JP2003072238A - Optical recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording medium, which has a high sensitivity even in high-speed recording, high-packing density recording, good recording characteristics, and also can obtain a sufficient signal amplitude particularly after recording with a high power laser. SOLUTION: An optical recording medium comprises at least a substrate, a recording layer and a reflecting layer. In this medium, the recording layer uses a phthalocyanine compound which has at least one of specific substituents (a-1) to (a-9) and in which a maximum value kmax of an extinction coefficient in a wavelength of 650 to 900 nm is 0.9 or more.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical recording medium such as an optical disc having a recording layer containing a phthalocyanine compound useful for optoelectronics such as optical disc recording materials, information recording, display sensors and optical cards. Regarding

[0002]

2. Description of the Related Art Compact disc (hereinafter abbreviated as CD)
A CD-R (CD
-Recordable) is known to be proposed and developed, and is widely used for information recording.

Recording / reproducing of this CD-R is generally 78
A 0 nm near infrared semiconductor laser is used, and signal recording is performed in a heat mode on a recording layer made of an organic dye or the like on a substrate. That is, when the recording layer is irradiated with laser light, the organic dye generates heat due to light absorption, and the generated heat forms pits in the recording layer. The signal recording is detected by the difference in reflectance between the portion where the pit is formed and the portion where the pit is not formed when the laser beam is irradiated. The CD-R is compatible with CD players and CD-ROM players because it complies with CD standards such as Red Book and Orange Book, and has been rapidly and inexpensively provided in recent years. From
It has become widely used explosively for personal computer image storage, backup, and music. At present, with the improvement of the laser power of the CD-R player, it has become possible to record at 12x speed and 16x speed, and the time required for 70 minutes or more per disc at first is shortened to 5 minutes or less.

In recent years, the demand for higher speeds such as 24 × speed and 32 × speed has been known to continue, and there is an increasing need for recording media having good high speed recording characteristics. So far, a phthalocyanine compound having improved high-speed recording characteristics has been disclosed in Japanese Patent Laid-Open No. Hei 8
-209010, JP-A-8-209111, JP-A-10
-45761, WO 97/23354. However, at present, a dye having sufficient recording characteristics at high speed recording of 24 times or more has not been developed yet.

Writing to and reading from a CD-R requires 7
Since the laser light in the vicinity of 80 nm is used, it is important to control the absorption coefficient, the refractive index and the like in the vicinity of the laser oscillation wavelength and to form the pits with high accuracy during writing. A method for improving recording characteristics by using a phthalocyanine compound and a metal complex compound in the recording layer is known (JP-A-7-98887), and as a specific form of using and in the recording layer. ,
And WO are linked via a linking group (WO 00/0
9522) is also known. By the way, at the time of high-speed recording, it is necessary to form accurate pits in a short time, so it is necessary to increase the laser output. As a result, more heat is accumulated during the formation of pits, and the residual heat adversely affects the formation of pits around the pits, which deteriorates the jitter and deviation values. It is believed that. As a solution to this problem, it has been known that a thin dye film and efficient heat diffusion can form good pits even when a laser is irradiated with high power. There is a problem in that the amplitude becomes small, and sometimes it is out of the standard and cannot be reproduced.

[0006]

The present invention has high sensitivity to the above problems even in high speed recording and high density recording.
An object of the present invention is to provide an optical recording medium having good recording characteristics, and in particular, capable of obtaining a sufficient signal amplitude after recording with a high power laser.

[0007]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, the dye used in the present invention has not only a good pit-forming ability but also when formed into a film. It has been found that when an optical recording medium is produced using this dye, it has particularly good recording characteristics in high-speed recording because it has a high absorbance.

That is, the present invention is an optical recording medium comprising at least a substrate, a recording layer and a reflective layer, wherein the recording layer contains at least one phthalocyanine compound represented by the following general formula (1). Optical recording medium,

[0009]

[Chemical 4]

[In the formula (1), M represents two hydrogen atoms, a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal, and R ^{1 to} R ¹⁶ are each independently represent a hydrogen atom, a halogen atom, a nitro group, a substituted or straight-chain or branched alkyl group having a total carbon number of 1 to 10 unsubstituted, substituted or total carbon number of 1 to 10 unsubstituted straight or branched alkoxy Group, a substituted or unsubstituted linear or branched alkylthio group having a total carbon number of 1 to 10, or the following formulas (a-1) to (a-
9) represents a substituent A selected from the group represented by 9), R ^1
At least one of R ¹⁶ to R ¹⁶ is the substituent A. ]

[0011]

[Chemical 5]

[In the formulas (a-1) to (a-9), Y is a substituted or unsubstituted alkylene group having 1 to 4 total carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 4 total carbon atoms, A substituted or unsubstituted arylene group having a total carbon number of 6 to 15 or a substituted or unsubstituted heteroarylene group having a total carbon number of 3 to 15, wherein Z is a substituted or unsubstituted alkyl group having a total carbon number of 1 to 10 A substituted or unsubstituted alkenyl group having 1 to 10 total carbon atoms, a substituted or unsubstituted alicyclic compound group having 3 to 15 total carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 total carbon atoms,
A substituted or unsubstituted aralkyl group having 7 to 15 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 15 carbon atoms,
Or represents a metal complex, Z ′ is a substituted or unsubstituted alkyl group having a total carbon number of 1 to 10, a substituted or unsubstituted total carbon number of 1 to 1
10 alkenyl groups, substituted or unsubstituted total carbon number 3 to 1
5 alicyclic compound group, substituted or unsubstituted total carbon number 6 to 1
5 represents an aryl group, a substituted or unsubstituted aralkyl group having a total of 7 to 15 carbon atoms, or a substituted or unsubstituted heteroaryl group having a total of 3 to 15 carbon atoms, and R and R ′ each independently represent hydrogen or a substituted group. Or an unsubstituted alkyl group having 1 to 10 carbon atoms,
It represents a substituted or unsubstituted aryl group having 6 to 15 total carbon atoms. ]

An optical recording medium, wherein the substituent A in the phthalocyanine compound is selected from groups represented by the following formulas (b-1) to (b-5).

[0014]

[Chemical 6]

[Z in the formulas (b-1) to (b-5),
Z ′, R and R ′ have the same meanings as Z, Z ′, R and R ′ in the formulas (a-1) to (a-9). ] The optical recording medium characterized in that the substituent A in the phthalocyanine compound is selected from the groups represented by formulas (b-1) to (b-3). The optical recording medium, wherein the substituent A in the phthalocyanine compound is a group represented by the formula (b-1). The phthalocyanine compound has a wavelength of 650 nm to 9
The optical recording medium as described in any one of (1) to (4) above, wherein kmax ≧ 0.9 is satisfied, where kmax is the maximum value of the extinction coefficient k at 00 nm.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. The substrate in the present invention basically need only be transparent at the wavelengths of recording light and reproducing light. As the material of the substrate, for example, a polymeric material such as a polycarbonate resin, a vinyl chloride resin, an acrylic resin such as polymethylmethacrylate, a polystyrene resin, an epoxy resin, or an inorganic material such as glass is used. These substrate materials are formed into a disc-shaped substrate by an injection molding method or the like. Guide grooves or pits may be formed on the surface of the substrate as needed. Such guide grooves and pits are preferably provided at the time of molding the substrate, but can be provided by using an ultraviolet curable resin layer on the substrate.

In the present invention, a recording layer is provided on the substrate. The recording layer of the present invention has a maximum absorption wavelength of 650 nm to 650 nm.
It contains a phthalocyanine compound represented by the general formula (1) existing in the vicinity of 900 nm. Above all, a moderate optical constant (optical constant is expressed by a complex refractive index (n + ki) for a recording and reproducing laser wavelength near 780 nm. In the formula, n and k correspond to a real part n and an imaginary part k. (Here, n is the refractive index and k is the extinction coefficient.)
Need to have.

Generally, organic dyes are characterized in that the refractive index n and the extinction coefficient k change greatly with respect to the wavelength λ. Assuming that the reproduction light wavelength is λ ₁ , if n is smaller than 1.8 at λ ₁ , the reflectance and signal modulation required for accurate signal reading cannot be obtained, and k exceeds 0.40. However, not only is the reflectance lowered and a good reproduction signal cannot be obtained, but the signal is also susceptible to change due to reproduction light, which is not suitable for practical use. In consideration of this feature, by selecting an organic dye having a preferable optical constant at a target laser wavelength and forming a recording layer, a medium having high reflectance and high sensitivity can be obtained. .

Further, in the wavelength region of 650 nm to 900 nm, assuming that the maximum value that k can take is kmax (the wavelength at that time is λmax), if kmax is smaller than 0.9, the signal modulation degree required for signal reading is obtained. Therefore, it is necessary to increase the thickness of the recording layer, but in high-speed recording, the heat generated during pit formation cannot be efficiently dissipated, and the signal characteristics deteriorate, so kmax is 0.9 or more. Is preferable, more preferably 1.0 or more, and further preferably 1.1 or more.

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

Here, the content of the phthalocyanine compound represented by the general formula (1) in the recording layer is 30% or more,
It is preferably 60% or more. It is also preferable that it is substantially 100%.

Examples of the method for providing the recording layer include a coating method such as a spin coating method, a spraying method, a casting method and a dipping method, a sputtering method, a chemical vapor deposition method and a vacuum vapor deposition method. The spin coating method is simple. Is preferred.

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

If desired, the dye in the recording layer may be dispersed in a polymer thin film or the like and used.

The thickness of the recording layer is not particularly limited, but is preferably 50 nm to 300 nm. When the film thickness of the recording layer is less than 50 nm, the thermal diffusion is too large to record, or the recording signal is distorted and the signal amplitude becomes small. Further, when the film thickness is thicker than 300 nm, the reflectance is lowered and the reproduction signal characteristic is deteriorated.

Next, the reflective layer formed on the recording layer will be described. The thickness of the reflective layer is 50 nm to 300
nm is preferred. The material of the reflective layer has a sufficiently high reflectance at the wavelength of the reproduction light, such as Au, Al, Ag,
The metals Cu, Ti, Cr, Ni, Pt, Ta, Cr and Pd can be used alone or as an alloy. Among these, Au, Al and Ag have high reflectance and are suitable as materials for the reflective layer. Other than the above, the following may be included. For example, Mg, Se, Hf, V, N
b, Ru, W, Mn, Re, Fe, Co, Rh, Ir,
Zn, Cd, Ga, In, Si, Ge, Te, Pb, P
Mention may be made of metals such as o, Sn and Bi and semimetals. Further, a material containing Au as a main component is preferable because a reflective layer having a high reflectance can be easily obtained. Here, the main component means that the content rate is 50% or more. It is also possible to stack a low refractive index thin film and a high refractive index thin film alternately with a material other than metal to form a multilayer film and use it as a reflective layer.

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

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

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

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

Printing such as a label can be further performed on the protective layer. Alternatively, a protective sheet or substrate may be attached to the reflective layer surface, or two optical recording media may be attached such that the reflective layer surfaces face each other and face each other. In addition, an ultraviolet curable resin, an inorganic thin film, or the like may be formed on the mirror surface side of the substrate in order to protect the surface or prevent the adhesion of dust or the like.

Next, the phthalocyanine compound used in the present invention will be described. The phthalocyanine compound used in the present invention has a large absorbance per unit film thickness, and when used as a medium, when the dye layer is formed into a thin film, even if high-speed recording is performed with a high-power laser, heat diffusion is efficient. Done,
Good recording characteristics are exhibited, and a sufficient signal amplitude is obtained during reproduction.

The phthalocyanine compound used in the present invention has an absorption in the range of 650 to 900 nm, a high molecular extinction coefficient, and excellent long-term stability and durability. Therefore, an optical recording medium (optical disk, optical card) using a semiconductor laser is used. ) And the like are suitable for recording materials.

In the formula (1), examples of the divalent metal represented by M include Cu (II), Zn (II), Fe (II) and Co.
(II), Ni (II), Ru (II), Rh (II), Pd
(II), Pt (II), Mn (II), Mg (II), Ti
(II), Be (II), Ca (II), Ba (II), Cd
(II), Hg (II), Pb (II), Sn (II), etc., 1
Examples of the substituted trivalent metal include Al-Cl, Al-Br,
Al-F, Al-I, Ga-Cl, Ga-F, Ga-
I, Ga-Br, In-Cl, In-Br, In-I,
In-F, Tl-Cl, Tl-Br, Tl-I, Tl-
_{F, Al-C 6 H 5} , Al-C 6 H 4 (CH 3), In-C 6
_{H 5, In-C 6 H} 4 (CH 3), In-C 10 H 7, Mn
(OH), Mn (OC ₆ H ₅ ), Mn [OSi (C
H _{3) 3],} FeCl, such as RuCl the like. Examples of di-substituted tetravalent metals include CrCl ₂ , SiCl ₂ , S
_{iBr 2, SiF 2, SiI 2} , ZrCl 2, GeCl 2,
GeBr ₂ , GeI ₂ , GeF ₂ , SnCl ₂ , SnB
r ₂ , SnI ₂ , SnF ₂ , TiCl ₂ , TiBr ₂ , Ti
F ₂ , Si (OH) ₂ , Ge (OH) ₂ , Zr (OH) ₂ ,
Mn (OH) ₂ , Sn (OH) ₂ , TiR ₂ , CrR ₂ , S
iR ₂ , SnR ₂ , GeR ₂ [R represents an alkyl group, a phenyl group, a naphthyl group and derivatives thereof], Si (O
R ') ₂ , Sn (OR') ₂ , Ge (OR ') ₂ , Ti
(OR ′) ₂ , Cr (OR ′) ₂ [R ′ represents an alkyl group, an alkylcarbonyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkylalkoxysilyl group and derivatives thereof] and the like. Examples of oxymetals include VO, MnO, TiO and the like. Of these, Cu (II), Zn (II) and Fe are preferable.
(II), Co (II), Ni (II), Ru (II), Rh
(II), Pd (II), Pt (II), Mn (II), Al-
Cl, Al-Br, Al- F, Al-I, SiCl 2,
SiBr ₂ , TiCl ₂ , TiBr ₂ , TiF ₂ , Si (O
H) ₂ and VO, and more preferably Cu (I
I) and Pd (II).

Further, in the formula (1), the substituted or unsubstituted linear or branched alkyl group having a total carbon number of 1 to 10 represented by R ^{1 to} R ¹⁶ includes a methyl group, an ethyl group and a propyl group. ,
Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, iso-propyl group, sec-butyl group, t-butyl group, neo-pentyl group, 1,2-dimethylpropyl group, cyclohexyl group, 1 , 3-dimethylbutyl group, 1-iso-propylpropyl group, 1,2
-Dimethylbutyl group, 1,4-dimethylpentyl group, 2
-Methyl-1-iso-propylpropyl group, 1-ethyl-3-methylbutyl group, 3-methyl-1-iso-propylbutyl group, 2-methyl-1-iso-propylbutyl group, 1-t-butyl- 2-methylpropyl group, 2,
4-dimethyl-3-propyl group, 2-methylpentyl group, 2-ethylhexyl group, 2-chloroethyl group, 3-
Bromopropyl group, 2,2,3,3-tetrafluoropropyl group, 1,1,1,3,3,3-hexafluoro-
2-propyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 1-ethoxy-2-
Propyl group, 3-methoxypropyl group, 3-methoxy-
Butyl group, 2,2-dimethyl-1,3dioxolane-4
-Methoxy group, 1,3-diethoxy-2-propoxy group, 2-dimethylaminoethyl group, 2-diethylaminoethyl group, 2-dibutylaminoethyl group, 2-diethylaminopropyl group, 1,3-diethylthio-2-propyl group Groups and the like,

Examples of the substituted or unsubstituted linear or branched alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group,
Hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, iso-propoxy group, sec-
Butoxy group, t-butoxy group, neo-pentyloxy group, 1,2-dimethylpropoxy group, cyclohexyloxy group, 1,3-dimethylbutoxy group, 1-iso-propylpropoxy group, 1,2-dimethylbutoxy group,
1,4-dimethylpentyloxy group, 2-methyl-1-
iso-propylpropoxy group, 1-ethyl-3-methylbutoxy group, 3-methyl-1-iso-propylbutoxy group, 2-methyl-1-iso-propylbutoxy group, 1-t-butyl-2-methylpropoxy group Group, 2, 4
-Dimethyl-3-propoxy group, 2-methylpentyloxy group, 2-ethylhexyloxy group, 2-chloroethoxy group, 3-bromopropoxy group, 2,2,3,3-tetrafluoropropoxy group, 1,1, 1,3,3,3-
Hexafluoro-2-propoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 1-ethoxy-2-propoxy group, 3-methoxypropoxy group, 3-methoxybutoxy group, 2,2 -Dimethyl-1,3dioxolane-4-methoxy group, 1,3-
Diethoxy-2-propoxy group, 2-dimethylaminoethoxy group, 2-diethylaminoethoxy group, 2-dibutylaminoethoxy group, 2-diethylaminopropoxy group, 1,3-diethylthio-2-propoxy group and the like,

The substituted or unsubstituted linear or branched alkylthio group having 1 to 10 carbon atoms includes methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group. Group, iso-propylthio group, sec
-Butylthio group, t-butylthio group, neo-pentylthio group, 1,2-dimethylpropylthio group, cyclohexylthio group, 1,3-dimethylbutylthio group, 1-is
o-propylpropylthio group, 1,2-dimethylbutylthio group, 1,4-dimethylpentylthio group, 2-methyl-1-iso-propylpropylthio group, 1-ethyl-
3-methylbutylthio group, 3-methyl-1-iso-propylbutylthio group, 2-methyl-1-iso-propylbutylthio group, 1-t-butyl-2-methylpropylthio group, 2,4- Dimethyl-3-propylthio group, 2-
Methylpentylthio group, 2-ethylhexylthio group, 2
-Chloroethylthio group, 3-bromopropylthio group,
2,2,3,3-tetrafluoropropylthio group, 1,
1,1,3,3,3-hexafluoro-2-propylthio group, 2-methoxyethylthio group, 2-ethoxyethylthio group, 2-butoxyethylthio group, 1-ethoxy-2
-Propylthio group, 3-methoxy-propylthio group, 3
-Methoxybutylthio group, 2,2-dimethyl-1,3dioxolane-4-methylthio group, 1,3-diethoxy-
Examples thereof include a 2-propylthio group, a 2-dimethylaminoethylthio group, a 2-diethylaminoethylthio group, a 2-dibutylaminoethylthio group, a 2-diethylaminopropylthio group, and a 1,3-diethylthio-2-propylthio group.

In the substituent A, formulas (a-1) to (a-
9) in, substituted or unsubstituted total carbon number 1 to 4 represented by Y
As the alkylene group of, methylene group, ethylene group, propylene group, butylene group, 1-methylethylene group, 2-methylpropylene group, 1,2-dimethylethylene group, 1-
Chloromethylene group, 2-chloroethylene group, 3-bromopropylene group, 2,2,3,3-tetrafluoropropylene group, 1,1,2,2,2,3,3,3,4,4-deca Fluorobutylene group, 2-methoxyethylene group, 2-
Ethoxyethylene group, 2-methoxypropylene group, 2-
Dimethylaminoethylene group, 2-aminopropylene group,
1,3-dimethylthiomethylene group and the like,

Examples of the substituted or unsubstituted alkenylene group having 2 to 4 carbon atoms include vinylene group, 1-propenylene group,
2-butenylene group, 1,3-butadienylene group, 1-methylvinylene group, 2-methyl-2-propenylene group,
1,2-dimethylvinylene group, 1,2-dichlorovinylene group, 2-bromo-1-propenylene group, 1,2-dimethoxyvinylene group, 1-dimethylaminovinylene group, 2
-Amino-1-propylenylene group, 1-methylthiovinylene group and the like, and a substituted or unsubstituted total carbon number of 6 to 1
As the arylene group of 5, phenyl group, nitrophenyl group, cyanophenyl group, hydroxyphenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, n-propylphenyl group Group, di (n-propyl) phenyl group, tri (n-propyl) phenyl group, iso-propylphenyl group, di (iso-propyl) phenyl group, tri (iso-propyl) phenyl group, n-butylphenyl group, Di (n-butyl) phenyl group, tri (n-butyl) phenyl group, iso-butylphenyl group, di (iso-butyl) phenyl group, tri (i)
so-butyl) phenyl group, sec-butylphenyl group, di (sec-butyl) phenyl group, t-butylphenyl group, di (t-butyl) phenyl group, dimethyl-t-
Butyl-phenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, methoxyphenyl group, ethoxyphenyl group, trifluoromethylphenyl group, N, N-dimethylaminophenyl group, naphthyl group, nitronaphthyl group, Aryl groups such as cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, fluoronaphthyl group, chloronaphthyl group, bromonaphthyl group, iodonaphthyl group, methoxynaphthyl group, trifluoromethylnaphthyl group, N, N-dimethylaminonaphthyl group Examples of the substituted or unsubstituted heteroarylene group having 3 to 15 carbon atoms include a pyrrolyl group, a thienyl group, a furanyl group, an oxazoyl group, an isoxazoyl group, an oxadiazoyl group, and an imidazoyl group. , Benzo Kisazoiru group, benzothiazoyl group, benzimidazoyl group, benzofuranyl group, indoyl group, divalent group derived from a heteroaryl group such as Isoindoiru group.

Examples of the substituted or unsubstituted alkyl group having 1 to 10 carbon atoms as Z, Z ', R and R'in the substituent A include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. , Hexyl group, heptyl group, octyl group, nonyl group, iso-propyl group, sec-butyl group, t-butyl group, neo-pentyl group, 1,2-dimethylpropyl group, cyclohexyl group, 1,3-dimethylbutyl group Group, 1
-Iso-propylpropyl group, 1,2-dimethylbutyl group, 1,4-dimethylpentyl group, 2-methyl-1-
iso-propylpropyl group, 1-ethyl-3-methylbutyl group, 3-methyl-1-iso-propylbutyl group, 2-methyl-1-iso-propylbutyl group, 1-
t-butyl-2-methylpropyl group, 2,4-dimethyl-3-propyl group, 2-methylpentyl group, 2-ethylhexyl group, 2-chloroethyl group, 3-bromopropyl group, 2,2,3,3 -Tetrafluoropropyl group, 1,
1,1,3,3,3-hexafluoro-2-propyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2
-Butoxyethyl group, 1-ethoxy-2-propyl group,
3-methoxypropyl group, 3-methoxy-butyl group,
2,2-dimethyl-1,3dioxolane-4-methoxy group, 1,3-diethoxy-2-propoxy group, 2-dimethylaminoethyl group, 2-diethylaminoethyl group, 2
-Dibutylaminoethyl group, 2-diethylaminopropyl group, 1,3-diethylthio-2-propyl group and the like, and examples of the substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms include vinyl group and 1-propenyl group. Group, 2-butenyl group, 1,3-butadienyl group, 1-methylvinyl group,
2-methyl-2-propenyl group, 1,2-dimethylvinyl group, 1,2-dichlorovinyl group, 2-bromo-1-propenyl group, 1,2-dimethoxyvinyl group, 1-dimethylaminovinyl group, 2 -Amino-1-propylenyl group,
1-methylthiovinyl group and the like, and as the substituted or unsubstituted alicyclic compound group having a total of 3 to 15 carbon atoms, a cyclopropyl group, a 2-methylcyclopropyl group, a 2,2-dimethylcyclopropyl group, Cyclobutyl group, 2-ethylcyclobutyl group, 2,3,4-trimethylcyclobutyl group, cyclopentyl group, 2-isopropylcyclopentyl group, 3,3,4,4-tetramethylcyclopentyl group, cyclohexyl group, 2-cyclohexenyl Base, 4-
Phenylcyclohexyl group, tetralyl group, adamantyl group, N-pyrrolidyl group, tetrahydrofuryl group, tetrahydrothiophenyl group, piperidinyl group, piperazinyl group, tetrahydropyranyl group, tetrahydrothiopyranyl group, oxazinanyl group, thiomorpholinyl group, Hexahydrotriazinyl group, hexamethylene tetraminyl group and the like can be mentioned.

Examples of the substituted or unsubstituted aryl group having 6 to 15 carbon atoms include phenyl group, nitrophenyl group, cyanophenyl group, hydroxyphenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group and ethylphenyl group. , Diethylphenyl group, triethylphenyl group, n-propylphenyl group, di (n-propyl) phenyl group, tri (n-propyl) phenyl group, iso-
Propylphenyl group, di (iso-propyl) phenyl group, tri (iso-propyl) phenyl group, n-butylphenyl group, di (n-butyl) phenyl group, tri (n-)
Butyl) phenyl group, iso-butylphenyl group, di (iso-butyl) phenyl group, sec-butylphenyl group, di (sec-butyl) phenyl group, t-butylphenyl group, di (t-butyl) phenyl group, Dimethyl-t
-Butylphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, methoxyphenyl group, ethoxyphenyl group, trifluoromethylphenyl group, N, N-dimethylaminophenyl group, naphthyl group, nitronaphthyl group, Examples include cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, fluoronaphthyl group, chloronaphthyl group, bromonaphthyl group, iodonaphthyl group, methoxynaphthyl group, trifluoromethylnaphthyl group, N, N-dimethylaminonaphthyl group. ,

Examples of the substituted or unsubstituted aralkyl group having 7 to 15 carbon atoms include benzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group and dichlorobenzyl group. , Methoxybenzyl group, ethoxybenzyl group, trifluoromethylbenzyl group, naphthylmethyl group, nitronaphthylmethyl group, cyanonaphthylmethyl group, hydroxynaphthylmethyl group, methylnaphthylmethyl group, trifluoromethylnaphthylmethyl group, and the like,

Examples of the substituted or unsubstituted heteroaryl group having 3 to 15 carbon atoms include pyrrolyl group, thienyl group, furanyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, imidazoyl group, benzoxazoyl group and benzothiazoyl group. And a heteroaryl group such as a benzimidazoyl group, a benzofuranyl group, an indoyl group and an isoindoyl group.

The metal complex represented by Z may be any compound containing a metal, preferably a metallocene compound, specifically Fe (Cp) ₂
(However, Cp represents a cyclopentadienyl group), Co
(Cp) ₂ , Ni (Cp) ₂ , Ru (Cp) ₂ , Os (C
p) ₂ , Mn (Cp) ₂ , Cr (Cp) ₂ , W (Cp) ₂ ,
V (Cp) ₂ , Sc (Cp) ₃ , Y (Cp) ₃ , La (C
p) ₃ , Ce (Cp) ₃ , Pr (Cp) ₃ , Nd (C
p) ₃ , Sm (Cp) ₃ , Gd (Cp) ₃ , Er (C
p) ₃ , Tm (Cp) ₃ , Yb (Cp) ₃ , metallocene compounds such as cyclopentadienylmanganocentricarbonyl, titanocene diphenoxide, bis (cyclopentadienyl) bis (2,6-difluoro-3-) Examples thereof include metallocene compounds having a substituted metal such as (1H-pyrrol-1-yl) phenyltitanium and cyclopentadienylmanganocentricarbonyl. These metallocene compounds are substituted with an alkyl group, an aryl group or an acyl group. The bond with the metallocene compound may be a bond with a cyclopentadienyl ring, a direct bond with a metal, or the like, and examples thereof include a bond with a cyclopentadienyl ring.

The compound represented by the general formula (1) is
A method of producing a monoimine from a diamine or hydrazine and an aldehyde and then coupling it with a formylated phthalocyanine compound, a diamine is reacted with an acid halide to form an acid amide, and then a formylated phthalocyanine compound is coupled. How to make
It can be synthesized by a method of esterifying an acid halide with a hydroxymethyl derivative of a phthalocyanine compound.

As is well known, the phthalocyanine compound has structural isomers, and the obtained compound is a mixture thereof. Furthermore, in the present invention, in addition to the formation of many structural isomers, a mixture of compounds having different substitution numbers is obtained. The compound described in the present invention is a mixture mainly containing the compound represented by the structural formula, and is not limited to the compound represented by the structural formula.

The substituent A is preferably one containing CH═N—N or CH ₂ —O— (C═O).

Next, specific examples of the phthalocyanine compound represented by the general formula (1) of the present invention will be shown. Each substituent described outside the parentheses is substituted at the α-position of phthalocyanine.

[0049]

[Chemical 7]

[0050]

[Chemical 8]

[0051]

[Chemical 9]

[0052]

[Chemical 10]

[0053]

[Chemical 11]

[0054]

[Chemical 12]

[0055]

[Chemical 13]

[0056]

[Chemical 14]

[0057]

[Chemical 15]

[0058]

[Chemical 16]

[0059]

[Chemical 17]

[0060]

[Chemical 18]

[0061]

[Chemical 19]

[0062]

[Chemical 20]

[0063]

[Chemical 21]

[0064]

[Chemical formula 22]

[0065]

[Chemical formula 23]

[0066]

[Chemical formula 24]

[0067]

[Chemical 25]

[0068]

[Chemical formula 26]

[0069]

[Chemical 27]

[0070]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 Phthalocyanine compound (1-
1) Synthetic dry dimethylformamide (hereinafter abbreviated as DMF) 4.38
g (60 mmol), under water cooling, phosphorus oxychloride 9.2
After g (60 mmol) was added dropwise, the mixture was stirred at room temperature to prepare a Vilsmeier reagent. With stirring, a solution of 10.76 g (10 mmol) of the phthalocyanine compound described in JP-A-5-247363 in 100 ml of chlorobenzene was added and the reaction was carried out at 80 to 90 ° C. for 4 hours. After completion of the reaction, after cooling to room temperature, sodium acetate aqueous solution was added, extracted with chloroform, washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off, and purified by column chromatography. Formyl phthalocyanine compound 8.28 g represented by structural formula (3)
(7.5 mmol) (yield 75%) was obtained.

This formyl phthalocyanine compound (3)
4.4 g (4.0 mmol) of trichloroethane (25 m)
1, dissolved in 10 ml of water, heated to 50 ° C., and then 1.28 g (8.0 mmol) of bromine trichloroethane 6.
A 5 ml solution was added dropwise and reacted. After the reaction was completed, an aqueous sodium hydrogen sulfite solution was added, the mixture was extracted with chloroform, washed with water, and the solvent was distilled off to obtain 4.91 g (3.89 mmol) of a halogenated formyl phthalocyanine compound (yield 97
%)Obtained.

On the other hand, 195 g of hydrazine monohydrate (3.
8.3 g (0.0 mol) of formylferrocene in 9 mol).
A solution of 39 mol) in 50 ml of methanol was added dropwise at room temperature for reaction. It was discharged into water, and the precipitated solid was separated by filtration and washed with water to obtain 6.8 g (0.030 mol) of ferrocene ardazone represented by the following structural formula (4) (yield 79%).

[0074]

[Chemical 28]

After dissolving 3.78 g (3.0 mmol) of the halogenated formyl phthalocyanine compound obtained above in 50 ml of toluene, 1.37 g (6.0 mmol) of ferrocene ardazone (4) was added, and the mixture was allowed to stand at room temperature. After reaction, the solvent was distilled off and the residue was purified by column chromatography to give 3.75 g (2.55 mol) of a phthalocyanine compound represented by the following structural formula (1-1) (yield 8
5%) was obtained. The kmax of this dye was 1.36, and the λmax at that time was 726.5 nm.

[0076]

[Chemical 29]

Maximum absorption wavelength in solution: 713.5 nm
(Solvent: Toluene) Gram extinction coefficient: εg = 151,000 (Solvent: Toluene) Thermal decomposition start temperature: 280 ° C Elemental analysis value: C ₇₂ H ₈₀ Br ₂ N ₁₀ O ₄ PdFe Calculated value (%) C: 58.77% , H: 5.48%, N: 9.52% Analytical value (%) C: 58.56%, H: 5.52%, N: 9.47%

Example 2 Phthalocyanine compound (1-
Synthesis of 7) 9.78 g of a phthalocyanine compound represented by the following structural formula (5) synthesized by the method described in JP-A-5-247363.
6.84 g (6.8 mmol) of formylphthalocyanine compound represented by the following structural formula (6) (yield 68%) in the same manner as in Example 1 except that (10 mmol) is used.
Got

This formyl phthalocyanine compound (6)
4.03 g (4.0 mmol) of trichloroethane 25
ml and 10 ml of water are mixed, heated to 50 ° C. and dissolved,
Cooled to 0 ° C. Sulfuryl chloride 1.78 g (8.0 m
10 ml solution of trichloroethane (mol) was added dropwise, and the mixture was reacted at room temperature for 1 hour. After the reaction was completed, an aqueous solution of calcium carbonate was added, the mixture was extracted with toluene, washed with water, and the solvent was distilled off to give a halogenated formylphthalocyanine compound of 3.9.
9 g (3.6 mmol) (yield 90%) was obtained.

On the other hand, Example 1 was repeated except that 1.52 g (7.5 mmol) of p-toluenesulfonyl chloride was used.
1.20 g of p-toluenesulfonyl hydrazide represented by the following structural formula (7) is condensed with hydrazine in the same manner as in.
(5.2 mmol) (yield 53%) was obtained.

[0081]

[Chemical 30]

2.22 g (2.0 mmol) of the halogenated formyl phthalocyanine compound obtained above, and p
-Toluenesulfonyl hydrazide (7) 0.92 g
(4.0 mmol) was dissolved in 30 ml of toluene and reacted at room temperature for 2 hours. After the solvent was distilled off, the residue was purified by column chromatography, and 1.89 g (1.4 mo of a phthalocyanine compound represented by the following structural formula (1-7) was obtained.
l) (yield 70%) was obtained. The kmax of this dye is 0.9
2, the λmax at that time was 734.5 nm.

[0083]

[Chemical 31]

Maximum absorption wavelength in solution: 725 nm (solvent: toluene) Gram extinction coefficient: εg = 122,000 (solvent: toluene) Thermal decomposition start temperature: 285 ° C Elemental analysis value: C ₆₈ H ₇₇ Cl ₃ N ₁₀ O ₇ SZn Calculated value (%) C: 61.49% H: 5.75% N: 10.37% Analytical value (%) C: 61.78% H: 5.51% N: 10.39%

Example 3 Phthalocyanine compound (1
Synthesis of -13) Using 2.94 g (3.0 mmol) of the phthalocyanine compound represented by the following structural formula (8) synthesized in the same manner as in the method described in JP-A-5-247363, the same method as in Example 1 was used. Formylation was performed to obtain 2.06 g (2.1 mmol) of a formylated phthalocyanine compound (yield 69%). 1.0 g of this formylated phthalocyanine compound
(1.0 mmol) was dissolved in 50 ml of toluene, 0.37 g (10 mmol) of sodium borohydride was added, the mixture was stirred at room temperature for 6 hours, 200 ml of 1% hydrochloric acid was added, and then extracted with toluene, dried and concentrated. As a result, 0.92 g (9.1 mmol) of phthalocyanine hydroxymethyl compound represented by the following structural formula (9) (yield 92%) was obtained.

Phthalocyanine hydroxymethyl derivative (9)
0.03 g (0.16 g) of p-toluenesulfonic acid monohydrate in 0.51 g (0.5 mmol) and 0.11 g (1.0 mmol) of pyrrole-2-carboxylic acid in toluene.
(mmol) and refluxed for 4 hours. After cooling to room temperature, the mixture was discharged into methanol and the precipitated solid was collected and purified by column chromatography to give 0.49 g (0.44 mm) of a phthalocyanine compound represented by the following structural formula (1-13).
ol) (90%). The kmax of this dye is 1.22
Then, λmax at that time was 725.5 nm.

[0087]

[Chemical 32]

Maximum absorption wavelength in solvent: 713.5 nm
(Solvent: Toluene) Gram extinction coefficient: εg = 126,000 (Solvent: Toluene) Thermal decomposition start temperature: 260 ° C Elemental analysis value: C ₅₈ H ₆₁ CoN ₉ O ₂ S ₄ calculated value (%) C: 63.14% H : 5.57% N: 11.43% Analytical value (%) C: 63.27% H: 5.31% N: 11.75%

Example 4 0.2 g of the phthalocyanine compound (1-1) described in Example 1 was dissolved in 10 ml of dimethylcyclohexane to prepare a dye solution. The substrate is made of polycarbonate resin and has a continuous guide groove (track pitch: 1.6 μm) with a diameter of 120 mm and a thickness of 1.2.
A disc-shaped one having a size of mm was used.

The dye solution is spun on the substrate at a rotation number of 1000 to
A recording layer was formed by spin coating at 1500 rpm and drying at 70 ° C. for 3 hours.

Au was sputtered on the recording layer using a sputtering apparatus (CDI-900) manufactured by Balzers Co., Ltd. to form a reflective layer having a thickness of 100 nm. Sputter gas includes
Argon gas was used. Sputtering conditions are sputtering power 2.5 kW, sputtering gas pressure 1.33 Pa (1.0 x
It was carried out at 10 ^-2 Torr).

Further, an ultraviolet curable resin SD- is formed on the reflective layer.
After spin-coating 1700 (manufactured by Dainippon Ink and Chemicals, Inc.), it was irradiated with ultraviolet rays to form a protective layer having a thickness of 6 μm to prepare an optical recording medium.

An optical disk evaluation device (DDU-manufactured by Pulstec Industrial Co., Ltd.) in which a semiconductor laser head having a wavelength of 780 nm and a lens numerical aperture of 0.5 is mounted on the obtained optical recording medium.
1000), and at a high linear velocity of 28.8 m / s, E
FM signals were recorded with a laser power of 27-31 mW. The signal was reproduced using the evaluation device, and the jitter, deviation and error rate of the shortest pit (length 0.8 μm) were measured. As a result, the laser power was 29 mW, and the jitter was 25 ns, the deviation was 15 ns, and the error rate was 100 or less. It showed a large value.

Comparative Example 1 A CD-R medium was prepared in the same manner as in Example 4 except that the phthalocyanine compound represented by the following structural formula (10) (kmax = 0.76, then λmax = 722.0 nm) was used. Was produced and evaluated in the same manner,
With a laser power of 29 mW, the jitter was 63 ns, the deviation was 50 ns, and the error rate was 1200 or more, which was not sufficient characteristics.

[0095]

[Chemical 33]

[Comparative Example 2] A phthalocyanine compound represented by the following structural formula (11) described in WO98014520 (kmax = 0.69, λmax = 729.0n at that time).
m) was used to prepare a CD-R medium in the same manner as in Example 4 and evaluated in the same manner. Laser power was 28 mW.
Then, jitter 50 ns, deviation 45 ns,
The error rate was 450 or more, which was not a sufficient characteristic.

[0097]

[Chemical 34]

[Examples 5 to 14] (1-2) to (1-2)
A CD-R medium was prepared in the same manner as in Example 4 except that the phthalocyanine compound described in 1) was used, and recording was performed with a laser power of 29 mW, and the shortest pit (length was about 0.8 μm).
The jitter, deviation and error rate of m) were evaluated. The results are shown in Table 1. As described in Table 1,
All showed good values. -As for the evaluation of jitter, ◯ is 35 ns or less and × is 3
It shows that it is 5 ns or more.・ For the evaluation of deviation, ○ is 40 ns or less,
× 40 ns or more. -As for the evaluation of the error rate, ◯ indicates less than 220 and x indicates 220 or more.

[0099]

[Table 1]

[0100]

The optical recording medium of the present invention has a wavelength of 6 at the recording layer.
Maximum extinction coefficient kmax at 50 nm to 900 nm
Contains 0.9 or more phthalocyanine.
The present invention provides an optical recording medium exhibiting good recording characteristics in high speed recording.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kazuhiro Seino             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company (72) Inventor Yasunori Saito             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company (72) Inventor Denmi Misawa             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company F-term (reference) 2H111 EA03 EA12 EA22 EA25 EA33                       EA37 EA43 FA01 FA12 FB45                 5D029 JA04 JC05

Claims (5)

[Claims] 1. An optical recording medium comprising at least a substrate, a recording layer and a reflective layer, wherein the recording layer contains at least one phthalocyanine compound represented by the following general formula (1). . [Chemical 1] [In the formula (1), M is two hydrogen atoms, a divalent metal atom,
Represents a trivalent or tetravalent substituted metal atom or an oxymetal, and R ^{1 to} R ¹⁶ each independently represent a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted total carbon number 1 to
10 straight-chain or branched alkyl group, substituted or unsubstituted straight-chain or branched alkoxy group having 1 to 10 total carbon atoms, substituted or unsubstituted straight-chain or branched alkylthio group having 1 to 10 total carbon atoms, or Represents a substituent A selected from the groups represented by the following formulas (a-1) to (a-9), and at least one of R ^{1 to} R ¹⁶ is the substituent A. ] [Chemical 2] [In the formulas (a-1) to (a-9), Y is a substituted or unsubstituted alkylene group having a total carbon number of 1 to 4, a substituted or unsubstituted alkenylene group having a total carbon number of 2 to 4, a substituted or unsubstituted A substituted arylene group having a total carbon number of 6 to 15, or a substituted or unsubstituted heteroarylene group having a total carbon number of 3 to 15, wherein Z is a substituted or unsubstituted alkyl group having a total carbon number of 1 to 10, substituted or Unsubstituted alkenyl group having 1 to 10 carbon atoms, substituted or unsubstituted alicyclic compound group having 3 to 15 total carbon atoms, substituted or unsubstituted aryl group having 6 to 15 total carbon atoms, substituted or unsubstituted Represents an aralkyl group having a total carbon number of 7 to 15, a substituted or unsubstituted heteroaryl group having a total carbon number of 3 to 15, or a metal complex, and Z ′ represents a substituted or unsubstituted alkyl group having a total carbon number of 1 to 10. A substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, substituted or unsubstituted An alicyclic compound group having 3 to 15 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms,
Represents a substituted or unsubstituted aralkyl group having a total carbon number of 7 to 15 or a substituted or unsubstituted heteroaryl group having a total carbon number of 3 to 15, wherein R and R'independently represent hydrogen, a substituted or unsubstituted total group. It represents an alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 15 carbon atoms in total. ] 2. The optical recording medium according to claim 1, wherein the substituent A in the phthalocyanine compound is selected from the groups represented by the following formulas (b-1) to (b-5). [Chemical 3] [Z, Z ', R and R'in Formulas (b-1) to (b-5)
Is Z, Z ′ in the above formulas (a-1) to (a-9),
It has the same meaning as R and R '. ] 3. The optical recording medium according to claim 2, wherein the substituent A in the phthalocyanine compound is selected from the groups represented by formulas (b-1) to (b-3). 4. The optical recording medium according to claim 3, wherein the substituent A in the phthalocyanine compound is a group represented by the formula (b-1). 5. The phthalocyanine compound has a wavelength of 65.
The maximum value of the extinction coefficient k in 0 nm to 900 nm is represented by kma
The optical recording medium according to any one of claims 1 to 4, wherein when x, kmax ≥ 0.9 is satisfied.