JPH09202860A - Phthalocyanine compound, its production and optical recording medium using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phthalocyanlie compound having absorbability in a far infrared region of 600-1000nm and excellent in solubility, to provide a method for producing the compound, and to obtain an optical recording medium using the same. SOLUTION: A phthalocyanine compound in which one to eight positions among the sixteen substitutive positions of the benzene nuclei in the phthalocyanine skeleton are substituted with one to eight phenoxy groups and further with aryl groups which may have substituents. The compound is produced by reacting a metal compound with a phthalonitrile compound substituted by the phenoxy groups replaced with aryl groups which may have substituents. The optical recording medium contains the compound in a recording layer disposed on a substrate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel phthalocyanine compound, a method for producing the same and an optical recording medium using them. The novel phthalocyanine compound according to the present invention absorbs in the near-infrared region of 600 to 1000 nm and has excellent solubility, so that it can be written or read in an optical recording medium using a semiconductor laser, a liquid crystal display, an optical character reader, or the like. Near-infrared absorbing dyes, near-infrared sensitizers, thermal transfer agents, photothermal conversion agents such as thermosensitive paper / thermosensitive stencils, near-infrared absorption filters, anti-eye fatigue agents, near-infrared absorption used as photoconductive materials Color separation filters, liquid crystal display devices, color CRT selective absorption filters, color toners, inkjet inks, barcode inks to prevent tampering and counterfeiting as materials or for imaging tubes, microbial deactivators, photosensitizers for tumor treatment It exerts an excellent effect when used as a coloring matter.

In particular, they exhibit a very excellent effect as a near-infrared absorbing dye for use in a write-once optical recording medium compatible with a compact disk.

[0003]

2. Description of the Related Art In recent years, the development of optical recording media, such as compact disks, laser disks, optical memory disks, and optical cards, using a semiconductor laser as a light source has been active. In particular, CD, PHOTO-CD or CD-RO
M is widely used as a large-capacity, high-speed access digital recording medium for storing and reproducing voices, images, code data, and the like. These systems all require so-called near-infrared absorbing dyes which are sensitive to semiconductor lasers, and those dyes having good properties are required.

[0004] Among them, many phthalocyanine compounds which are stable to light, heat, temperature, etc. and have excellent fastness have been studied.

The characteristics required for use in a write-once optical recording medium compatible with a compact disk include (1) that the maximum absorption wavelength of the thin film is controlled to 700 to 730 nm (the peak due to association is small, and High absorbance and sharp peaks are key components for optical properties such as reflectivity),
(2) It can be applied onto a substrate by a simple and highly productive method such as spin coating, and has excellent solubility in a solvent that does not attack the substrate. (3) Heat resistance and light resistance Good, (4) good thermal decomposition characteristics (a main constituent factor for sensitivity), (5) a compound excellent in economy in the production method, and the like.

For example, Japanese Patent Laid-Open No. 58-56892 discloses that
A method using a perfluorophthalocyanine compound has been proposed. However, these compounds have poor solubility in organic solvents and cannot be controlled to a satisfactory absorption wavelength.

JP-A-61-192780, JP-A-61-192780
JP-A-246091, JP-A-63-37991, JP-A-64-42283, JP-A-2-276677, JP-A-2-91360, JP-A-2-265788, JP-A-3-215466, JP-A-3-215466 No. 4-226390 proposes a phthalocyanine skeleton in which a substituent is introduced into the benzene ring via oxygen. However, these compounds have poor light resistance depending on the type, number and position of the substituents of the dye, have low reflectivity, and do not dissolve in a solvent that can be directly applied to a substrate such as a commonly used polycarbonate. Or there is a problem in controlling the absorption wavelength.

Japanese Patent Application Laid-Open No. Hei 5-12772 and the like propose a method in which four alkoxy groups are introduced at the α-position of phthalocyanine and a halogen compound or the like is partially introduced into the residue. Have been. However, those having a substituent introduced at the α-position have a problem in terms of economic efficiency such as poor productivity from phthalonitrile as a raw material. Further, such a phthalocyanine compound does not necessarily satisfy all the properties, and thus further better properties are desired.

The present applicants have proposed a phthalocyanine compound in which a phenoxy group having a bulky substituent is substituted at the β-position (JP-A-5-345861,
JP-A-6-107766, JP-A-6-328856 and JP-A-8-225751.

However, these compounds also have problems in reflectance, sensitivity, and the like in optical recording media, and the phthalocyanine compounds proposed so far do not satisfy all of the above characteristics.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in consideration of the above circumstances of the prior art. That is, the object of the present invention is to enable absorption control according to the purpose in the absorption wavelength range of 600 to 1000 nm, and to have excellent solubility in a solvent suitable for the application, such as an alcohol solvent, and heat resistance. Another object of the present invention is to provide a novel phthalocyanine compound having high light resistance.

Another object of the present invention is to provide a method for efficiently producing a phthalocyanine compound with high purity.

Still another object of the present invention is an optical recording medium,
In particular, it is an object of the present invention to provide a phthalocyanine compound exhibiting excellent effects in solubility, absorption wavelength, sensitivity, reflectance, light resistance, and thermal decomposition characteristics required for an optical recording medium compatible with a compact disk. .

[0014]

The above objects are achieved by the following (1) to (11).

(1) An aryl in which 1 to 8 out of 16 substitutable positions of the benzene nucleus of the phthalocyanine skeleton are substituted with a phenoxy group, and the phenoxy group may have a substituent. A phthalocyanine compound substituted with a group.

(2) The phthalocyanine compound as described in (1) above, wherein the ortho position of the phenoxy group is substituted with the aryl group.

(3) One of the ortho positions of the phenoxy group is substituted with the aryl group, and at least the remaining ortho position is a substituent of the following groups (1) to (7):

[0018]

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(Wherein R ¹ represents a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group which may have a substituent,
R ² , R ³ , R ⁴ and R ⁵ each independently have 1 carbon atom
To 20 linear, branched or cyclic alkyl groups or aryl groups which may have a substituent, R ⁶ represents an aryl group which may have a substituent, and A represents C
Represents an H group or a nitrogen atom, B represents an oxygen atom, a sulfur atom, a CH ₂ group, an NH group or an alkylamino group having 1 to 4 carbon atoms, and a, b, c and e are integers of 1 to 5 And d and f are integers of 0 to 6, and g and h are each independently an integer of 1 to 4. The phthalocyanine compound according to (1) or (2) above, which is substituted with at least one substituent selected from

(4) The above (1) to (1) wherein the benzene nucleus of the phthalocyanine skeleton is further substituted with a halogen atom.
The phthalocyanine compound according to any one of (3).

(5) General formula (1)

[0022]

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[Wherein, X, Y and Z represent a hydrogen atom or a fluorine atom, at least one of X, Y and Z is a fluorine atom, and W represents an optionally substituted aryl group. , V are defined in claim 3 (1)-
It represents at least one substituent selected from the substituents of group (7), n is an integer of 0 to 4, and M represents a metal, a metal oxide or a metal halide. ] The phthalocyanine compound as described in any one of said (1)-(4) shown by these.

(6) The phthalocyanine compound according to the above (5), wherein in the general formula (1), one of V and W are at both ortho positions.

(7) In the general formula (1), V is 2
The phthalocyanine compound according to (5) or (6) above, which is an alkoxycarbonyl group in which a higher-grade alkyl group is directly bonded to a carbonyl group.

(8) In the general formula (1), each of X, Y and Z is a fluorine atom (5) to (7).
The phthalocyanine compound according to any one of 1.

(9) substituted with a phenoxy group,
The phenoxy group is characterized by reacting a metal compound with a phthalonitrile compound substituted with an optionally substituted aryl group or a mixture of the phthalonitrile compound not substituted with the phenoxy group. The method for producing a phthalocyanine compound according to any one of (1) to (8) above.

(10) An optical recording medium containing the phthalocyanine compound according to any one of (1) to (8) in a recording layer provided on a substrate.

(11) In a write-once type optical recording medium for a compact disc, which has a recording layer and a metallic reflecting layer provided on a transparent resin substrate, the recording layer is the recording layer described in (10) above. An optical recording medium.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION The phthalocyanine compound according to the present invention has 1 to 8 of the 16 substitutable positions of the benzene nucleus of the phthalocyanine skeleton substituted with a phenoxy group, and the phenoxy group is a substituent. And a phthalocyanine compound substituted with an aryl group which may have. Examples of the aryl group which may have a substituent include a phenyl group and a naphthyl group.
Preferably it is a phenyl group. Substituents optionally present in the aryl group are, for example, halogen atoms, alkyl groups, alkoxy groups, halogenated alkyl groups, halogenated alkoxy groups, nitro groups, amino groups, alkylamino groups, alkoxycarbonyl groups and the like. Among the novel phthalocyanine compounds, preferred ones are those represented by the above general formula (1).
Which will be described in detail below.

In the general formula (1), M is a metal, a metal oxide or a metal halide. Specific examples of the central metal of the phthalocyanine compound represented by M include iron chloride,
Magnesium, nickel, cobalt, copper, palladium,
Zinc, aluminum chloride, indium chloride, germanium chloride, tin chloride, silicon chloride, titanyl, vanadyl and the like, in terms of good light resistance, cobalt, copper, zinc, tin chloride or vanadyl is preferable, particularly vanadyl preferable.

The substituent on the phenoxy group represented by W represents an aryl group which may have a substituent. Examples of the aryl group include a phenyl group and a naphthyl group. Particularly preferred is a phenyl group.
Substituents optionally present in the aryl group are, for example, a halogen atom, an alkyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, a nitro group, an amino group, an alkylamino group, an alkoxycarbonyl group and the like.

Here, the halogen atom means fluorine, chlorine, bromine and iodine, of which bromine is preferable.

The alkyl group is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferably having 1 carbon atom.
To 8 alkyl groups. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, 2-ethylhexyl group. Group, n-decyl group, lauryl group, stearyl group and the like.

The alkoxy group is a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 8 carbon atoms. Specifically, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-octyl group. An oxy group, a 2-ethylhexyloxy group, an n-decyloxy group and the like are shown.

The halogenated alkyl group has 1 to 2 carbon atoms.
A part of the straight-chain, branched-chain or cyclic alkyl group of 0 is halogenated, preferably a part of the alkyl group having 1 to 8 carbon atoms is halogenated. Particularly preferably, part of the alkyl group having 1 to 8 carbon atoms is brominated. Specifically, monobromoalkyl groups such as bromomethyl group, bromoethyl group, bromopropyl group, bromobutyl group, bromopentyl group, bromohexyl group, bromoheptyl group, bromooctyl group, 1,
A dibromoalkyl group and the like such as a 3-dibromopropyl group and a 1,3-dibromobutyl group are shown.

The halogenated alkoxy group has 1 to 1 carbon atoms.
A part of 20 linear, branched or cyclic alkoxy groups is halogenated, preferably having 1 to 8 carbon atoms.
Some of the alkoxy groups are halogenated. Particularly preferably, part of the alkoxy group having 1 to 8 carbon atoms is brominated. Specifically, a monobromoalkoxy group such as bromomethoxy group, bromoethoxy group, bromopropoxy group, bromobutoxy group, bromopentoxy group, bromohexyloxy group, bromoheptyloxy group, bromooctyloxy group, 1,3 A dibromoalkoxy group such as a dibromopropoxy group or a 1,3-dibromobutoxy group.

The alkoxycarbonyl group means an alkoxycarbonyl having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms which may contain a hetero atom in the alkyl group portion of the alkoxy group, or 3 to 8 carbon atoms which may contain a hetero atom, Preferably, it represents 5 to 8 cyclic alkoxycarbonyl. Specifically, methoxycarbonyl group, ethoxycarbonyl group, n
-Butoxycarbonyl group, tcrt-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, methoxyethoxycarbonyl group, ethoxyethoxycarbonyl group, butoxyethoxycarbonyl group, diethylaminoethoxycarbonyl Group, methylthioethoxycarbonyl group, methoxypropyloxycarbonyl group, (3,6,9-oxa) decyloxycarbonyl group, tetrahydrofurfuryloxycarbonyl group, pyranoxycarbonyl group, piperidinooxycarbonyl group, piperidinoethoxy Carbonyl group, tetrahydropyrroleoxycarbonyl group, tetrahydropyranmethoxycarbonyl group, tetrahydrothiopheneoxycarbonyl group, cyclohexyl Shows the alkoxycarbonyl group or the like.

The substitution position of W on the phenoxy group is not particularly limited, but it is more preferably at the ortho position of the phenoxy group. By having the aryl group which may have a substituent at the ortho position of the phenoxy group, the absorption peak derived from the aggregate (hereinafter referred to as the association peak) in the absorption spectrum of the thin film of the phthalocyanine compound is greatly suppressed, An absorption peak derived from a monomer (hereinafter referred to as a monomer peak) becomes sharp, which is preferable.

The substituent on the phenoxy group represented by V is a substituent of the following groups (1) to (7):

[0041]

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(In the formula, R ¹ represents a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group which may have a substituent,
R ² , R ³ , R ⁴ and R ⁵ each independently have 1 carbon atom
To 20 linear, branched or cyclic alkyl groups or aryl groups which may have a substituent, R ⁶ represents an aryl group which may have a substituent, A represents a CH group or Represents a nitrogen atom, B is an oxygen atom, a sulfur atom, C
H ₂ group, NH group or an alkylamino group having 1 to 4 carbon atoms, a, b, c and e are integers of 1 to 5, d and f are integers of 0 to 6 and g And h are each independently an integer of 1 to 4. Represents at least one kind of substituent selected from Specific examples of these substituents include the following substituent groups.

Group (1): fluorine, chlorine, bromine, iodine,
Methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl, tert
-Butyl, straight-chain or branched pentyl, straight-chain or branched hexyl, cyclohexyl, straight-chain or branched heptyl, straight-chain or branched octyl, straight-chain or branched nonyl, straight-chain or branched decyl, straight-chain or Branched undecyl, linear or branched dodecyl, phenyl, o-methylphenyl, m-
Methylphenyl, p-methylphenyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, o-
Propylphenyl, m-propylphenyl, p-propylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, o-butylphenyl, m-butylphenyl, p-butylphenyl,
o-tert-butylphenyl, m-tert-butylphenyl, p-tert-butylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-ethoxyphenyl, m-ethoxyphenyl,
p-ethoxyphenyl, o-propoxyphenyl, m-
Propoxyphenyl, p-propoxyphenyl, o-isopropoxyphenyl, m-isopropoxyphenyl,
p-isopropoxyphenyl, o-butoxyphenyl,
m-butoxyphenyl, p-butoxyphenyl, 2,6
-Dimethylphenyl, 2,6 diethylphenyl, 2,6
-Dipropylphenyl, 2,6-diisopropylphenyl, 2,6-dibutylphenyl, 2,6-ditert-
Butylphenyl, 2,6-dimethoxyphenyl, 2,6
-Diethoxyphenyl, 2,6-dipropoxyphenyl, 2,6-diisopropoxyphenyl, 2,6-dibutoxyphenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-iodophenyl, 3
-Fluorophenyl, 3-chlorophenyl, 3-bromophenyl, 3-iodophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 2,3 difluorophenyl, 2,3-dichlorophenyl, 2 , 4-difluorophenyl, 2,4
-Dichlorophenyl, 2,4-dibromophenyl, 2,
5-difluorophenyl, 2,5-dichlorophenyl,
2,6-difluorophenyl, 2,6-dichlorophenyl, 2,6-dibromophenyl, 3,4-difluorophenyl, 3,4-dichlorophenyl, 3,5-difluorophenyl, 3,5-dichlorophenyl, 2,3,3 4-
Trifluorophenyl, 2,3,4-trichlorophenyl, 2,3,5-trifluorophenyl, 2,3,5-
Trichlorophenyl, 2,3,6-trifluorophenyl, 2,3,6-trichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl, 2,4,6-tribromophenyl , 2,4,6-triiodophenyl, 2,3,5,6-tetrafluorophenyl, pentafluorophenyl, pentachlorophenyl.

Group (2): methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, linear or branched pentyloxycarbonyl, linear or Branched hexyloxycarbonyl, cyclohexyloxycarbonyl, linear or branched heptyloxycarbonyl, linear or branched octyloxycarbonyl, linear or branched nonyloxycarbonyl, linear or branched decyloxycarbonyl, linear or branched Undecyloxycarbonyl, linear or branched dodecyloxycarbonyl, cyclohexanemethoxycarbonyl, cyclohexaneethoxy Carbonyl, 3-cyclohexyl -1
-Propoxycarbonyl, tert-butylcyclohexyloxycarbonyl, phenoxycarbonyl, 4-methylphenoxycarbonyl, 4-chlorophenoxycarbonyl, 4-cyclohexylphenoxycarbonyl, 4
-Phenylphenoxycarbonyl, 2-fluorophenoxycarbonyl, 4-ethoxyphenoxycarbonyl.

Group (3): methoxyethoxycarbonyl,
Ethoxyethoxycarbonyl, 3 ', 6'-oxaheptyloxycarbonyl, 3', 6'-oxaoctyloxycarbonyl, 3 ', 6', 9'-oxadecyloxycarbonyl, 3 ', 6', 9 ', 12 '-Oxatridecyl oxydicarbonyl.

Group (4): methoxypropyloxycarbonyl, ethoxypropyloxycarbonyl, 4 ', 8'
-Oxanonyloxycarbonyl, 4 ', 8'-oxadecyloxycarbonyl, 4', 8 ', 12'-oxatridecyloxycarbonyl.

Group (5): methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec
-Butoxy, tert-butoxy, straight-chain or branched pentyloxy, straight-chain or branched hexyloxy, cyclohexyloxy, straight-chain or branched heptyloxy, straight-chain or branched octyloxy, straight-chain or branched nonyloxy, direct Chain or branched decyloxy, straight chain or branched undecyloxy, straight chain or branched dodecyloxy, methoxyethoxy, ethoxyethoxy, 3 ', 6'-oxaheptyloxy, 3', 6'-oxaoctyloxy, 3 ',
6 ', 9'-oxadecyloxy, 3'6', 9 ', 1
2'-oxatridecyloxy, methoxypropyloxy, ethoxypropyloxy, 4 ', 8'-oxanonyloxy, 4', 8'-oxadecyloxy.

Group (6): benzyloxycarbonyl, phenethyloxycarbonyl, 3-fer-1-propoxycarbonyl, 4-phenyl-1-butoxycarbonyl, 5-phenyl-1-pentoxycarbonyl, 6-phenyl-1-. Hexyloxycarbonyl.

Group (7): 2-tetrahydroxyfuranoxycarbonyl, 4-tetrahydropyranooxycarbonyl, 2-pyrrolidinooxycarbonyl, 2-piperidinooxycarbonyl, 2-tetrahydrothiopheneoxycarbonyl, tetrahydrofurfuryloxy Carbonyl, 4-tetrahydropyranooxycarbonyl, 2-morpholinoethoxycarbonyl, 2-pyrrolidinoethoxycarbonyl, 2-piperazinoethoxycarbonyl.

Among the substituents of the groups (1) to (7),
It is preferably a group (2). Particularly, an alkoxycarbonyl group in which a secondary or higher alkyl group such as isopropoxycarbonyl or tert-butoxycarbonyl is directly bonded to a carbonyl group is preferable. By using a phthalocyanine compound in which an alkoxycarbonyl group in which a secondary or higher alkyl group is directly bonded to a carbonyl group is a substituent, optical characteristics such as reflectance and recording sensitivity when the phthalocyanine compound is used in an optical recording medium, It is particularly preferable because it has excellent recording sensitivity.

The substitution position of the substituent V on the phenoxy group is not particularly limited, but it is preferably at the ortho position of the phenoxy group, and particularly V and W are both at the ortho position of the phenoxy group, that is, at the 2,6 position. Preferably there is.
By having V and W at the 2,6 positions of the phenoxy group,
The association peak in the absorption spectrum of the thin film of the phthalocyanine compound is largely suppressed, and the monomer peak becomes sharp. Therefore, it is preferable because the phthalocyanine compound is excellent in optical characteristics such as reflectance and recording sensitivity when used in an optical recording medium.

Particularly preferably, V and W are at the 2 and 6-positions of the phenoxy group, and V is an alkoxycarbonyl group in which a secondary or higher alkyl group is directly bonded to the carbonyl group. As a result, optical characteristics such as reflectance and recording sensitivity when this phthalocyanine compound is used for an optical recording medium are particularly excellent.

New substituents may be introduced at the positions remaining after the above-mentioned substituents V and W are introduced into the phenoxy group in order to further improve the solubility and control the absorption wavelength. Examples of these substituents include a halogen atom, an alkoxycarbonyl consisting of a linear or branched alkoxy having 1 to 20 carbon atoms which may be substituted with an alkoxy group, an aryloxycarbonyl group which may be substituted, and a direct substituent. Chain or branched alkyl group having 1 to 12 carbon atoms which may be substituted, linear or branched alkoxy group having 1 to 12 carbon atoms, linear or branched carbon number 1 to 1 20 monoalkylamino groups, linear or branched C1-20 dialkylamino groups, cyclohexyl groups, optionally substituted phenoxy groups, optionally substituted anilino groups or nitro groups, etc. Is mentioned.

Of these, a halogen atom is preferable, and a bromine atom is particularly preferable.

X, Y and Z represent a hydrogen atom or a fluorine atom, and at least one of X, Y and Z is a fluorine atom. It is preferable that all of X, Y and Z are fluorine atoms from the viewpoint of excellent solubility of the phthalocyanine compound.

Further, V and W are at the 2 and 6 positions of the phenoxy group, V is an alkoxycarbonyl group in which a secondary or higher alkyl group is directly bonded to the carbonyl group, and X, Y and Z are all fluorine. Since it is an atom, it is excellent in solubility and therefore excellent in film forming property. Further, when this phthalocyanine compound is used for an optical recording medium, optical characteristics such as reflectance and recording sensitivity are particularly excellent. Therefore, it is particularly preferable because it has a performance corresponding to a high-speed recording type compact disc.

Specific examples of the phthalocyanine compound used in the present invention include the following compounds.

Compound 1: Tetrakis (2-phenyl-6)
-Isopropylphenoxy) dodecafluorozinc phthalocyanine, general formula (2)

[0059]

[Chemical 6]

In the above, A is a compound represented by the following formula (M: Zn)

[0061]

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Similarly, a compound (M: VO) in which A is similarly represented by the following formula 2: tetrakis (2,6-diphenylphenoxy) dodecafluorovanadyl phthalocyanine,

[0063]

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Compound 3: tetrakis (2,4-diphenylphenoxy) dodecafluorotitanyl phthalocyanine,

[0065]

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Compound 4: tetrakis (2,4,6-triphenylphenoxy) dodecafluorovanadyl phthalocyanine,

[0067]

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Compound 5: tetrakis (2-isopropoxycarbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine,

[0069]

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Compound 6: Tetrakis (2- (3-pentoxy) carbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine,

[0071]

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Compound 7: tetrakis (2- (3-pentoxy) carbonyl-4-phenylphenoxy) dodecafluorocopper phthalocyanine,

[0073]

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Compound 8: tetrakis (2-tertbutoxycarbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine,

[0075]

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Compound 9: tetrakis (2,4-diisopropoxycarbonyl-6-phenylphenoxy) dodecafluoroiron phthalocyanine,

[0077]

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Compound 10: tetrakis (2- (2-butoxy) carbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine,

[0079]

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Compound 11: tetrakis (2- (2-pentoxy) carbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine,

[0081]

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Compound 12: tetrakis (2- (3-methoxypropoxy) carbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine,

[0083]

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Compound 13: Tetrakis (2,4-di (2
-Methoxyethoxy) carbonyl-6-phenylphenoxy) dodecafluoronickel phthalocyanine,

[0085]

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Compound 14: tetrakis (2-ethoxy-
6-phenylphenoxy) dodecafluorovanadyl phthalocyanine,

[0087]

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Compound 15: tetrakis (2,4-diethoxy-6-phenylphenoxy) dodecafluoropalladium phthalocyanine,

[0089]

[Chemical 21]

Compound 16: tetrakis (2-benzyloxycarbonyl-6-phenylphenoxy) dodecafluorotitanyl phthalocyanine,

[0091]

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Compound 17: tetrakis (2-phenethyloxycarbonyl-6-phenylphenoxy) dodecafluorozinc phthalocyanine,

[0093]

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Compound 18: tetrakis (2- (2-tetrahydrofurfuryloxy) carbonyl-6-phenylphenoxy) dodecafluoro (dichlorotin) phthalocyanine,

[0095]

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Compound 19: tetrakis (4- (2-tetrahydrofurfuryloxy) carbonyl-6-phenylphenoxy) dodecafluoro (dichlorotin) phthalocyanine,

[0097]

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Compound 20: Tetrakis (2,4-di (2
-Tetrahydrofurfuryloxy) carbonyl-6-phenylphenoxy) dodecafluorocobalt phthalocyanine,

[0099]

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Compound 21: Tetrakis (6- (bromophenyl) -2-isopropoxycarbonylphenoxy)
Dodecafluorovanadyl phthalocyanine,

[0101]

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Compound 22: tetrakis (bromo-2-isopropoxycarbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine,

[0103]

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Compound 23: tetrakis (6- (4-chlorophenyl) -2-isopropoxycarbonylphenoxy) dodecafluorotitanyl phthalocyanine,

[0105]

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Compound 24: tetrakis (4-fluoro-
2- (2-methoxyethoxy) carbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine,

[0107]

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Compound 25: tetrakis (6- (4-bromomethylphenyl) -2- (2-tetrahydrofurfuryloxy) carbonylphenoxy) dodecafluorotitanyl phthalocyanine,

[0109]

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Compound 26: tetrakis (6- (4-bromomethoxyphenyl) -2-isopropoxycarbonylphenoxy) dodecafluorovanadyl phthalocyanine,

[0111]

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Compound 27: bis (2-isopropoxycarbonyl-6-phenylphenoxy) tetradecafluorovanadyl phthalocyanine (general formula (3)),

[0113]

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However, in the formula, two of Y ^{1 to} Y ⁴ are fluorine atoms, and the remaining two are represented by the following formula:

[0115]

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Compound (M: VO) represented by the following: Similarly, in the general formula (3), two of Y ^{1 to} Y ⁴ are fluorine atoms, and the other two are compounds represented by the following formula (M: VO). : TiO) Compound 28: Bis (2- (2-methoxyethoxy) carbonyl-6-phenylphenoxy) tetradecafluorotitanyl phthalocyanine,

[0117]

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Compound 29: octakis (2-isopropoxycarbonyl-6-phenylphenoxy) octafluorovanadyl phthalocyanine (general formula (4)),

[0119]

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Where Z is the following formula

[0121]

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Compound (M: VO) represented by the following: Similarly, a compound (M: V) in which Z is represented by the following formula:
O) compound 30: octakis (2-tert-butoxycarbonyl-6-phenylphenoxy) octafluorovanadyl phthalocyanine,

[0123]

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The method for producing the novel phthalocyanine compound of the present invention will be described in detail below.

First, the novel phthalocyanine compound of the present invention is substituted with a phenoxy group, and the phthalonitrile compound substituted with an aryl group which may have a substituent is used alone or with the phenoxy group. It can be produced by reacting a mixture of an unsubstituted phthalonitrile and a metal compound.

In the phthalonitrile compound substituted with the phenoxy group, some or all of the residues may be further substituted with a substituent other than the phenoxy group. That is, the term phthalonitrile compound substituted with the phenoxy group alone is not limited to one kind of the phthalonitrile compound substituted only with the phenoxy group.In addition, it is further substituted with the above-mentioned phenoxy group, A phthalonitrile compound in which some or all of its residues are substituted with a substituent other than a phenoxy group, or a phthalonitrile compound in which both are combined may be used. Also,
Phthalonitrile which is not substituted with the phenoxy group may further be partially or entirely substituted with a substituent other than the phenoxy group at a substitutable position of the benzene nucleus. That is, the term phthalonitrile not substituted with the phenoxy group is not limited to only phthalonitrile not substituted with the phenoxy group.In addition, it is not substituted with the above-mentioned phenoxy group. A phthalonitrile compound in which part or all of the substitutable positions of the benzene nucleus with a substituent other than a phenoxy group is substituted with a substituent other than a phenoxy group, or a phthalonitrile compound in which both are combined may be used. Therefore, in the case of a mixture of a phthalonitrile compound substituted with a phenoxy group and a phthalonitrile not substituted with the phenoxy group, one or more of the above-mentioned phthalonitrile compounds substituted with a phenoxy group may be used. And one or more of phthalonitriles not substituted with the phenoxy group.

Examples of the substituent other than the phenoxy group in the phthalonitrile compound substituted with the phenoxy group alone or in the phthalonitrile not substituted with the phenoxy group include a halogen atom, an alkyl group, an aryl group and a hetero group. Ring group, cyano group, hydroxy group, nitro group, amino group (including substituted amino group), alkoxy group, acylamino group, aminocarbonylamino group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group , Sulfonylamino group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group,
Azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, imide group,
Examples include a heterocyclic thio group, a sulfinyl group, a phosphoryl group, and an acyl group. The kind of the substituent may be one kind or two or more kinds. Preferred substituents are a halogen atom, especially a chlorine atom and a fluorine atom, especially a fluorine atom.

The phthalonitrile used in the production of the phthalocyanine compound of the present invention may be the above-mentioned phthalonitrile compound substituted with a phenoxy group alone or a mixture with a phthalonitrile not substituted with the phenoxy group. Is preferably a phthalonitrile compound substituted with a phenoxy group.

A method for producing a preferable compound represented by the general formula (1) among the novel phthalocyanine compounds of the present invention will be described in detail below.

Suitable novel phthalocyanine compounds represented by the general formula (1) include, for example, the following general formula (5)

[0131]

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[Wherein, X, Y and Z represent a hydrogen atom or a fluorine atom, at least one of X, Y and Z is a fluorine atom, and W represents an optionally substituted aryl group. , V is a substituent of the following groups (1) to (7):

[0133]

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(In the formula, R ¹ represents a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group which may have a substituent,
R ² , R ³ , R ⁴ and R ⁵ each independently have 1 carbon atom
To 20 linear, branched or cyclic alkyl groups or aryl groups which may have a substituent, R ⁶ represents an aryl group which may have a substituent, and A represents C
Represents an H group or a nitrogen atom, B represents an oxygen atom, a sulfur atom, a CH ₂ group, an NH group or an alkylamino group having 1 to 4 carbon atoms, and a, b, c and e are integers of 1 to 5 And d and f are integers of 0 to 6, and g and h are each independently an integer of 1 to 4. Represents at least one kind of substituent selected from the group, and n is an integer of 0-4. The phthalonitrile compound represented by the formula [1] is reacted with a metal compound.

In this case, in the general formula (5), X, Y
It is desirable that both Z and Z are fluorine atoms.

In the method for producing a novel phthalocyanine compound of the present invention, the reaction between the phthalonitrile compound alone or a mixture of the phthalonitrile not substituted with the phenoxy group and the metal compound can be carried out in the absence of a solvent. It is preferable to use it. The organic solvent may be any inert solvent that is not reactive with the starting materials, for example, benzene, toluene, xylene, nitrobenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene Inert solvents such as glycol and benzonitrile or non-protons such as pyridine, N, N-dimethylformamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethylsulfoxide and sulfolane A polar solvent or the like can be used, and preferred are 1-chloronaphthalene, 1-methylnaphthalene and benzonitrile.

In the present invention, 2 to 40 parts, preferably 20 parts, of a mixture of a phthalonitrile compound or a phthalonitrile which is not substituted with the phenoxy group is added to 100 parts (hereinafter, parts by weight) of an organic solvent. To 35 parts, 1 to 2 mol, preferably 1.1 to 1. 1 mol, based on 4 mol of a mixture of the metal compound with the phthalonitrile compound or phthalonitrile not substituted with the phenoxy group.
It is charged in the range of 5 mol and reacted at a reaction temperature of 30 to 250 ° C, preferably 80 to 200 ° C.

Examples of the metal compound include halogen compounds such as chlorides, bromides and iodides, organic acid metal salts such as metal oxides and acetates, complex compounds such as acetylacetonate, metal carbonyl compounds and metal powders. .

In the present invention, the phthalocyanine compound as a starting material can be synthesized according to step A of the following scheme, for example, using the phthalonitrile compound represented by the general formula (5) as an example. Then, the general formula (1) of the present invention
The synthesis of the novel phthalocyanine compound represented by
The target product can be obtained according to the above.

[0140]

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The novel phthalocyanine compounds represented by the general formulas (3) and (4) can be synthesized by the same method as the method for synthesizing the novel phthalocyanine compound represented by the general formula (1). That is, the novel phthalocyanine compound represented by the general formula (3) is prepared in step B of the above synthesis scheme as 3,4,5,6-
It can be synthesized by using a 1: 1 (molar ratio) mixture of tetrafluorophthalonitrile and a phthalonitrile compound represented by the general formula (5). In addition, the novel phthalocyanine compound represented by the general formula (4) can be prepared by using the phenol as a raw material in Step A of the above synthesis scheme in a double amount to obtain the following general formula (6)

[0142]

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It can be synthesized by producing the phthalonitrile compound represented by: and then using the phthalonitrile compound represented by the general formula (6) as a raw material in step B.

The phthalocyanine compound of the present invention has high solubility, a small association peak in the absorption spectrum of a thin film, a sharp monomer peak, and excellent light resistance. Further, since the phthalocyanine compound of the present invention is excellent in reflectance and sensitivity when used in an optical recording medium, it is particularly necessary to have those characteristics, a transparent resin substrate, and a recording layer provided on the substrate. As a write-once optical recording medium for a compact disc, which comprises a metal and a metal reflection layer, for example, a CD for reproducing music such as audio and a PHO for storing photographs
The effect can be exerted as a write-once type optical recording medium having compatibility and commonality with a TO-CD or a CD-ROM player for a computer.

As an optical recording medium containing a phthalocyanine compound in a recording layer provided on a substrate, a thin film of a phthalocyanine compound in which the substituents V and W are at the 2 and 6-positions of the phenoxy group in the general formula (1) is used. The association peak in the absorption spectrum is largely suppressed, and the monomer peak becomes sharp. Therefore, the phthalocyanine compound is preferable in terms of reflectance and recording sensitivity when used in an optical recording medium. In the general formula (1), n is an integer of 0 to 4, preferably an integer of 1 to 2.

The novel phthalocyanine compound of the present invention is excellent in the control of the absorption wavelength while maintaining the light resistance, the optical characteristics in the thin film (the association peak is suppressed and the monomer peak becomes sharp), and the solubility in the organic solvent. The characteristics described above are obtained, and excellent effects can be exhibited in an optical recording medium compatible with compact discs.

The disk substrate used in this case is preferably one through which light for recording or reading a signal is transmitted. It is desirable that the light transmittance is 85% or more and the optical anisotropy is small. For example, a substrate made of glass, acrylic resin, polycarbonate resin, polyester resin, polyamide resin, vinyl chloride resin, polystyrene resin, epoxy resin, or the like can be used. Of these, polycarbonate resins are preferred from the viewpoint of optical properties, ease of molding, mechanical strength, and the like.

The above-mentioned dye is first formed on this substrate, and a metal reflection film layer is formed thereon. The metal used as the reflective film layer includes aluminum, silver, gold, copper, platinum and the like, and this reflective film layer is usually formed by a method such as vacuum evaporation or sputtering.

In order to form the recording layer containing the dye on the substrate in the optical recording medium of the present invention, it is usually preferable to use a coating method. The method can be a spin coating method, a dip method or a roll coating method, and a spin coating method is particularly preferable. The organic solvent used at that time does not damage the substrate. For example, hexane,
Aliphatic or alicyclic hydrocarbon solvents such as octane and cyclohexane or methyl alcohol, ethyl alcohol, isopropyl alcohol, allyl alcohol, 2-
Alcohol solvents such as methoxyethanol, 2-ethoxyethanol and diacetone alcohol are preferred.
Since the dye of the present invention dissolves particularly well in alcohol solvents, these solvents are preferably used.

The CD which is one kind of the optical recording medium of the present invention is
From the viewpoint of compatibility with players, it is required that the reflectivity to read laser light through the substrate be 60% or more.

These are possible by optimizing the film thickness according to each dye, and usually 50 nm to 3
00 nm, particularly 80 nm to 200 nm, is preferable.

[0152]

The present invention will be described below in more detail with reference to examples.

Example 1 Preparation of Compound 5 In a 100 ml four-necked flask, 4.36 g (0.01 mol) of a phthalonitrile compound represented by the following structural formula (7) and 0.47 g (3 mmol) of vanadium trichloride. Then, 15 ml of benzonitrile was charged and reacted at 175 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to obtain a target green cake (tetrakis (2-isopropoxycarbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine (Compound 5). ) 4.0 g were obtained.
(Yield, 88.4% based on phthalonitrile).

[0154]

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Visible absorption spectrum Maximum absorption wavelength 715.2 nm in 2-ethoxyethanol (ε = 1.45 × 10 5) Thin film 731.4 nm Solubility 14% by weight with respect to 2-ethoxyethanol Elemental analysis H C N F Theoretical value 3 0.34% 63.62% 6.18% 12.58% Analytical value 3.41% 62.93% 6.31% 13.01% Example 2 Preparation of compound 6 The following structure was prepared in a 100 ml four-necked flask. 4.64 g (0.01 mol) of the phthalonitrile compound represented by the formula (8), 0.47 g (3 mmol) of vanadium trichloride and 15 ml of benzonitrile were charged and reacted at 175 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to give the desired green cake (tetrakis (2- (3-pentoxy) carbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine ( Compound 6)) 4.4 g was obtained. (Yield, 91.1% based on phthalonitrile).

[0156]

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Visible absorption spectrum Maximum absorption wavelength 713.1 nm (ε = 1.61 × 10 5) in 2-ethoxyethanol Thin film 729.6 nm Solubility 15% by weight with respect to 2-ethoxyethanol Elemental analysis H C N F Theoretical value 3 .98% 64.90% 5.82% 11.84% Analytical value 4.02% 64.36% 5.93% 11.65% Example 3 Preparation of compound 8 The following structure was prepared in a 100 ml four-necked flask. 4.50 g (0.01 mol) of the phthalonitrile compound represented by the formula (9), 0.47 g (3 mmol) of vanadium trichloride and 15 ml of benzonitrile were charged and reacted at 175 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to give the desired green cake (tetrakis (2-tertbutoxycarbonyl-6-phenylphenoxy) dodecafluorovanadyl phthalocyanine (Compound 8). ) 4.3 g were obtained. (Yield, 91.1% based on phthalonitrile).

[0158]

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Visible absorption spectrum Maximum absorption wavelength 714.2 nm (ε = 1.61 × 10 5) in 2-ethoxyethanol Thin film 727.5 nm Solubility 15% by weight with respect to 2-ethoxyethanol Elemental analysis H C N F Theoretical value 3 .67% 64.28% 6.00% 12.20% Analytical value 3.81% 64.54% 5.96% 11.93% Examples 4 to 8 Phthalonitrile compounds and metals shown in Table 1 and Table 2 A phthalocyanine compound was produced in the same manner as in Examples 1 to 3 using the compound. The yield with respect to the phthalonitrile compound and the maximum absorption wavelength in 2-ethoxyethanol at this time were as shown in Tables 1 and 2.

[0160]

[Table 1]

[0161]

[Table 2]

Example 9 Compounds 21 and / or 22
Manufacturing of

[0163]

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In a 100 ml four-necked flask, 10.2 g (0.04 mol) of the ester compound represented by the above structural formula (10), isopropyl 3-phenylsalicylate,
Iron powder 0.1 g (1.8 mmol), chloroform 20 m
1 was charged and stirred at room temperature. Bromine 6.23 g (0.0
4 mol) was added with a dropping funnel in about 30 minutes. After completion of dropping, stirring was continued at room temperature for 5 hours. After completion of the reaction, the reaction solution was poured into distilled water, extracted and concentrated to give a crude product 12.1
g was obtained. Column purification of the crude product (silica gel, solvent =
Toluene / hexane / = 1/2)
9.5 g of a brominated ester compound represented by 1) and / or (12) was obtained.

[0165]

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[0166]

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Mass spectrum Parent peaks 334, 336 Elemental analysis H COF theoretical value 4.53% 57.48% 14.37% 23.63% Analytical value 4.48% 57.56% 15.14% 22. 82% Next, in a 100 ml four-necked flask, 6.72 g (0.02 mol) of the brominated ester compound represented by the above structural formula (11) and / or (12), and tetrafluorophthalonitrile 3. 81 g (0.02 mol),
3.48 g (0.06 mol) of potassium fluoride and 50 ml of acetonitrile were charged and reacted for 5 hours under reflux. After completion of the reaction, potassium fluoride was filtered off and the solvent was distilled off. The obtained solid content was washed with 200 ml of hexane to obtain 9.1 g of a phthalonitrile compound represented by the following structural formulas (13) and / or (14).

[0168]

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[0169]

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Mass spectrum Parent peaks 514, 516 Elemental analysis H C N F Br theoretical value (%) 2.74 56.03 5.45 11.09 15.35 Analytical value (%) 2.81 55.72 5. 42 10.86 15.27 Next, in a 100 ml four-necked flask, 5.15 g (0.01 mol) of the phthalonitrile compound represented by the above structural formula (13) and / or (14), and vanadium trichloride 0. 0.47 g (3 mmol) and benzonitrile 1
5 ml was charged and reacted at 175 ° C. for 4 hours. After the completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to obtain 4.2 g of a target green cake (yield: 78.
3%).

Visible absorption spectrum Maximum absorption wavelength 712.5 nm (ε = 1.45 × 10 5) in 2-ethoxyethanol Thin film 730.5 nm Solubility 12% by weight with respect to 2-ethoxyethanol Elemental analysis H C N F Br theoretical value (%) 2.66 54.26 5.28 10.74 14.87 Analytical value (%) 2.71 54.92 5.15 10.34 14.26 Comparative Example 1 Preparation of Comparative Compound 1 100 ml of four A 4-necked flask was charged with 4.16 g (0.01 mol) of a phthalonitrile compound represented by the following structural formula (10), 0.47 g (3 mmol) of vanadium trichloride and 15 ml of benzonitrile and reacted at 175 ° C. for 4 hours. Let After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to give the target green cake (tetrakis (2- (2-tetrahydrofurfuryloxy) carbonyl-6-methylphenoxy) dodecafluoro). Vanadyl phthalocyanine) 3.60
g was obtained. (Yield, 83.2 based on phthalonitrile
%).

[0172]

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Visible absorption spectrum Maximum absorption wavelength 711.5 nm (ε = 8.22 × 10 4) in 2-ethoxyethanol Thin film 672.5 nm Solubility 12 wt% with respect to 2-ethoxyethanol Elemental analysis H C N F Theoretical value 3 .49% 58.24% 6.47% 18.16% Analytical value 3.67% 58.39% 6.55% 13.02% Comparative Example 2 Preparation of Comparative Compound 2 In a 100 ml four neck flask. 4.46 g (0.01 mol) of a phthalonitrile compound represented by the following structural formula (11), 0.47 g (3 mmol) of vanadium trichloride and 15 ml of benzonitrile were charged and reacted at 175 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to give the target green cake (tetrakis (2- (2-tetrahydrofurfuryloxy) carbonyl-6-ethoxyphenoxy) dodecafluoro). Vanadyl phthalocyanine) 3.8
9 g were obtained. (Yield, 84.1 based on phthalonitrile
%).

[0174]

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Visible absorption spectrum Maximum absorption wavelength 711.5 nm (ε = 1.37 × 10 5) in 2-ethoxyethanol Thin film 729.0 nm Solubility 13 wt% with respect to 2-ethoxyethanol Elemental analysis H C N F Theoretical value 3 .70% 57.06% 6.05% 12.31% Analytical value 3.55% 56.84% 6.00% 12.41% Example 10 Depth of 80 nm, spiral guide groove with a pitch of 1.6 μm Having a thickness of 1.2 nm, an outer diameter of 120 mm, and an inner diameter of 15 mm, a coating solution prepared by dissolving the phthalocyanine compound of Example 1 in 2-methoxyethanol at a concentration of 5% by weight was formed to a thickness of 120 nm using a spin coater. A film was formed. Next, a gold film having a film thickness of 75 nm was formed on the coating film thus obtained by vacuum evaporation. Further, a protective coating film made of an ultraviolet curable resin was provided on the above to prepare an optical recording medium. When the reflectance of the optical recording medium thus obtained was measured, it was found to be 770 nm to 80.
It was 82% in the wavelength range of 0 nm, and stable optical characteristics were obtained.

Using this optical recording medium, a semiconductor laser having a wavelength of 780 nm was used, and an output of 5.7 mW and a linear velocity of 1.
When the EMF signal was recorded at 4 m / s, recording was possible and the error rate was less than 0.2%. As a result of analyzing the obtained signal, it was at a level that can be reproduced by a commercially available CD player.

Examples 11 to 14 Optical recording media were prepared in the same manner as in Example 10, except that the compounds whose production methods were shown in Examples 2 to 5 were used. This optical recording medium was used and evaluated in the same manner as in Example 10. As a result, the reflectance was 80% or more, and stable optical characteristics were obtained.

Using these optical recording media, a semiconductor laser having a wavelength of 780 nm was used, and an EMF signal was recorded at a linear velocity of 1.3 m / s at an output of 5.8 mW. It was As a result of analyzing the obtained signal, it was at a level that can be reproduced by a commercially available CD player.

Examples 15 to 17 Optical recording media were prepared in the same manner as in Example 10, except that the compounds shown in the production methods in Examples 6 to 8 were used. This optical recording medium was used and evaluated in the same manner as in Example 10. As a result, the reflectance was 80% or more, and stable optical characteristics were obtained.

Using these optical recording media, a semiconductor laser having a wavelength of 780 nm was used to record an EMF signal at an output of 6.0 mW and a linear velocity of 1.3 m / s. It was As a result of analyzing the obtained signal, it was at a level that can be reproduced by a commercially available CD player.

Example 18 An optical recording medium was prepared in the same manner as in Example 10, except that the compound whose production method was shown in Example 9 was used. Example 10 using this optical recording medium
The evaluation was performed in the same manner as described above. As a result, the reflectance is 83
%, And stable optical characteristics were obtained.

Using this optical recording medium, a semiconductor laser having a wavelength of 780 nm was used and an output of 5.6 mW and a linear velocity of 1.
When the EFM signal was recorded at 4 m / s, recording was possible and the error rate was less than 0.2%. As a result of analyzing the obtained signal, it was at a level that could be reproduced by a commercially available CD player.

Examples 19 to 20 Optical recording media were prepared in the same manner as in Example 10 except that the compounds shown in Comparative Examples 1 to 2 were used. This optical recording medium was used and evaluated in the same manner as in Example 10. As a result, the created reflectance had an optical characteristic of about 75%.

When an EMF signal was recorded at a linear velocity of 1.3 m / s at a power of 6.0 mW using a semiconductor laser having a wavelength of 780 nm using these optical recording media, a high error rate was recorded. Was impossible.

Further, the phthalocyanine compounds obtained in Examples 1 to 9 and Comparative Examples 1 and 2 were measured for light resistance, solubility, association property and thermal decomposability, and the results shown in Table 3 were obtained.

The light resistance was evaluated by the following method.

[0187] 1 g of the dye was dissolved in 20 g of methyl ethyl ketone, and a dye thin film was formed on a glass substrate by a spin coating method to prepare a sample. This sample was set in a xenon light resistance tester (irradiation light amount: 120,000 Lux), and the decrease in absorbance with time was measured. Then, the following three-stage evaluation was performed based on the residual ratio of the absorbance after 100 hours.

Residual rate of absorbance after 100 hours is 80% or more. Δ Residual rate of absorbance after 100 hours is 30% to less than 80% × Residual rate of absorbance after 100 hours is less than 30%. Measure the solubility in ethanol,
The following three-stage evaluation was performed.

○ Solubility of 5% or more △ Solubility of 2% to less than 5% × less than 2% Further, the absorption wavelength was formed by using a spin coater to form a coating liquid dissolved in 2-methoxyethanol at a concentration of 5% by weight. The coating film was measured.

The association peak was evaluated in the following two stages.

○ Association peak of 50% or less × Association peak of more than 50% Here, in the evaluation of the association peak, the absorbance of the association peak when the absorbance of the absorption spectrum of the monomer peak is 100% is calculated, This is evaluated based on 50%.

The thermal decomposability was evaluated in the following three stages by the thermal decomposition start temperature with a differential thermogravimetric analyzer.

Thermal decomposition start temperature of 300 ° C. or lower Δ Thermal decomposition start temperature of more than 300 ° C. to 350 ° C. × Thermal decomposition start temperature of more than 350 ° C.

[0194]

[Table 3]

[0195]

As described above, the novel compound of the present invention is excellent in absorption characteristics, solubility, light resistance, thermal decomposition characteristics and economic efficiency as compared with the conventionally known phthalocyanine compounds. Can be used practically as a near-infrared absorbing dye.
In particular, when used in a write-once optical recording medium having compatibility and sharability with a CD, PHOTO-CD or CD-ROM player, excellent effects can be exhibited.

According to the production method of the present invention, it is possible to regioselectively introduce a substituent into the phthalocyanine skeleton. That is, according to the production method of the present invention, it becomes possible to design a molecule of a compound having a near infrared absorption wavelength region or solubility changed according to the application, and at that time, industrially without the need for complicated production steps. It is advantageous. Fluorine atoms in the novel phthalocyanine compound of the present invention have the effect of enhancing solubility.

Claims (11)

[Claims] 1. The benzene nucleus of a phthalocyanine skeleton
A phthalocyanine compound in which 1 to 8 of the substitutable positions are substituted with a phenoxy group, and the phenoxy group is substituted with an aryl group which may have a substituent. 2. The phthalocyanine compound according to claim 1, wherein the ortho position of the phenoxy group is substituted with the aryl group. 3. One of the ortho positions of the phenoxy group is substituted with the aryl group, and at least the remaining ortho position is a substituent of the following groups (1) to (7): (In the formula, R ¹ represents a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group which may have a substituent, and R ² , R ³ and R ^Four
And R ⁵ are each independently a straight chain having 1 to 20 carbon atoms,
Represents a branched or cyclic alkyl group or an aryl group which may have a substituent, R ⁶ represents an aryl group which may have a substituent, A represents a CH group or a nitrogen atom, and B represents Is an oxygen atom, a sulfur atom, a CH ₂ group, NH
Represents a group or an alkylamino group having 1 to 4 carbon atoms, a, b, c and e are integers of 1 to 5, d and f are integers of 0 to 6, and g and h are each independently. To 1
-4. The phthalocyanine compound according to claim 1 or 2, which is substituted with at least one kind of substituent selected from 4. The phthalocyanine compound according to claim 1, wherein the benzene nucleus of the phthalocyanine skeleton is further substituted with a halogen atom. 5. A compound represented by the general formula (1): [Wherein, X, Y and Z represent a hydrogen atom or a fluorine atom, at least one of X, Y and Z is a fluorine atom, W represents an optionally substituted aryl group, and V represents It represents at least one substituent selected from the substituents of the groups (1) to (7) defined in claim 3, n is an integer of 0 to 4, and M is a metal, a metal oxide or a metal halide. Represents ] The phthalocyanine compound as described in any one of Claims 1-4 shown by these. 6. The phthalocyanine compound according to claim 5, wherein in the general formula (1), one of V and W are at both ortho positions. 7. The phthalocyanine compound according to claim 5, wherein in the general formula (1), V is an alkoxycarbonyl group in which a secondary or higher alkyl group is directly bonded to a carbonyl group. 8. In the general formula (1), X, Y and Z
Is a fluorine atom, The phthalocyanine compound according to any one of claims 5 to 7. 9. A phthalonitrile compound which is substituted with a phenoxy group, wherein the phenoxy group is substituted with an aryl group which may have a substituent, or a phthalonitrile which is not substituted with the phenoxy group. The mixture is allowed to react with a metal compound.
8. The method for producing a phthalocyanine compound according to any one of 8. 10. An optical recording medium comprising the phthalocyanine compound according to claim 1 in a recording layer provided on a substrate. 11. A write-once type optical recording medium for a compact disc, which has a recording layer and a metal reflection layer provided on a transparent resin substrate, wherein the recording layer is the recording layer according to claim 10. recoding media.