl] amino group, [4- (2-acetoxyethyl) benzyl] amino group, etc. Aralkylamino group.

(3) Anilino, naphthylamino, toluidino, xylidino, ethylanilino, isopropylanilino, methoxyanilino, ethoxyanilino, chloroanilino, acetylanilino, methoxycarbonylanilino, ethoxycarbonyl Anilino group, propoxycarbonylanilino group, 4-methylanilino group, 4-ethylanilino group, ferrocenylamino group, cobaltcenylamino group, nickelocenylamino group, zirconocenylamino group, octamethylferrocenylamino A monoarylamino group having a prime number of 6 to 10, such as a group, an octamethylcobalcenylamino group, an octamethylnickelocenylamino group, and an octamethylzirconocenylamino group.

(4) 2-10 carbon atoms such as vinylamino group, allylamino group, butenylamino group, pentenylamino group, hexenylamino group, cyclohexenylamino group, cyclopentadienylamino group, octadienylamino group, adamantenylamino group, etc. A monoalkenylamino group.

(5) 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 , Tolylcarbonylamino group, propylbenzoylamino group, 4-t-butylbenzoylamino group, nitrobenzylcarbonylamino group, 3-butoxy-2-naphthoylamino group, cinnamoylamino group, B Sen carbonylamino group, 1-methyl-ferrocene-1'-carbonyl group, cobaltocene carbonylamino group, an amino group such as an acylamino group having 1 to 16 carbon atoms such as nickel Russia Sen carbonylamino group.

Specific examples of the case where R ^{1 to} R ⁸ are disubstituted amino groups include disubstituted amino groups having the same substituents as in the case of the alkyl group described above, and the following (1 ) To (6).

(1) 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- (2-cyanoethyl) A dialkylamino group having 2 to 16 carbon atoms such as an amino group and a di (propionyloxyethyl) amino group;

(2) Diaralkylamino groups having 14 to 20 carbon atoms such as dibenzylamino group, diphenethylamino group, bis (4-ethylbenzyl) amino group, and bis (4-isopropylbenzyl) amino group.

(3) A diarylamino group having 12 to 14 carbon atoms such as a diphenylamino group, a ditolylamino group, or an N-phenyl-N-tolylamino group.

(4) C4-C12 such as divinylamino group, diallylamino group, dibutenylamino group, dipentenylamino group, dihexenylamino group, bis (cyclopentadienyl) amino group, N-vinyl-N-allylamino group, etc. Dialkenylamino group.

(5) 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 (sec-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 (tolyl) Carbonyl) amino group, di (propylbenzoyl) amino group, di (4-t-butylbenzoy) ) Amino group, di (nitrobenzylcarbonyl) amino group, di (3-butoxy-2-naphthoyl) amino group, di (cinnamoyl) amino group, a diacylamino group having 2 to 30 carbon atoms such as succinic acid imino group.

(6) 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 -Number of carbons having a substituent selected from a substituted or unsubstituted alkyl group such as methyl-octamethylcobaltenylcenylamino group, N-methyl-octamethylnickelocenylamino group, aralkyl group, aryl group, alkenyl group 3-24 disubstituted amino groups.

In addition, specific examples in the case where R ^{1 to} R ⁸ are substituted or unsubstituted acyl groups include acyl groups having the same substituents as in the case of the alkyl group described above, preferably a formyl group, Methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neopentylcarbonyl group, 2-methylbutylcarbonyl group, benzoyl group, methylbenzoyl group, ethylbenzoyl group, tolylcarbonyl group, propylbenzoyl group, 4-t-butylbenzoyl group, nitrobenzylcarbonyl group, 3-butoxy-2-naphthoyl group, cinna Yl group, ferrocene carbonyl group, a 1-methyl-ferrocene-1'-carbonyl group, cobaltocene carbonyl group, an acyl group having 1 to 16 carbon atoms such as nickel Russia Sen carbonyl group.

In addition, specific examples in the case where R ^{1 to} R ⁸ are substituted or unsubstituted alkoxycarbonyl groups include alkoxycarbonyl groups having the same substituents as in the case of the alkyl groups described above. (1) to (7).

(1) Methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, iso-propoxycarbonyl group, n-butoxycarbonyl group, iso-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-pen Toxylcarbonyl group, iso-pentoxycarbonyl group, neopentoxycarbonyl group, 2-pentoxycarbonyl group, 2-ethylhexyloxycarbonyl group, 3,5,5-trimethylhexyloxycarbonyl group, decalyloxycarbonyl group, cyclohexyl An alkoxycarbonyl group having 2 to 11 carbon atoms such as an oxycarbonyl group, a chloroethoxycarbonyl group, a hydroxymethoxycarbonyl group, and a hydroxyethoxycarbonyl group;

(2) Methoxymethoxycarbonyl group, methoxyethoxycarbonyl group, ethoxyethoxycarbonyl group, propoxyethoxycarbonyl group, butoxyethoxycarbonyl group, pentoxyethoxycarbonyl group, hexyloxyethoxycarbonyl group, butoxybutoxycarbonyl group, hexyloxybutoxycarbonyl group , An alkoxycarbonyl group having 3 to 11 carbon atoms substituted with an alkoxy group such as a hydroxymethoxymethoxycarbonyl group or a hydroxyethoxyethoxycarbonyl group.

(3) Alkoxyalkoxy such as methoxymethoxymethoxycarbonyl group, methoxyethoxyethoxycarbonyl group, ethoxyethoxyethoxycarbonyl group, propoxyethoxyethoxycarbonyl group, butoxyethoxyethoxycarbonyl group, pentoxyethoxyethoxycarbonyl group, hexyloxyethoxyethoxycarbonyl group An alkoxycarbonyl group having 4 to 11 carbon atoms substituted by the group;

(4) Ferrocenylmethoxycarbonyl group, ferrocenylethoxycarbonyl group, ferrocenylpropoxycarbonyl group, ferrocenylbutoxycarbonyl group, ferrocenylpentyloxycarbonyl group, ferrocenylhexyloxycarbonyl group, ferrocenylheptyl An oxycarbonyl group, a ferrocenyloctyloxycarbonyl group, a ferrocenylnonyloxycarbonyl group, and a ferrocenyldecyloxycarbonyl group.

(5) Cobaltcenylmethoxycarbonyl group, cobaltcenylethoxycarbonyl group, cobaltcenylpropoxycarbonyl group, cobaltcenylbutoxycarbonyl group, cobaltcenylpentyloxycarbonyl group, cobaltcenylhexyloxycarbonyl group, cobaltcenylheptyl An oxycarbonyl group, a cobaltcenyloctyloxycarbonyl group, a cobaltcenylnonyloxycarbonyl group, and a cobaltcenyldecyloxycarbonyl group.

(6) Nickelocenylmethoxycarbonyl group, Nickelocenylethoxycarbonyl group, Nickelocenylpropoxycarbonyl group, Nickelocenylbutoxycarbonyl group, Nickelocenylpentyloxycarbonyl group, Nickelocenylhexyloxycarbonyl group, Nickelocenyl Heptyloxycarbonyl group, nickelocenyloctyloxycarbonyl group, nickelocenylnonyloxycarbonyl group, nickelocenyldecyloxycarbonyl group.

(7) Dichlorotitanosenyl methoxycarbonyl group, trichlorotitanium cyclopentadienyl methoxycarbonyl group, bis (trifluoromethanesulfonato) titanocene methoxycarbonyl group, dichlorozirconocenylmethoxycarbonyl group, dimethylzirconocenylmethoxycarbonyl group, di Ethoxyzirconocenyl methoxycarbonyl group, bis (cyclopentadienyl) chromium methoxycarbonyl group, bis (cyclopentadienyl) dichlorohafnium methoxycarbonyl group, bis (cyclopentadienyl) dichloroniobium methoxycarbonyl group, bis (cyclopenta Dienyl) ruthenium methoxycarbonyl group, bis (cyclopentadienyl) vanadium methoxycarbonyl group, bis (cyclopentadienyl) dichlorovanadium group Alkoxycarbonyl group, bis (cyclopentadienyl) alkoxycarbonyl group having a carbon number of 11 to 20 was substituted with metallocenyl group such as osmium methoxycarbonyl group.

In addition, specific examples in the case where R ^{1 to} R ⁸ are substituted or unsubstituted aralkyloxycarbonyl groups include aralkyloxycarbonyl groups having the same substituents as in the case of the alkyl groups described above, and are preferable. Benzyloxycarbonyl group, nitrobenzyloxycarbonyl group, cyanobenzyloxycarbonyl group, hydroxybenzyloxycarbonyl group, methylbenzyloxycarbonyl group, trifluoromethylbenzyloxycarbonyl group, naphthylmethoxycarbonyl group, nitronaphthylmethoxycarbonyl group, cyano Naphthylmethoxycarbonyl group, hydroxynaphthylmethoxycarbonyl group, methylnaphthylmethoxycarbonyl group, trifluoromethylnaphthylmethoxycarbonyl group, fluoren-9-ylethoxycarbo Le group is an aralkyloxycarbonyl group having 8 to 16 carbon atoms, etc., such as.

In addition, specific examples in the case where R ^{1 to} R ⁸ are substituted or unsubstituted aryloxycarbonyl groups include aryloxycarbonyl groups having the same substituents as in the case of the alkyl groups described above, and are preferable. Phenoxycarbonyl group, 2-methylphenoxycarbonyl group, 4-methylphenoxycarbonyl group, 4-t-butylphenoxycarbonyl group, 2-methoxyphenoxycarbonyl group, 4-iso-propylphenoxycarbonyl group, naphthoxycarbonyl group, ferro Cenyloxycarbonyl group, cobaltcenyloxycarbonyl group, nickelocenyloxycarbonyl group, zirconocenyloxycarbonyl group, octamethylferrocenyloxycarbonyl group, octamethylcobaltenyloxycarbonyl group, octamethylnickelo Aryloxycarbonyl group, an aryloxycarbonyl group having 7 to 11 carbon atoms such as octamethyl zirconyl placed aryloxycarbonyl group.

Further, specific examples in the case where R ^{1 to} R ⁸ are substituted or unsubstituted alkenyloxycarbonyl groups include alkenyloxycarbonyl groups having the same substituents as in the case of the alkyl groups described above, and are preferable. Vinyloxycarbonyl group, propenyloxycarbonyl group, 1-butenyloxycarbonyl group, iso-butenyloxycarbonyl group, 1-pentenyloxycarbonyl group, 2-pentenyloxycarbonyl group, cyclopentadienyloxycarbonyl group, 2 -Methyl-1-butenyloxycarbonyl group, 3-methyl-1-butenyloxycarbonyl group, 2-methyl-2-butenyloxycarbonyl group, 2,2-dicyanovinyloxycarbonyl group, 2-cyano-2 -Methylcarboxylvinyloxycarbonyl group, 2-sia -2-methyl sulfone vinyl oxycarbonyl group, styryl oxycarbonyl group, an alkenyloxycarbonyl group having a carbon number of 3 to 11, such as 4-phenyl-2-butenyl oxy carbonyl group.

In addition, specific examples in the case where R ^{1 to} R ⁸ are mono-substituted aminocarbonyl groups include mono-substituted aminocarbonyl groups having the same substituents as in the case of the alkyl group described above. It is group (1)-(4).

(1) methylaminocarbonyl group, ethylaminocarbonyl group, propylaminocarbonyl group, butylaminocarbonyl group, pentylaminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group, octylaminocarbonyl group, (2-ethylhexyl) aminocarbonyl Groups, cyclohexylaminocarbonyl groups, (3,5,5-trimethylhexyl) aminocarbonyl groups, nonylaminocarbonyl groups, decylaminocarbonyl groups and other monoalkylaminocarbonyl groups having 2 to 11 carbon atoms.

(2) benzylaminocarbonyl group, phenethylaminocarbonyl group, (3-phenylpropylaminocarbonyl group, (4-ethylbenzyl) aminocarbonyl group, (4-isopropylbenzyl) aminocarbonyl group, (4-methylbenzyl) aminocarbonyl Group, (4-ethylbenzyl) aminocarbonyl group, (4-allylbenzyl) aminocarbonyl group, [4- (2-cyanoethyl) benzyl] aminocarbonyl group, [4- (2-acetoxyethyl) benzyl] aminocarbonyl group A monoaralkylaminocarbonyl group having 8 to 11 carbon atoms, such as

(3) Anilinocarbonyl group, naphthylaminocarbonyl group, toluidinocarbonyl group, xylidinocarbonyl group, ethylanilinocarbonyl group, isopropylanilinocarbonyl group, methoxyanilinocarbonyl group, ethoxyanilinocarbonyl group, chloroaniline Linocarbonyl group, acetylanilinocarbonyl group, methoxycarbonylanilinocarbonyl group, ethoxycarbonylanilinocarbonyl group, propoxycarbonylanilinocarbonyl group, 4-methylanilinocarbonyl group, 4-ethylanilinocarbonyl group, etc. 7-11 monoarylaminocarbonyl groups.

(4) vinylaminocarbonyl group, allylaminocarbonyl group, butenylaminocarbonyl group, pentenylaminocarbonyl group, hexenylaminocarbonyl group, cyclohexenylaminocarbonyl group, octadienylaminocarbonyl group, adamantenylaminocarbonyl group, etc. A monoalkenylaminocarbonyl group having 3 to 11 carbon atoms.

In addition, specific examples in the case where R ^{1 to} R ⁸ are disubstituted aminocarbonyl groups include disubstituted aminocarbonyl groups having the same substituents as in the case of the alkyl group described above. It is group (1)-(5).

(1) Dimethylaminocarbonyl group, diethylaminocarbonyl group, methylethylaminocarbonyl group, dipropylaminocarbonyl group, dibutylaminocarbonyl group, di-n-hexylaminocarbonyl group, dicyclohexylaminocarbonyl group, dioctylaminocarbonyl group, pyrrolidino Carbonyl group, piperidinocarbonyl group, morpholinocarbonyl group, bis (methoxyethyl) aminocarbonyl group, bis (ethoxyethyl) aminocarbonyl group, bis (propoxyethyl) aminocarbonyl group, bis (butoxyethyl) aminocarbonyl group, di (Acetyloxyethyl) aminocarbonyl group, di (hydroxyethyl) aminocarbonyl group, N-ethyl-N- (2-cyanoethyl) aminocarbonyl group, di (propionyloxye) Le) dialkylaminocarbonyl group having a carbon number of 3 to 17, such as an amino group.

(2) Diaralkylaminocarbonyl groups having 15 to 21 carbon atoms such as dibenzylaminocarbonyl group, diphenethylaminocarbonyl group, bis (4-ethylbenzyl) aminocarbonyl group, bis (4-isopropylbenzyl) aminocarbonyl group.

(3) A diarylaminocarbonyl group having 13 to 15 carbon atoms such as a diphenylaminocarbonyl group, a ditolylaminocarbonyl group, and an N-phenyl-N-tolylaminocarbonyl group.

(4) C5-C13 di, such as divinylaminocarbonyl group, diallylaminocarbonyl group, dibutenylaminocarbonyl group, dipentenylaminocarbonyl group, dihexenylaminocarbonyl group, N-vinyl-N-allylaminocarbonyl group Alkenylaminocarbonyl group.

(5) N-phenyl-N-allylaminocarbonyl group, N- (2-acetyloxyethyl) -N-ethylaminocarbonyl group, N-tolyl-N-methylaminocarbonyl group, N-vinyl-N-methylamino A disubstituted aminocarbonyl group having 4 to 11 carbon atoms having a substituent selected from a substituted or unsubstituted alkyl group such as a carbonyl group and an N-benzyl-N-allylaminocarbonyl group, an aralkyl group, an aryl group, and an alkenyl group;

Further, specific examples in the case where R ^{1 to} R ⁸ are substituted or unsubstituted acyloxycarbonyl groups include acyloxycarbonyl groups having the same substituents as in the case of the alkyl groups described above, and preferably formyl Oxy group, methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, n-butylcarbonyloxy group, iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t- Butylcarbonyloxy group, n-pentylcarbonyloxy group, iso-pentylcarbonyloxy group, neopentylcarbonyloxy group, 2-methylbutylcarbonyloxy group, benzoyloxy group, methylbenzoyloxy group, ethylbenzoyloxy group, tolyluca Bonyloxy group, propylbenzoyloxy group, 4-t-butylbenzoyloxy group, nitrobenzylcarbonyloxy group, 3-butoxy-2-naphthoyloxy group, cinnamoyloxy group, ferrocenecarbonyloxy group, 1-methylferrocene-1 And an acyloxy group having 2 to 16 carbon atoms such as a '-carbonyloxy group, a cobaltocenecarbonyloxy group, and a nickelocenecarbonyloxy group.

Further, specific examples in the case where R ^{1 to} R ⁸ are substituted or unsubstituted heteroaryl groups include heteroaryl groups having the same substituents as in the case of the alkyl groups described above. An unsubstituted heteroaryl group represented by (a), or a heteroaryl group substituted by a substituent represented by (b).
(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 group 2-yl group, benzotriazol-1-yl group, purinyl group, quinolinyl group, isoquinolinyl group, coumarinyl group, cinnolinyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group, phenanthronyl group, phenothiazinyl group, flavonyl group Group, phthali Unsubstituted heteroaryl groups such as amide group and naphthylimide group.

(B) Substituent of heteroaryl group (b-1) Halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom;
(B-2) a cyano group;
(B-3) methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, methoxymethyl group, ethoxyethyl group, ethoxyethyl group, trifluoromethyl group, etc. An alkyl group;
(B-4) aralkyl groups such as benzyl group and phenethyl group;
(B-5) aryl groups such as phenyl group, tolyl group, naphthyl group, xylyl group, mesyl group, chlorophenyl group, methoxyphenyl group;
(B-6) 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- Alkoxy groups such as trimethylhexyloxy group, ferrocenemethoxy group, cobaltcenemethoxy group, nickelocenemethoxy group;

(B-7) aralkyloxy groups such as benzyloxy group and phenethyloxy group;
(B-8) aryloxy groups such as phenoxy group, tolyloxy group, naphthoxy group, xylyloxy group, mesityloxy group, chlorophenoxy group, methoxyphenoxy group;
(B-9) Alkenyl groups such as vinyl group, allyl group, butenyl group, butadienyl group, pentenyl group, cyclopentadienyl group, octenyl group;
(B-10) Alkenyloxy groups such as vinyloxy group, allyloxy group, butenyloxy group, butadienyloxy group, pentenyloxy group, cyclopentadienyloxy group, octenyloxy group;
(B-11) Methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, decylthio, methoxymethylthio, ethoxyethylthio, ethoxyethylthio, trifluoromethylthio Alkylthio groups such as
(B-12) aralkylthio groups such as benzylthio group and phenethylthio group;
(B-13) arylthio groups such as phenylthio group, tolylthio group, naphthylthio group, xylylthio group, mesylthio group, chlorophenylthio group, methoxyphenylthio group;

(B-14) Dialkylamino groups such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group;
(B-15) acyl groups such as acetyl group, propionyl group, butanoyl group, ferrocenecarbonyl group, cobaltocenecarbonyl group, nickelocenecarbonyl group;
(B-16) alkoxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a ferrocene methoxycarbonyl group, a 1-methylferrocene-1′-ylmethoxycarbonyl group, a cobaltcenylmethoxycarbonyl group, and a nickelocenylmethoxycarbonyl group;
(B-17) aralkyloxycarbonyl groups such as benzyloxycarbonyl group and phenethyloxycarbonyl group;
(B-18) aryloxycarbonyl groups such as phenoxycarbonyl group, tolyloxycarbonyl group, naphthoxycarbonyl group, xylyloxycarbonyl group, mesyloxycarbonyl group, chlorophenoxycarbonyl group, methoxyphenoxycarbonyl group;

(B-19) Alkenyloxycarbonyl such as vinyloxycarbonyl group, allyloxycarbonyl group, butenyloxycarbonyl group, butadienyloxycarbonyl group, cyclopentadienyloxy group, pentenyloxycarbonyl group, octenyloxycarbonyl group, etc. Group;
(B-20) methylaminocarbonyl group, ethylaminocarbonyl group, propylaminocarbonyl group, butylaminocarbonyl group, pentylaminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group, octylaminocarbonyl group, nonylaminocarbonyl group, A monoalkylaminocarbonyl group having 2 to 10 carbon atoms such as 3,5,5-trimethylhexylaminocarbonyl group and 2-ethylhexylaminocarbonyl group;
(B-21) Dimethylaminocarbonyl group, diethylaminocarbonyl group, dipropylaminocarbonyl group, dibutylaminocarbonyl group, dipentylaminocarbonyl group, dihexylaminocarbonyl group, diheptylaminocarbonyl group, dioctylaminocarbonyl group, piperidinocarbonyl Group, morpholinocarbonyl group, 4-methylpiperazinocarbonyl group, alkylaminocarbonyl group such as C3-C20 dialkylaminocarbonyl group such as 4-ethylpiperazinocarbonyl group.

(B-22) 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 Nil , Carbazolyl group, phenanthridine Roni Lil group, phenothiazinyl group, a heterocyclic group such as Furaboniru group;
(B-23) Metallocenyl groups such as a ferrocenyl group, a cobaltcenyl group, a nickelocenyl group, a ruthenocenyl group, an osmocenyl group, and a titanocenyl group.

L ^{1, L 2,} and examples of the substituents ^{R 9,} R ^{10, R 11} of the optionally substituted methine group represented by ^{L 3} is cyano group; shown in the above ^R 1 to R ⁸ And the same halogen atom as that described above, and a substituted or unsubstituted “alkyl group, aralkyl group, aryl group”.

Examples of the linking group when R ^{1 to} R ¹¹ each form a ring via a linking group include a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a metal atom, and a metalloid atom, and a carbon atom. Examples of a preferable linking group are a group formed by suitably selecting from among them, -O-, -S-, -C (= O)-, or an optionally substituted methylene group, imino group, A metal atom etc. are mentioned, The desired ring can be obtained combining suitably. Examples of the ring formed by the linking group include a chain, planar or steric ring linked by a linking group.

Preferable examples of the linked skeleton include the following (1) to (3).
_{(1) -CH 2 -CH 2 -CH} 2 -CH 2 -, - CH 2 (NO 2) -CH 2 -CH 2 -CH 2 -, - CH (CH 3) -CH 2 -CH 2 -CH 2 _{-, - CH (Cl) -CH} 2 -CH 2 -, etc. (to form an aliphatic fused rings).

_{(2) -CH = CH-CH} = CH -, - C (NO 2) = CH-CH = CH -, - C (CH 3) = CH-CH = CH -, - C (CH 3) = CH- _{CH = CH -, - C (} CH 3) = CH-CH = C (CH 3) -, - C (OCH 3) = CH-CH = C (OCH 3) -, - C (OCH 2 CH 2 CH ( _{CH 3) - (OCH 3)} ) = C (Cl) -C (Cl) = C (OCH 2 CH 2 CH (CH 3) - (OCH 3)) -, - C (OCH 2 CH 2 CH (CH 3 _{) 2) = C (Cl)} -C (Cl) = C (OCH 2 CH 2 CH (CH 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)-and the like (forms an aromatic condensed ring).

(3) —O—CH ₂ —CH ₂ —O—, —O—CH (CH ₃ ) —CH (CH ₃ ) —O—, —COO—CH ₂ —CH ₂ —, —COO—CH ₂ —, _{-CONH-CH 2 -CH 2 -,} - CONH-CH 2 -, - CON (CH 3) -CH 2 -CH 2 -, - CON (CH 3) -CH 2 - ( forming a heterocyclic ring) etc.

ただし、式中、Ｍ′は、Ｆｅ、Ｒｕ、Ｃｏ、Ｎｉ、Ｏｓ又はＭ″Ｒ′_２（ただし、Ｍ″は、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｍｏ、Ｖの何れかを表す。Ｒ′は、ＣＯ、Ｆ、Ｃｌ、Ｂｒ、Ｉ、前述のＲ^１〜Ｒ^８と同様の置換基を有する炭素数１〜１０のアルキル基、アルコキシ基、アリール基、アリールオキシ基、アラルキル基、アラルキルオキシ基の何れかを表す。）の何れかを表す（金属錯体残基を含む複素環を形成する）。

In the formula, M ′ represents Fe, Ru, Co, Ni, Os, or M ″ R ′ ₂ (where M ″ represents any of Ti, Zr, Hf, Nb, Mo, and V). Is CO, F, Cl, Br, I, a C1-C10 alkyl group having the same substituent as R ^{1 to} R ⁸ described above, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group Represents any one of the groups) (forms a heterocyclic ring containing a metal complex residue).

When R ^{1 to} R ¹¹ are each linked to an adjacent substituent via a linking group, preferred combinations of linkage are R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ² and R ⁹ , R ³ and R ⁹ , R ⁴ and R ¹¹ , R ⁵ and R ¹¹ , R ⁶ and R ¹⁰ , R ⁷ and R ^{10 and the} like.

Specific examples in the case where M ¹ is a divalent unsubstituted metal atom include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Sn, Mg, Pb, Hg, Cd, Ba , Ti, Be, Ca and the like.
Specific examples in the case where M ¹ is a divalent metal atom having a ligand include Cu (NH ₃ ) ₂ , Fe (NH ₃ ) ₂ , Fe (pyridine) ₂ , Fe (γ-picoline) ₂ , Fe (tosylmethylisocyanide) _2, Fe (benzyl isocyanide) nitrogen-containing compounds such as ₂ include divalent metal atoms coordinated.

Specific examples in the case where M ¹ is a trivalent metal atom having a substituent include Al—F, Al—Cl, Al—Br, Al—I, Ga—F, Ga—Cl, Ga—Br, and Ga. -I, In-F, In- Cl, In-Br, In-I, Ti-F, Ti-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 (CH 3), Mn (OH), Mn (OCH 3), Mn (OC 6 H 5), Mn [OSi _{(CH 3)} 3], Examples thereof include monosubstituted trivalent metal atoms such as Fe-F, Fe-Cl, Fe-Br, Fe-I, Ru-F, Ru-Cl, Ru-Br, and Ru-I.

Specific examples in the case where M ¹ is a tetravalent metal atom having a substituent include CrCl ₂ , SnF ₂ , SnCl ₂ , SnBr ₂ , SnI ₂ , ZnF ₂ , ZnCl ₂ , ZnBr ₂ , ZnI ₂ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , TiF ₂ , TiCl ₂ , TiBr ₂ , TiI ₂ , Sn (OH) ₂ , Ge (OH) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , TiA ₂ , CrA _{2, SiA 2, SnA 2,} GeA 2, Ti (OA) 2, Cr (OA) 2, Sn (OA) 2, Ge (OA) 2, Ti (SA) 2, Cr (SA) 2, Sn (SA ) ₂ , Ge (SA) ₂ [wherein A represents a substituted or unsubstituted “alkyl group, aryl group, heteroaryl group” similar to those described above for R ^{1 to} R ⁸ . ] Disubstituted tetravalent metal atoms such as

Specific examples in the case where M ¹ is a trivalent or tetravalent metalloid atom having a substituent include BF, B—Cl, B—Br, B—I, B—A, B (OH), B (OA), B [OSi (CH ₃ ) ₃ ] [A is the same as A described above], etc., monosubstituted trivalent metalloid atoms, SiF ₂ , SiCl ₂ , SiBr ₂ , SiI ₂ , Si (OH) ₂ , SiA ₂ , Si (OA) ₂ , Si (SA) ₂ [A is the same as A described above] and the like, and disubstituted tetravalent metalloid atoms.
Specific examples in the case where M ¹ is an oxy metal atom include VO, MnO, TiO and the like.

Among these, preferred as M ¹ are Pd, Cu, Pt, Ni, Co, Rh, Zn, Fe, Fe (pyridine) ₂ , Fe (γ-picoline) ₂ , Fe (tosylmethyl isocyanide) ₂ , Fe ( benzyl _{isocyanide) 2, Fe-F, Fe} -Cl, Fe-Br, Fe-I, VO, TiO, TiA 2, SiA 2, SnA 2, RuA 2, RhA 2, GeA 2, SiA 2, Si (OA) ₂ , Sn (OA) ₂ , Ge (OA) ₂ , Si (SA) ₂ , Sn (SA) ₂ , Ge (SA) ₂ [A is the same as A described above].

In the diazaporphyrin compound represented by the general formula (3), examples of the substituents R ^{12 to} R ¹⁹ on the pyrrole ring include a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, Sulfonic acid group or the halogen atom, alkyl group, aralkyl group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio represented by the aforementioned R ^{1 to} R ⁸ Group, arylthio group, alkenylthio group, monosubstituted amino group, disubstituted amino group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, monosubstituted aminocarbonyl group, disubstituted amino group Carbonyl group, acyloxy group, The same halogen atom as the aryl group, substituted or unsubstituted alkyl group, aralkyl group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group, arylthio group, Alkenylthio group, monosubstituted amino group, disubstituted amino group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, monosubstituted aminocarbonyl group, disubstituted aminocarbonyl group, acyloxy group And a heteroaryl group.

Examples of the substituent of the optionally substituted methine group represented by R ²⁰ and R ²¹ include a cyano group; or the same halogen atom, substituted or the same as those shown in the above R ^{1 to} R ⁸ . An unsubstituted “alkyl group, aralkyl group, aryl group” can be mentioned. In particular, in order to improve solubility and optical properties, the substituents R ²⁰ and R ²¹ are preferably substituted or unsubstituted groups having 1 or more carbon atoms, and more preferably substituted or unsubstituted phenyl groups.
Examples of the ring formed by R ^{12 to} R ¹⁹ via a linking group include the same aliphatic condensed ring, aromatic condensed ring, and heterocyclic ring as those described above for R ^{1 to} R ¹¹ . Can be mentioned.
Examples of the central atom represented by M ² include two hydrogen atoms; or the same divalent unsubstituted or ligand-containing metal atom and substituent as those shown in M ¹ above. And a trivalent or tetravalent metal atom, a semimetal atom, or an oxymetal atom.

In the monoazaporphyrin compound represented by the general formula (4), examples of the substituents R ^{22 to} R ²⁹ on the pyrrole ring include a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, Sulfonic acid group, or halogen atom, alkyl group, aralkyl group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio shown in the above-mentioned R ^{1 to} R ⁸ Group, arylthio group, alkenylthio group, monosubstituted amino group, disubstituted amino group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, monosubstituted aminocarbonyl group, disubstituted amino group Carbonyl group, acyloxy , Halogen atoms similar to heteroaryl groups, substituted or unsubstituted alkyl groups, aralkyl groups, aryl groups, alkenyl groups, alkoxy groups, aralkyloxy groups, aryloxy groups, alkenyloxy groups, alkylthio groups, aralkylthio groups, arylthio Group, alkenylthio group, mono-substituted amino group, di-substituted amino group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, mono-substituted aminocarbonyl group, di-substituted aminocarbonyl group, Examples include an acyloxy group and a heteroaryl group.

Further, examples of the substituent of the optionally substituted methine group represented by R ³⁰ to R ³² is a cyano group; or same halogen atoms as those indicated in R ¹ to R ⁸ mentioned above, substituted or Examples thereof include an unsubstituted alkyl group, an aralkyl group, and an aryl group.
Examples of the ring formed by R ^{22 to} R ³² via a linking group include the same aliphatic condensed ring, aromatic condensed ring, and heterocyclic ring as those described above for R ^{1 to} R ¹¹ . .
Examples of the central atom represented by M ³ include two hydrogen atoms; or the same divalent unsubstituted or ligand-containing metal atom and substituent as those shown in M ¹ above. A trivalent or tetravalent metal atom, a semimetal atom, or an oxymetal atom is exemplified.

In the azaporphyrin compound represented by the general formula (5), examples of the substituents R ^{33 to} R ⁴⁴ on the pyrrole ring include a halogen atom, a hydroxyl group, or a halogen atom shown in the aforementioned R ^{1 to} R ⁸ . , An alkyl group, an aryl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an alkenyloxy group, an alkylthio group, an arylthio group, a halogen atom similar to a heteroaryl group, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group Aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, arylthio group, and heteroaryl group.
Examples of the ring formed by each of R ^{33 to} R ⁴⁴ via a linking group include the same aliphatic condensed ring, aromatic condensed ring and heterocyclic ring as those described above for R ^{1 to} R ¹¹ . .
Examples of the central atom represented by M ⁴ include two hydrogen atoms; or the same divalent unsubstituted or ligand-containing metal atom and substituent as those described for M ¹ above. A trivalent or tetravalent metal atom, a semimetal atom, or an oxymetal atom is exemplified.

In the azaporphyrin compound represented by the general formula (6), examples of the substituents R ^{45 to} R ⁵⁶ on the pyrrole ring include a halogen atom, a hydroxyl group, or a halogen atom shown in the aforementioned R ^{1 to} R ⁸ . , An alkyl group, an aryl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an alkenyloxy group, an alkylthio group, an arylthio group, a halogen atom similar to a heteroaryl group, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group Aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, arylthio group, and heteroaryl group.
Examples of the ring formed by each of R ^{45 to} R ⁵⁶ via a linking group include the same aliphatic condensed ring, aromatic condensed ring and heterocyclic ring as those described above for R ^{1 to} R ¹¹ . .
Examples of the central atom represented by M ⁵ include two hydrogen atoms; or the same divalent unsubstituted or ligand-containing metal atom or substituent as shown in M ¹ above. A trivalent or tetravalent metal atom, a semimetal atom, or an oxymetal atom is exemplified.

In the azaporphyrin compound represented by the general formula (7), examples of the substituents R ^{57 to} R ⁶⁸ on the pyrrole ring include a halogen atom, a hydroxyl group, or a halogen atom shown in the aforementioned R ^{1 to} R ⁸ . , An alkyl group, an aryl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an alkenyloxy group, an alkylthio group, an arylthio group, a halogen atom similar to a heteroaryl group, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group Aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, arylthio group, and heteroaryl group.
Examples of the ring formed by each of R ^{57 to} R ⁶⁸ via a linking group include the same aliphatic condensed ring, aromatic condensed ring and heterocyclic ring as those described above for R ^{1 to} R ¹¹ . .
Examples of the central atom represented by M ⁶ include two hydrogen atoms; or the same divalent unsubstituted or ligand-containing metal atom and substituent as those shown in the aforementioned M ¹ A trivalent or tetravalent metal atom, a semimetal atom, or an oxymetal atom is exemplified.

In the azaporphyrin compound represented by the general formula (8), examples of the substituents R ^{69 to} R ⁸⁰ on the pyrrole ring include a halogen atom, a hydroxyl group, or a halogen atom shown in the aforementioned R ^{1 to} R ⁸ . , An alkyl group, an aryl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an alkenyloxy group, an alkylthio group, an arylthio group, a halogen atom similar to a heteroaryl group, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group Aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, arylthio group, and heteroaryl group.
Examples of the ring formed by R ^{69 to} R ⁸⁰ via a linking group include the same aliphatic condensed ring, aromatic condensed ring, and heterocyclic ring as those described above for R ^{1 to} R ¹¹ . .
Examples of the central atom represented by M ⁷ include two hydrogen atoms; or the same divalent unsubstituted or ligand-containing metal atom and substituent as those shown in M ¹ above. A trivalent or tetravalent metal atom, a semimetal atom, or an oxymetal atom is exemplified.

  The method for producing the azaporphyrin-based compound as described above is not particularly limited. For example, in the case of the compound (3), J.P. Chem. Soc. (C), 22-29 (1996), J. MoI. Biochem. 121, 654-660 (1997), Z. Physiol. Chem, 214, 145 (1933), Die Chemie des Pyrrols, Band II, Halfte 2, pp. 411-414, Academische Verlagesellschuft, Leipzig (1940), etc.

Typically, it can be produced by the following three-stage reaction.
First, in the first step, a dipyrromethane compound represented by the following general formula (A) and the following general formula (B) is brominated in a carboxylic acid solvent such as acetic acid or a halogenated hydrocarbon solvent such as methylene chloride. , Iodine, N-bromosuccinimide, N-iodosuccinimide and the like, and halogenated with a halogenating agent to obtain dipyrromethene compounds represented by the following general formula (C) and the following general formula (D), respectively.

ただし、式中、Ｒ^１２〜Ｒ^２１は、前記一般式（３）のＲ^１２〜Ｒ^２１とそれぞれ同一の基を表し、ｒは水素原子又はカルボキシル基を表す。

ただし、式中、Ｒ^１２〜Ｒ^２１は、前記一般式（３）のＲ^１２〜Ｒ^２１とそれぞれ同一の基を表し、ａはハロゲン原子を表す。

ただし、前記一般式（Ｃ）及び（Ｄ）中、Ｒ^１２〜Ｒ^２１は、前記一般式（３）のＲ^１２〜Ｒ^２１とそれぞれ同一の基を表し、ａはハロゲン原子を表す。

In the ^formula, R 12 ^{to R 21} are respectively a ^R 12 ^{to R 21} in the general formula (3) represent the same group, r represents a hydrogen atom or a carboxyl group.

In the ^formula, R 12 ^{to R 21} each represent a same group as ^R 12 ^{to R 21} in the general formula (3), a represents a halogen atom.

However, in said general formula (C) and (D), R < ¹² > -R < ²¹ > represents the same group as R < ¹² > -R < ²¹ > of the said general formula (3), respectively, and a represents a halogen atom.

  Next, in the second step, the dipyrromethene compound represented by the general formula (C) and the general formula (D) is respectively an alcohol solvent such as ethanol and / or an organic solvent such as an amide solvent such as dimethylformamide. In the presence of an oxidizing agent such as air, using a metal or metalloid compound such as an inorganic salt such as a metal or metalloid sulfate, nitrate or halide, or an organic metal salt such as acetate or acetylacetonate, or By reacting in the absence, a dipyrromethene metal complex represented by the general formula (E) is obtained.

ただし、式中、Ｒ^１２〜Ｒ^２１及びａは、前記一般式（３）のＲ^１２〜Ｒ^２１及びａとそれぞれ同一の基を表す。Ｍ^２は、前記一般式（３）のＭ^２と同一の意味を表す。

In the ^formula, R 12 ^{to R 21} and a represent the ^R 12 ^{to R 21} and a respectively identical groups of the formula (3). M ² represents the same meaning as ^{M 2} in the general formula (3).

Next, in the third stage, the dipyrromethene metal complex (general formula (E)) is reacted with an azide salt such as sodium azide in an organic solvent such as an alcohol solvent such as ethanol and / or an amide solvent such as dimethylformamide. By doing so, the diazaporphyrin compound of the present invention represented by the general formula (3) can be obtained.
Here, the dipyrromethene compound represented by the general formula (C) and the general formula (D) obtained in the first stage is respectively in an organic solvent such as an alcohol solvent such as ethanol and / or an amide solvent such as dimethylformamide. In the presence or absence of an oxidizing agent such as air, using an inorganic salt such as a metal or metalloid sulfate, nitrate, halide, or an organic metal salt such as acetate or acetylacetonate, A compound of the general formula (3) can also be obtained by reacting with an azide salt such as sodium azide.
Further, the metal-free diazaporphyrin compound represented by the general formula (3) [M is two hydrogen atoms] is obtained by converting a dipyrromethene compound represented by the general formulas (7) and (8) into an alcohol type such as methanol. Reaction with sodium azide or the like in an organic solvent such as a solvent and / or an amide solvent such as dimethylformamide, or trifluoroacetic acid or the like in a solvent such as chloroform with a metal complexed compound of formula (2) It can be obtained by reacting with an organic acid.

  Specific examples of the diazaporphyrin compound represented by the general formula (3) include compounds (1-1) to (1-65) having substituents described in Tables 8 to 12. .

ただし、前記一般式（１７）中、Ａ^１〜Ａ^４、及びＢ^１〜Ｂ^８は、水素原子、アルキル基、シクロアルキル基、フェニル基のいずれかを表す。Ｂ^ｎとＢ^ｎ＋１（ただしｎ＝１、３、５、７）は、Ｃ_４Ｈ_４残基を介して環状に結合してもよい。Ｍは２個又は４個のプロトン或いは１個の金属原子を表す。
これらの中でも、下記一般式（１８）で表される化合物が好ましく、特に下記一般式（１９）で表される化合物が好ましい。 Moreover, as a preferable porphyrin, the compound represented by following General formula (17) is mentioned.

In the general formula ^{(17), A 1 ~A 4} , and ^B 1 .about.B ⁸ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a phenyl group. B ⁿ and B ^{n + 1} (where n = 1, 3, 5, 7) may be linked cyclically via a C ₄ H ₄ residue. M represents 2 or 4 protons or 1 metal atom.
Among these, the compound represented by the following general formula (18) is preferable, and the compound represented by the following general formula (19) is particularly preferable.

ただし、前記一般式（１８）中、Ｒ_１は水素原子、メチル基、アリル基、又はフェニル基を表す。Ｒ_２は水素原子、メチル基、アリル基、フェニル基、メトキシフェニル基、トリル基、ニトロ基、アミノ基、又はシアノ基を表す。Ｒ_３は水素原子、メチル基、ハロゲン原子、アリル基、フェニル基、メトキシフェニル基、トリル基、ニトロ基、アミノ基、又はシアノ基を表す。Ｍは２個又は４個のプロトン或いはＭｎ、Ｃｏ、Ｎｉ、Ｃｕ及びＺｎから選択される２価の金属を表す。

In the general formula (18), R ₁ represents a hydrogen atom, a methyl group, an allyl group, or a phenyl group. R ₂ represents a hydrogen atom, a methyl group, an allyl group, a phenyl group, a methoxyphenyl group, a tolyl group, a nitro group, an amino group, or a cyano group. R ₃ represents a hydrogen atom, a methyl group, a halogen atom, an allyl group, a phenyl group, a methoxyphenyl group, a tolyl group, a nitro group, an amino group, or a cyano group. M represents a divalent metal selected from 2 or 4 protons or Mn, Co, Ni, Cu and Zn.

ただし、前記一般式（１９）中、Ａ^１〜Ａ^４は、水素原子又はフェニル基を表す。Ｍは、２個又は４個のプロトン或いはＺｎを表す。

In the general formula ^(19), A 1 ~A ⁴ represents a hydrogen atom or a phenyl group. M represents 2 or 4 protons or Zn.

  In addition, for example, azo dyes represented by the following general formulas and organic dyes represented by the following general formulas (I) to (V) have a large degree of modulation, and good recording can be achieved.

ただし、前記一般式（Ｉ）及び（ＩＩ）中、Ａは置換基を有していてもよい芳香環を表し、ＢはＯＨ以外の置換基を有していてもよい芳香環を表す。ｎは１〜３の整数、ｍは２〜６の整数を表す。Ｌは置換されてもよい２価の連結基または単結合を表す。ＶはＬ以外に置換基を有していてもよい芳香環を表す。

However, in said general formula (I) and (II), A represents the aromatic ring which may have a substituent, and B represents the aromatic ring which may have substituents other than OH. n represents an integer of 1 to 3, and m represents an integer of 2 to 6. L represents a divalent linking group or a single bond which may be substituted. V represents an aromatic ring which may have a substituent other than L.

ただし、前記一般式（ＩＩＩ）及び（ＩＶ）中、Ｒ^１及びＲ^２は互いに同一であっても異なっていてもよい置換基を表し、ｐ及びｑは０乃至３の整数を表す。ｍは２〜６の整数を表す。Ｌは置換されてもよい２価の連結基または単結合を表す。ＶはＬ以外に置換基を有していてもよい芳香環を表す。

However, in said general formula (III) and (IV), R < ¹ > and R < ² > represents the substituent which may mutually be same or different, p and q represent the integer of 0-3. m represents an integer of 2 to 6. L represents a divalent linking group or a single bond which may be substituted. V represents an aromatic ring which may have a substituent other than L.

ただし、前記一般式（Ｖ）中、Ｒ^１及びＲ^２は互いに同一であっても異なっていてもよい置換基を表し、ｐ及びｑは０乃至３の整数を表す。ｍは２または３の整数を表す。Ｖは置換基を有していてもよい芳香環を表す。

However, in said general formula (V), R < ¹ > and R < ² > represents the substituent which may mutually be same or different, p and q represent the integer of 0 thru | or 3. m represents an integer of 2 or 3. V represents an aromatic ring which may have a substituent.

    As an organic pigment | dye represented by the said general formula (I), the compounds 1-20 represented by the following structural formula are mentioned suitably, for example.

  As an organic pigment | dye represented by the said general formula (III), the compounds 21-34 represented by the following structural formula are mentioned suitably, for example.

  As an organic pigment | dye represented by the said general formula (II) or (IV), the compounds 35-40 represented by the following structural formula are mentioned suitably, for example.

Moreover, 1 type, or 2 or more types of pigment | dye materials selected from the said organic pigment | dye group can also be disperse | distributed and used in resin.
Examples of the resin that can disperse the organic dye include polyester resins, polyether resins, polystyrene resins, polyurethane resins, cellulose resins, fatty acid resins, gelatin, cellulose derivatives, dextran, rosin, rubber, and other natural organic polymer substances; polyethylene Hydrocarbon resins such as polypropylene and polyisobutylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride and polyvinyl chloride / polyvinyl acetate copolymers; acrylic resins such as polymethyl acrylate and polymethyl methacrylate; Examples thereof include polyvinyl alcohol, chlorinated polyethylene, phenol resin, fluorine resin, silicone resin, polyamide resin, epoxy resin, butyral resin, rubber derivative, and the like.
The amount of the resin used is preferably 0.01 to 50 times (mass ratio), more preferably 0.1 to 5 times the amount of the organic dye. It is possible to improve the storage stability of the recording layer by incorporating the resin into the recording layer.

  The recording layer can contain various anti-fading agents in order to improve the light resistance of the recording layer. As the antifading agent, for example, a singlet oxygen quencher is suitable. Examples of the singlet oxygen quencher include JP-A Nos. 58-175893, 59-81194, 60-18387, 60-19586, 60-19587, and 60-35054. Publication No. 60-36190 Publication No. 60-36191 Publication No. 60-44554 Publication No. 60-44555 Publication No. 60-44389 Publication No. 60-44390 Publication No. 60-54892 Publication No. 60-54892 Publication No. JP-A-60-47069, JP-A-63-209995, JP-A-4-25492, JP-B-1-38680, JP-A-6-26028, etc., German Patent Invention No. 350399 No. specification, Journal of the Chemical Society of Japan, October 1992, page 1141, and the like.

  The content of the antifading agent such as the singlet oxygen quencher is generally preferably 0.1 to 50% by mass, more preferably 0.5 to 45% by mass, based on the total solid content of the recording layer. 40 mass% is still more preferable, and 5-25 mass% is especially preferable.

  The recording layer is prepared by dissolving the organic dye and, if necessary, a binder and an anti-fading agent in an appropriate solvent to prepare a recording layer coating solution. After coating on the surface to form a coating film, it can be formed by drying. Furthermore, various additives such as an antioxidant, a UV absorber, a plasticizer, and a lubricant may be appropriately added to the recording layer coating liquid according to the purpose. In addition, as a method for dissolving the organic dye or the binder, methods such as ultrasonic treatment, homogenizer treatment, disper treatment, sand mill treatment, stirrer stirring treatment, and the like can be applied.

  Examples of the solvent for the coating solution in the recording layer include esters such as butyl acetate and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chloroform; Amides such as formamide; Hydrocarbons such as cyclohexane; Ethers such as tetrahydrofuran, ethyl ether and dioxane; Alcohols such as ethanol, n-propanol, isopropanol, n-butanol and diacetone alcohol; 2,2,3,3-tetrafluoro Fluorine solvents such as propanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, etc. That. The said solvent may be used independently in consideration of the solubility of the organic dye to be used and the binder, and two or more kinds may be used in combination as appropriate.

  The concentration of the organic dye in the recording layer coating solution is preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass.

  Examples of the method for applying the recording layer-requiring liquid include a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, and a screen printing method. Moreover, as said application | coating temperature, 18-40 degreeC is preferable, 20-40 degreeC is more preferable, and 20-30 degreeC is still more preferable.

  The recording layer may be a single layer or a multilayer, and the thickness of the recording layer is preferably 20 to 500 nm, more preferably 30 to 150 nm. If the layer thickness is less than 20 nm, the recording layer is thin, so that defects occur and it is inappropriate. If it exceeds 500 nm, the volume becomes too large and good recording may not be possible.

A barrier layer may be formed on the surface of the recording layer in order to improve adhesion to the surface protective layer and dye storage stability. Examples of the material of the barrier layer include inorganic materials such as oxides, nitrides, carbides, sulfides, and the like composed of any one or more of Zn, Si, Ti, Te, Sm, Mo, Ge, and the like, and photocurability. It can be formed using an organic material such as a resin. In addition, it may be hybrid as ZnS-SiO _2.
The protective layer made of the inorganic material can be formed by a vacuum film forming method. The protective layer made of the organic material can be formed by spin-coating a photocurable resin film (for example, SD1700, SD318, SD301 manufactured by Dainippon Ink & Chemicals, Inc.) and then irradiating resin curing light.
There is no restriction | limiting in particular in the thickness of the said barrier layer, According to the objective, it can select suitably, 1-100 nm is preferable.
In order to increase the density, when using a lens with a high NA (Numerical Aperture), the barrier layer needs to be light transmissive.
When the NA is increased, it is necessary to reduce the thickness of the portion through which the reproduction laser beam is transmitted. This is due to the angle at which the disk surface deviates from the optical axis of the optical pickup as the NA increases (so-called tilt angle, proportional to the square of the product of the reciprocal of the wavelength of the light source and the numerical aperture of the objective lens). This is because the allowable amount of generated aberration is reduced, and this tilt angle is easily affected by the aberration due to the thickness of the substrate.
Therefore, it is necessary to reduce the thickness of the substrate so that the influence of aberration on the tilt angle is as small as possible.

-Surface protective layer-
The surface protective layer 8 is formed on the surface on the recording layer side using an adhesive or an adhesive (via an adhesive layer or an adhesive layer). The surface protective layer preferably has a transmittance of 80% or more, more preferably 90% or more, with respect to laser light used for recording and reproduction. The surface protective layer is preferably a resin sheet having a surface roughness Ra of 5 nm or less. The surface roughness Ra of the surface protective layer is the type of resin, the film forming method, the presence or absence of a filler to be contained, and the like. It depends on. Here, the surface roughness Ra of the surface protective layer is measured by, for example, HD2000 manufactured by WYKO.
Examples of the resin sheet include polycarbonate (manufactured by Teijin Ltd., Pure Ace, Teijin Chemicals Ltd., Panlite), cellulose acetate, (manufactured by Fujifilm Corporation, Fujitac), polyethylene terephthalate (PET) (Toray Industries, Inc.) (Manufactured by Lumiller) and the like. Among these, polycarbonate and cellulose triacetate are more preferable.

  The thickness of the surface protective layer is appropriately determined depending on the wavelength and NA of the laser beam irradiated for recording and reproduction, but is preferably 0.03 to 0.15 mm, and 0.05 to 0.12 mm. More preferred. The total thickness of the surface protective layer, the adhesive layer, and the adhesive layer is preferably 0.09 to 0.11 mm, and more preferably 0.095 to 0.105 mm.

  For example, a UV curable resin, an EB curable resin, a thermosetting resin, or the like is preferably used as the adhesive, and in particular, a UV curable resin is preferably used. For example, a predetermined amount of the adhesive is applied onto the bonding surface (recording layer or the like) of the laminate, and after the resin sheet is bonded, the adhesive is uniformly applied between the laminate and the resin sheet by spin coating. It is preferable to spread and harden. 0.1-100 micrometers is preferable, as for the thickness of the contact bonding layer finally formed, 0.5-50 micrometers is more preferable, and 10-30 micrometers is still more preferable.

  When a UV curable resin is used as the adhesive, the UV curable resin may be used as it is or dissolved in an appropriate solvent such as methyl ethyl ketone or ethyl acetate to prepare a coating solution, which may be supplied from the dispenser to the laminate surface. Good. Further, in order to prevent warpage of the produced optical information recording medium, it is preferable that the UV curable resin constituting the adhesive layer has a small curing shrinkage rate. Examples of the UV curable resin include “SD-640” (manufactured by Dainippon Ink & Chemicals, Inc.).

In addition, any UV irradiator used for curing these UV curable resins can be used. For example, a pulsed UV irradiator is suitable. Here, as the UV irradiation condition, the pulse interval is preferably 1 msec or less, and more preferably 1 μsec or less. The irradiation watt one pulse is not particularly limited and may be suitably selected according to the purpose, preferably 3 kW / cm ² or less, 2 kW / cm ² or less being more preferred. Furthermore, the number of times of UV irradiation is not particularly limited and can be appropriately selected according to the purpose, preferably 20 times or less, and more preferably 10 times or less.

  As the pressure-sensitive adhesive, for example, an acrylic-based, rubber-based, or silicone-based pressure-sensitive adhesive can be used. From the viewpoint of transparency and durability, an acrylic pressure-sensitive adhesive is preferable. As such an acrylic pressure-sensitive adhesive, 2-ethylhexyl acrylate, n-butyl acrylate and the like are the main components, and in order to improve cohesion, short-chain alkyl acrylates and methacrylates such as methyl acrylate, ethyl acrylate, and methyl methacrylate are used. And acrylic acid, methacrylic acid, acrylamide derivatives, maleic acid, hydroxylethyl acrylate, glycidyl acrylate, and the like, which can be crosslinking points with the crosslinking agent, are preferably used. The glass transition temperature (Tg) and the crosslinking density can be changed by appropriately adjusting the mixing ratio and type of the main component, the short chain component, and the component for adding a crosslinking point.

  As a crosslinking agent used together with the said adhesive, an isocyanate type crosslinking agent is mentioned, for example. Examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluidine isocyanate, isophorone diisocyanate, triphenylmethane triisocyanate. Isocyanates such as isocyanate, products of these isocyanates and polyalcohols, and polyisocyanates formed by condensation of isocyanates can be used.

  Commercially available products of these isocyanates include Coronate L, Coronate HL, Coronate 2030, Coronate 2031, Millionate MR, Millionate HTL manufactured by Nippon Polyurethane Co., Ltd .; Takenate D-102, Takenate manufactured by Takeda Pharmaceutical Company Limited. D-110N, Takenate D-200, Takenate D-202; Death Module L, Death Module IL, Death Module N, Death Module HL;

  In addition, it is preferable to form an undercoat layer on the substrate surface on the side where the reflective layer is provided for the purpose of improving flatness and adhesion. Examples of the material for the undercoat layer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleic anhydride copolymer, polyvinyl alcohol, N-methylol acrylamide, styrene / vinyl toluene copolymer, chloro. Polymer materials such as sulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate, etc .; silane coupling Surface modifiers such as agents; and the like.

  The undercoat layer is prepared by dissolving or dispersing the above materials in an appropriate solvent to prepare a coating solution, and then applying the coating solution to the substrate surface by a coating method such as spin coating, dip coating, or extrusion coating. Can be formed. There is no restriction | limiting in particular in the layer thickness of the said undercoat layer, According to the objective, it can select suitably, 0.005-20 micrometers is preferable and 0.01-10 micrometers is more preferable.

  The optical information recording medium of the present invention may further include various intermediate layers in addition to the above-mentioned arbitrary layers. For example, an intermediate layer for improving reflectance and adhesion may be provided between the reflective layer and the recording layer. As the material for the intermediate layer, the materials listed so far can be appropriately used according to the purpose.

  The surface roughness on the laser light incident side of the optical information recording medium of the present invention is the surface roughness of the surface protective layer used, the surface roughness of the substrate, the creation conditions of the reflective layer, the type of the recording layer, and the film formation conditions. The type of the adhesive layer, the coating conditions, the type of the surface protective layer, and the coating conditions are appropriately selected.

(Recording and playback method)
In the recording / reproducing method of the present invention, at least one of information recording and reproducing is performed by irradiating a laser beam having an oscillation wavelength of 500 nm or less from the surface protective layer side in the optical information recording medium of the present invention.
Specifically, a blue-violet laser (from the surface protective layer side through the objective lens while rotating the optical information recording medium at a predetermined linear velocity (0.5 to 10 m / second) or a predetermined constant angular velocity ( For example, recording light having a wavelength of 405 nm is irradiated. By this irradiation light, the recording layer absorbs the light and the temperature rises locally. For example, information is recorded by generating pits and changing their optical characteristics. The information recorded as described above is reproduced by irradiating a blue-violet laser beam from the surface protective layer side while rotating the optical information recording medium at a predetermined constant linear velocity and detecting the reflected light. Can do.

  Examples of the laser light source having an oscillation wavelength of 500 nm or less include a blue-violet semiconductor laser having an oscillation wavelength in the range of 390 to 415 nm, a blue-violet SHG laser having a central oscillation wavelength of 425 nm, and the like. In order to increase the recording density, the NA (numerical aperture) of the objective lens used for the pickup is preferably 0.7 or more, more preferably 0.80 or more, and further preferably 0.85 or more.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

  In the following examples, the pre-format cross-sectional shape of the reflective layer, the film thickness of the reflective layer, and the film thickness of the recording layer are obtained by cleaving the produced optical information recording medium in the rack transverse direction. The measurement was performed using an electron microscope (TEM) (trade name: JEM2010, manufactured by JEOL Ltd.) and an atomic force microscope (AFM) (trade name: SPI3800N type, manufactured by Seiko Instruments Inc.).

(Example 1)
-Production of optical information recording media-
First, a polycarbonate resin substrate having a thickness of 1.1 mm, an outer diameter of 120 mm, an inner diameter of 15 mm and a spiral groove (groove depth of 45 nm, half-value width of 150 nm, track pitch of 320 nm) was produced by injection molding.
On the surface having the groove of the substrate, a reflective layer made of aluminum (Al: purity 99.9% by mass or more) was formed by DC sputtering in an Ar atmosphere so as to have a thickness of 95 nm. The sputtering conditions were an Ar flow rate of 5 sccm, a sputtering power of 1.6 kW, and a film formation time of 4 seconds.

As shown in FIG. 2, the cross-sectional shape of the obtained reflective layer in the track transverse direction is CL = 180 nm, BL = 112 nm, UL = 85 nm, depth (d1) = 45 nm, depth (d2) = 40 nm, angle (Θ ₁ ) = 55 ° and angle (θ ₂ ) = 49 °.

Next, a phthalocyanine dye represented by the following structural formula on the reflective layer is mixed with THF (tetrahydrofuran), ethylcyclohexane, IPA (isopropyl alcohol), and 1-methoxy-2-propanol at a mixing ratio of 17: 39: 15: 29 ( The recording layer was formed by spin coating so as to have a thickness of 60 nm.
This phthalocyanine dye is a dye material exhibiting a reflectance of 8% or more at a wavelength λ = 405 ± 20 nm, and a reflectance of 4% or more was obtained in the range of a film thickness of 5 to 150 nm.

  The position of the reflection maximum at λ = 500 nm or less after film formation of the dye was λ = 405 nm. Further, since the laser light wavelength has a width of λ = 405 ± 20 nm due to environmental conditions such as temperature and manufacturing variations, the reflectance in these wavelength ranges needs to be 4% or more. If it is less than 4%, the reflectance decreases and tracking may not be performed satisfactorily.

ただし、前記構造式中、中心金属Ｍは、ＶＯを表す。４個のＲは、Ｃ_６Ｈ_５−（ＣＦ_３）_２Ｃ−Ｏ−を表す。

However, in the structural formula, the central metal M represents VO. Four R _{is, C 6 H 5 - (CF} 3) 2 represents a C-O-.

After forming the recording layer, an annealing treatment was performed at 100 ° C. for 15 minutes. Thereafter, a barrier layer made of ZnS—SiO ₂ (ZnS: SiO ₂ = 8: 2 (mass ratio)) was formed on the recording layer so as to have a thickness of 50 nm by RF sputtering. The barrier layer was formed under the conditions of a power of 4 kW, a pressure of 2 × 10 ⁻² Pa, and a time of 10 seconds.

  Next, a UV curable adhesive (Dainippon Ink Co., Ltd., SD-661) is applied on the barrier layer at a rotational speed of 100 to 300 rpm by a spin coating method to form an adhesive layer, and polycarbonate is formed on the adhesive layer. Sheets (manufactured by Teijin Ltd., Pure Ace, film thickness of 80 μm) were overlapped, and the adhesive was spread while changing to 300 to 4000 rpm. At this time, the thickness of the adhesive layer was 20 μm, and the total thickness of the polycarbonate sheet (surface protective layer) and the adhesive layer was 100 μm. Thus, the optical information recording medium of Example 1 was produced.

(Examples 2-6 and Comparative Examples 1-5)
For Examples 2 to 6 and Comparative Examples 1 to 5, an undercoat layer is formed on the substrate surface on the side where the reflective layer is provided in Example 1 under appropriate conditions, and a reflective layer is formed on the undercoat layer Thus, cross-sectional shapes in the cross-track direction of different reflective layers were prepared. Specifically, a 2.5 mass% polyvinyl alcohol aqueous solution was spin-coated at different rotation speeds, and the shape of the recesses was variously changed to form a reflective layer on the recesses. Table 13 shows the cross-sectional shape of the obtained reflective layer in the track crossing direction.

(Example 7)
-Production of optical information recording media-
In Example 1, except that a reflective layer made of an aluminum alloy (the content of Ta and Cr in (Al—Ta, Al—Cr) is both 2 atomic%) was formed to a thickness of 100 nm. In the same manner as in Example 1, an optical information recording medium was produced.
As shown in FIG. 2, the cross-sectional shape of the reflective layer in the obtained optical information recording medium in the cross-track direction is CL = 180 nm, BL = 112 nm, UL = 85 nm, depth (d1) = 45 nm, depth (d2 ) = 40 nm, angle (θ ₁ ) = 55 °, angle (θ ₂ ) = 50 °.

(Example 8)
-Production of optical information recording media-
An optical information recording medium was prepared in the same manner as in Example 1 except that the dye was replaced with a compound represented by the following structural formula as an azo dye.
As shown in FIG. 2, the cross-sectional shape of the reflective layer in the obtained optical information recording medium in the cross-track direction is CL = 180 nm, BL = 112 nm, UL = 85 nm, depth (d1) = 45 nm, depth (d2 ) = 40 nm, angle (θ ₁ ) = 55 °, angle (θ ₂ ) = 49 °.

Example 9
An optical information recording medium was prepared in the same manner as in Example 1, except that the dye was replaced with the compound 1 represented by [Chemical Formula 49] as the dye represented by the following general formula (I).
As shown in FIG. 2, the cross-sectional shape of the reflective layer in the obtained optical information recording medium in the cross-track direction is CL = 180 nm, BL = 112 nm, UL = 85 nm, depth (d1) = 45 nm, depth (d2 ) = 40 nm, angle (θ ₁ ) = 55 °, angle (θ ₂ ) = 49 °.

(Example 10)
An optical information recording medium was produced in the same manner as in Example 1, except that the dye was replaced with the compound 6 represented by [Chemical Formula 49] as the dye represented by the general formula (I).
As shown in FIG. 2, the cross-sectional shape of the reflective layer in the obtained optical information recording medium in the cross-track direction is CL = 180 nm, BL = 112 nm, UL = 85 nm, depth (d1) = 45 nm, depth (d2 ) = 40 nm, angle (θ ₁ ) = 55 °, angle (θ ₂ ) = 49 °.

(Example 11)
An optical information recording medium was produced in the same manner as in Example 1, except that the dye was replaced with the compound 17 shown in [Chemical Formula 50] as the dye represented by the above general formula (I).
As shown in FIG. 2, the cross-sectional shape of the reflective layer in the obtained optical information recording medium in the cross-track direction is CL = 180 nm, BL = 112 nm, UL = 85 nm, depth (d1) = 45 nm, depth (d2 ) = 40 nm, angle (θ ₁ ) = 55 °, angle (θ ₂ ) = 49 °.

(Example 12)
An optical information recording medium was produced in the same manner as in Example 1, except that the dye was replaced with the compound 21 represented by [Chemical Formula 52] as the dye represented by the following general formula (III).
As shown in FIG. 2, the cross-sectional shape of the reflective layer in the obtained optical information recording medium in the cross-track direction is CL = 180 nm, BL = 112 nm, UL = 85 nm, depth (d1) = 45 nm, depth (d2 ) = 40 nm, angle (θ ₁ ) = 55 °, angle (θ ₂ ) = 49 °.

(Example 13)
An optical information recording medium was produced in the same manner as in Example 1, except that the dye was replaced with the compound 38 represented by [Chemical Formula 55] as the dye represented by the following general formulas (II) and (IV). .
As shown in FIG. 2, the cross-sectional shape of the reflective layer in the obtained optical information recording medium in the cross-track direction is CL = 180 nm, BL = 112 nm, UL = 85 nm, depth (d1) = 45 nm, depth (d2 ) = 40 nm, angle (θ ₁ ) = 55 °, angle (θ ₂ ) = 49 °.

(Example 14)
An optical information recording medium was produced in the same manner as in Example 1, except that the dye was replaced with a compound represented by the following structural formula as a phthalocyanine dye.
As shown in FIG. 2, the cross-sectional shape of the reflective layer in the obtained optical information recording medium in the cross-track direction is CL = 180 nm, BL = 112 nm, UL = 85 nm, depth (d1) = 45 nm, depth (d2 ) = 40 nm, angle (θ ₁ ) = 55 °, angle (θ ₂ ) = 49 °.

ただし、前記構造式中、中心金属ＭはＶＯを表す。Ｒは下記構造式を表す。

However, in the structural formula, the central metal M represents VO. R represents the following structural formula.

(Example 15)
An optical information recording medium was produced in the same manner as in Example 1, except that the dye was replaced with a compound represented by the following structural formula as a phthalocyanine dye.
As shown in FIG. 2, the cross-sectional shape of the reflective layer in the obtained optical information recording medium in the cross-track direction is CL = 180 nm, BL = 112 nm, UL = 85 nm, depth (d1) = 45 nm, depth (d2 ) = 40 nm, angle (θ ₁ ) = 55 °, angle (θ ₂ ) = 49 °.

ただし、前記構造式中、中心金属ＭはＶＯを表す。Ｒは下記構造式を表す。

However, in the structural formula, the central metal M represents VO. R represents the following structural formula.

(Example 16)
An optical information recording medium was produced in the same manner as in Example 1, except that the dye was replaced with a compound represented by the following structural formula as a phthalocyanine dye.
As shown in FIG. 2, the cross-sectional shape of the reflective layer in the obtained optical information recording medium in the cross-track direction is CL = 180 nm, BL = 112 nm, UL = 85 nm, depth (d1) = 45 nm, depth (d2 ) = 40 nm, angle (θ ₁ ) = 55 °, angle (θ ₂ ) = 49 °.

ただし、前記構造式中、中心金属ＭはＶＯを表す。Ｒは下記構造式を表す。

However, in the structural formula, the central metal M represents VO. R represents the following structural formula.

(Example 17)
An optical information recording medium was produced in the same manner as in Example 1, except that the dye was replaced with a compound represented by the following structural formula as a phthalocyanine dye.
As shown in FIG. 2, the cross-sectional shape of the reflective layer in the obtained optical information recording medium in the cross-track direction is CL = 180 nm, BL = 112 nm, UL = 85 nm, depth (d1) = 45 nm, depth (d2 ) = 40 nm, angle (θ ₁ ) = 55 °, angle (θ ₂ ) = 49 °.

ただし、前記構造式中、中心金属ＭはＶＯを表す。Ｒは下記構造式を表す。

However, in the structural formula, the central metal M represents VO. R represents the following structural formula.

(Example 18)
An optical information recording medium was produced in the same manner as in Example 1, except that the dye was replaced with a compound represented by the following structural formula as a phthalocyanine dye.
As shown in FIG. 2, the cross-sectional shape of the reflective layer in the obtained optical information recording medium in the cross-track direction is CL = 180 nm, BL = 112 nm, UL = 85 nm, depth (d1) = 45 nm, depth (d2 ) = 40 nm, angle (θ ₁ ) = 55 °, angle (θ ₂ ) = 49 °.

ただし、前記構造式中、中心金属ＭはＶＯを表す。Ｒは下記構造式を表す。

However, in the structural formula, the central metal M represents VO. R represents the following structural formula.

(Example 19)
An optical information recording medium was produced in the same manner as in Example 1, except that the dye was replaced with a compound represented by the following structural formula as a phthalocyanine dye.
As shown in FIG. 2, the cross-sectional shape of the reflective layer in the obtained optical information recording medium in the cross-track direction is CL = 180 nm, BL = 112 nm, UL = 85 nm, depth (d1) = 45 nm, depth (d2 ) = 40 nm, angle (θ ₁ ) = 55 °, angle (θ ₂ ) = 49 °.

ただし、前記構造式中、中心金属ＭはＣｕを表す。Ｒは−ＳＯ_２Ｃ_４Ｈ_９を表す。
得られた光情報記録媒体における反射層のトラック横断方向の断面形状は、図２に示すように、ＣＬ＝１８０ｎｍ、ＢＬ＝１１２ｎｍ、ＵＬ＝８５ｎｍ、深さ（ｄ１）＝４５ｎｍ、深さ（ｄ２）＝４０ｎｍ、角度（θ_１）＝５５°、角度（θ_２）＝４９°であった。

However, in the structural formula, the central metal M represents Cu. R represents _-SO 2 _C 4 _{H 9.}
As shown in FIG. 2, the cross-sectional shape of the reflective layer in the obtained optical information recording medium in the cross-track direction is CL = 180 nm, BL = 112 nm, UL = 85 nm, depth (d1) = 45 nm, depth (d2 ) = 40 nm, angle (θ ₁ ) = 55 °, angle (θ ₂ ) = 49 °.

  In each obtained optical information recording medium, a push-pull signal was measured as follows. The results are shown in Tables 13-15.

<Method for Measuring Push-Pull Signal>
The signal peaks l1 and trough l2 crossing the track with each optical information recording medium in focus are measured with an optical disk evaluation machine (DDU1000, manufactured by Pulstec Industrial Co., Ltd.). pull) signal = (l1-l2) / (l1 + l2).

<Measurement method of recording characteristics>
The optical information recording medium obtained in Example 1 was recorded while tracking (linear velocity: 3.5 m / sec) using a semiconductor laser beam having an oscillation wavelength of 405 nm and a beam diameter of 1.0 μm, and a semiconductor continuous wave having an oscillation wavelength of 405 nm. Reproduction was performed with laser light (reproduction power 0.7 mW), the reproduction waveform was measured, and the relationship between recording power and jitter was examined. The result is shown in the graph of FIG.
As is apparent from FIG. 3, it can be seen that the optical information recording medium of Example 1 has excellent recording characteristics with a recording power of 6.7 mW and a jitter of 8% or less.

  The optical information recording medium of the present invention can obtain a signal having a uniform and excellent contrast over the entire recording area, and is suitably used for a write-once disk system.

FIG. 1 is a schematic sectional view showing an example of the optical information recording medium of the present invention. FIG. 2 is an enlarged schematic cross-sectional view of the optical information recording medium of FIG. FIG. 3 is a graph showing the relationship between the recording power and jitter of the optical information recording medium.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Optical information recording medium 2 Board | substrate 3 Reflective layer 4 Recording layer 5 Barrier layer 6 Adhesive layer 7 Tracking track 8 Surface protective layer

Claims (23)

  An optical information recording medium in which a substrate on which concave guide grooves are formed, and at least a reflective layer, a recording layer containing an organic dye, and a surface protective layer are laminated on the substrate in this order, A push-pull (push) in the optical information recording medium has a concave portion corresponding to the concave guide groove in the substrate, the cross-sectional shape in the direction crossing the track of the concave portion is a substantially inverted trapezoid whose upper base is longer than the lower base -An optical information recording medium characterized in that the signal is 0.25 to 0.60.   The optical information recording medium according to claim 1, wherein at least one of recording and reproduction is performed by irradiating a laser beam having an oscillation wavelength of 500 nm or less from the surface protective layer side.   The cross-sectional shape of the interface between the substrate and the reflective layer in the direction crossing the track of the recess in the reflective layer is a substantially inverted trapezoid, and the length (CL) of the upper base of the substantially inverted trapezoid is 90 to 200 nm. Item 3. The optical information recording medium according to any one of Items 1 to 2.   The cross-sectional shape of the interface between the substrate and the reflective layer in a direction crossing the track of the recess in the reflective layer is a substantially inverted trapezoidal shape, and the length (BL) of the bottom of the substantially inverted trapezoidal shape is 25 nm or more. The optical information recording medium according to any one of 1 to 3.   5. The optical information recording medium according to claim 4, wherein the length (BL) of the lower base of the substantially inverted trapezoidal shape satisfies a relationship of the following formula: BL ≧ TP / 13 (where TP represents a track pitch (nm)). .   The cross-sectional shape of the interface between the reflective layer and the recording layer in a direction crossing the track of the recess in the reflective layer is a substantially inverted trapezoidal shape, and the length (UL) of the lower base of the substantially inverted trapezoidal shape is 10 nm or more. Item 6. The optical information recording medium according to any one of Items 1 to 5.   7. The optical information recording medium according to claim 6, wherein the length (UL) of the bottom of the substantially inverted trapezoidal shape satisfies the relationship of the following formula: UL ≧ TP / 32 (where TP represents the track pitch (nm)). .   The optical information recording medium according to any one of claims 1 to 7, wherein an angle θ formed by a surface connecting the upper base and the lower base in the trapezoidal portion of the concave portion of the reflective layer and the upper base and the lower base is 60 ° or less.   The optical information recording medium according to claim 1, wherein the reflective layer contains any one of aluminum and an aluminum alloy.   The optical information recording medium according to claim 1, wherein the reflective layer has a thickness of 20 to 200 nm.   11. The optical information recording medium according to claim 1, wherein the reflectance of the organic dye in the recording layer is 8% or more at the wavelength of light used for at least one of recording and reproduction.   The optical information recording medium according to claim 1, wherein the organic dye is a phthalocyanine dye. The optical information recording medium according to claim 12, wherein the phthalocyanine dye is a compound represented by the following structural formula.

However, in the structural formula, the central metal M represents one selected from Cu, VO, Ni, H, Zn, Pd, Cd, Co, and Fe. R represents an organic substituent. The optical information recording according to claim 13, wherein the central metal M represents one selected from VO, Zn, Pd, and Co, and R represents C ₆ H ₅ — (CF ₃ ) ₂ C—O—. Medium. The center metal M represents any one selected from Cu, VO, Ni, H, Zn, Pd, Cd, Co, and Fe, and R represents any one selected from the following structural formulas. The optical information recording medium described.

The optical information recording medium according to claim 13, wherein the central metal M is a substituent represented by the following structural formula, and R is —OCH ₂ CF ₂ CF ₂ H.

In Structural Formula, Cp represents _{Fe (C 5 H 5) 2} . The optical information recording medium according to claim 13, wherein the central metal M represents Cu and R represents —SO ₂ C ₄ H ₉ .   The optical information recording medium according to claim 1, wherein the organic dye is an azo dye. The optical information recording medium according to claim 18, wherein the azo dye is represented by the following structural formula.

The optical information recording medium according to claim 1, wherein the organic dye is represented by at least one of the following general formulas (I) to (V).

However, in said general formula (I) and (II), A represents the aromatic ring which may have a substituent, and B represents the aromatic ring which may have substituents other than OH. n represents an integer of 1 to 3, and m represents an integer of 2 to 6. L represents a divalent linking group or a single bond which may be substituted. V represents an aromatic ring which may have a substituent other than L.

However, in said general formula (III) and (IV), R < ¹ > and R < ² > represents the substituent which may mutually be same or different, p and q represent the integer of 0-3. m represents an integer of 2 to 6. L represents a divalent linking group or a single bond which may be substituted. V represents an aromatic ring which may have a substituent other than L.

However, in said general formula (V), R < ¹ > and R < ² > represents the substituent which may mutually be same or different, p and q represent the integer of 0 thru | or 3. m represents an integer of 2 or 3. V represents an aromatic ring which may have a substituent.   21. The optical information recording medium according to claim 1, wherein the track pitch on the substrate is 200 to 400 nm, the groove depth of the guide groove is 10 to 150 nm, and the half width of the guide groove is 50 to 250 nm.   The optical information recording medium according to any one of claims 1 to 21, wherein the transmittance of the surface protective layer is 80% or more with respect to light used for at least one of recording and reproduction. 23. At least one of information recording and reproduction is performed by irradiating a laser beam having an oscillation wavelength of 500 nm or less from the surface protective layer side in the optical information recording medium according to claim 1. Recording / playback method.

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