JPH08188718A - Phthalocyanine compound and optical recording medium containing the same - Google Patents

Abstract

PURPOSE: To provide the subject compound providing an optical recording medium having high sensitivity even in high-speed recording and high-density recording and excellent recording characteristics and light resistance, having structure of a phthalocyanine containing a substituted alkyl group and a substituted alkoxy group. CONSTITUTION: This compound is shown by formula I [M is two hydrogen, two metal atoms, trivalent monosubstituted metal atom, tetravalent disubstituted atom or oxy metal atom; L<1> is a group of formula II (OR<1> is a 1-10C alkoxy; R<2> is a 3-10C alkyl; X is a halogen; (n) is 0-2)]. The compound, for example, is obtained by reacting a compound of formula III or formula IV with a metal derivative in the presence of 1,8-diazabicyclo[5,4,0]-7-undecene in an alcohol under heating.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel recording material for optical disks, information recording, a display sensor, a compound useful as a near-infrared absorber which plays an important role in optoelectronics related to protective glasses, and the recording thereof. The present invention relates to an optical recording medium such as an optical disc and an optical card formed by containing it in a layer.

[0002]

2. Description of the Related Art Laser light is used for writing and reading in optical disks, optical card devices and the like. In particular, as a recording method of an optical recording medium used in these devices, heat mode recording (thermal recording) through light / heat conversion is usually adopted as a practical level, and therefore, a low melting point metal as a recording layer, Various organic polymers and further organic dyes that undergo physical or chemical changes such as melting, evaporation, decomposition, or sublimation have been proposed. Among them, organic dyes having a low melting and decomposition temperature are preferable in terms of recording sensitivity, and therefore cyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, azo dyes and the like have been developed as recording layers.

[0003] For example, in Japanese Patent Laid-Open No. 2-147286,
An optical recording medium containing a cyanine dye in the recording layer has been proposed. However, this medium system was inferior in long-term storage stability and light resistance, and further the recording characteristics were insufficient.

Anthraquinone dyes (for example, JP-A-58-2
24448), naphthoquinone dyes (see, for example, JP-A-58-
No. 224793) is also proposed, but all of them are inferior in long-term storability and light resistance like cyanine dyes, and also have insufficient recording characteristics.

In JP-A-61-25886, JP-A-2-43269 (USP 4960538), JP-A-2-296885 and the like, an optical recording medium containing a naphthalocyanine dye in a recording layer is proposed. There is. This medium system has excellent light resistance,
The reflectance of the recording layer was low and the recording characteristics were insufficient.

Further, a technique of using a phthalocyanine dye, particularly an alkoxy-substituted phthalocyanine in a recording layer of an optical recording medium is disclosed in JP-A-61-154888 (EP 186404) and JP-A-61-1.
97280, 61-246091, 62-39286 (U
SP 4769307), 63-37991, 63-39388 and the like. In the optical recording medium using the phthalocyanine dye disclosed in these patents,
It was hard to say that it has sufficient performance in terms of sensitivity, refractive index, and recording characteristics. The improvement is JP-A-3-6287
No. 8 (USP 5124067), even the improved compound thereof has a large error in high-speed recording and high-density recording by laser light, and is still not practically sufficient.

Alkoxy-substituted naphthalocyanines in JP-A-2-43269 (USP 4960538) and JP-A-2-296885, aliphatic hydrocarbon oxy-substituted phthalocyanines in JP-A-63-37991, JP-A-63-37991 Japanese Patent No. 39388 proposes the use of an alkenylthio-substituted phthalocyanine for an optical recording medium, but does not describe that it has an effect on sensitivity and recording characteristics.

It should be noted that no one having sufficient recording performance has been found in the recording characteristics of the optical recording medium using other known dyes.

Writing to and reading from an optical recording medium is 4
Since a laser beam having a wavelength of from 0 to 900 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 of the recording material and to form pits with high accuracy during writing. This is especially important in high-speed recording and high-density recording which have been recently desired. Therefore, it is necessary to develop a dye for an optical recording medium, which has high structural stability, a high refractive index for light in the vicinity of the laser oscillation wavelength, a good decomposition property, and a high sensitivity. However, conventionally developed dyes for optical recording media have drawbacks in sensitivity (C / N ratio, optimum recording power) and recording characteristics (jitter, deviation) particularly when used in recording media, for high speed recording and high density recording. There was a problem of having.

[0010]

DISCLOSURE OF THE INVENTION An object of the present invention is to improve the above-mentioned drawbacks, to provide an optical recording medium having high sensitivity even at high speed recording and high density recording, and having excellent recording characteristics and light resistance. Is to supply.

[0011]

The present inventors have completed the present invention as a result of extensive studies to solve the above-mentioned problems. That is, the present invention provides a phthalocyanine compound represented by the following general formula (1),

[0012]

Embedded image [In the formula (1), M is two hydrogen atoms, a divalent metal atom,
Represents a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxymetal atom, and L ¹ is represented by the formula (2)

[0013]

[Chemical 4] (In the formula (2), OR ¹ represents a linear or branched alkoxy group having 1 to 10 carbon atoms, R ² represents a linear or branched alkyl group having 3 to 10 carbon atoms, and X represents halogen. Represents an atom, and n represents a number of 0 to 2). ] The phthalocyanine compound shown by these.

In the general formula (1), the central metal represented by M is Pd, Cu, Pt, Ni, Co, Zn, M.
g, VO, TiO, Si (Y) ₂ , Sn (Y) ₂ (Y is a halogen atom, alkoxy group, aryloxy group, acyloxy group, hydroxy group, alkyl group, aryl group, alkylthio group, arylthio group, trialkyl A phthalocyanine compound which is a silyloxy group, a trialkyltinoxy group or a trialkylgermaniumoxy group.). An optical recording medium containing a phthalocyanine compound represented by the general formula (1). An optical recording medium has a structure in which a recording layer containing a phthalocyanine compound of the general formula (1), a reflective layer made of gold or aluminum, and a protective layer are further laminated on a base. The general formula (1) will be abbreviated as the following structural formula.

[0015]

Embedded image

The phthalocyanine compound of the present invention is 650-9.
It has a sharp absorption at 00 nm and a molecular extinction coefficient of 150,000.
It is high as above and has excellent long-term stability and light resistance.
It is suitable as a recording material for an optical recording medium (optical disk, optical card, etc.) using a semiconductor laser. In addition, since the phthalocyanine ring is substituted with an alkoxy group and an alkyl group, the compound of the present invention has good solubility in a solvent used when the substrate is applied by spin coating. Furthermore,
Although the mechanism is not yet clear and it is currently being investigated, the β-position alkyl group and the halogen atom substituted on the phthalocyanine ring, which are the features of the phthalocyanine compound of the present invention, contribute to the improvement of sensitivity during optical recording. , Is effective in reducing the error in the formed signal. That is, the decomposition and melting of the dye during optical recording were controlled to form highly accurate pits, and the damage to the resin substrate of the recording medium was reduced.
In the case of a recording medium having a reflective layer, the adhesion is improved between the recording layer and the metal layer which is the reflective layer. Not only the conventional recording method, but also the high-speed recording or the high-density recording method as compared with the conventional recording method is effective in improving the sensitivity and recording characteristics of the optical recording medium.

The preferred embodiments of the present invention will be described in detail below.

In the general formula (1), specific examples of the linear or branched alkoxy group having 1 to 10 carbon atoms represented by OR ¹ include methoxy group, ethoxy group, n-propoxy group and is.
o-propoxy group, n-butoxy group, iso-butoxy group, sec-
Butoxy group, t-butoxy group, n-pentyloxy group, iso-
Pentyloxy group, neo-pentyloxy group, 2-methylbutyl-3-oxy group, pentyl-2-oxy group, pentyl-3-
Oxy group, n-hexyloxy group, cyclo-hexyloxy group, 2-methylpentyl-4-oxy group, 2-methylpentyl-
3-oxy group, 3-methylpentyl-4-oxy group, 4-methylpentyl-4-oxy group, n-heptyloxy group, hexyl-
3-oxy group, 2-methylhexyl-5-oxy group, 2,4-dimethylpentyl-3-oxy group, 2-methylhexyl-3-oxy group, heptyl-4-oxy group, n-octyloxy group, 2-ethylhexyl-1-oxy group, 2,5-dimethylhexyl-3-oxy group, 2,4-dimethylhexyl-3-oxy group, 2,2,4-trimethylpentyl-3-oxy group, n-nonyloxy Base, 3,5
-Dimethylheptyl-4-oxy group, 2,6-dimethylheptyl
-3-oxy group, 2,4-dimethylheptyl-3-oxy group, 2,2,
Examples include 5,5-tetramethylhexyl-3-oxy group and 1-cyclo-pentyl-2,2-dimethylpropyl-1-oxy group.

In the general formula (1), the number of carbon atoms represented by R ² is 3
Specific examples of the linear or branched alkyl group of 10 include:
Propyl group, 1-methyl-propyl group, 1-ethyl-propyl group, 1-propyl-propyl group, 1,1-dimethyl-propyl group, butyl group, 1-methyl-butyl group, 2
-Methyl-butyl group, 3-methyl-butyl group, 2,3-
Dimethyl-butyl group, 1,1-dimethyl-butyl group, 1
-Ethyl-2-methyl-butyl group, pentyl group, 1-methyl-pentyl group, 2-methyl-pentyl group, 3-methyl-pentyl group, 4-methyl-pentyl group, 2,4-dimethyl-pentyl group, 1,4-dimethyl-pentyl group,
1-ethyl-2-methyl-pentyl group, n-hexyl group, 1-methyl-hexyl group, 3-methyl-hexyl group, n-heptyl group, 2-methyl-heptyl group, 3,
4,4-trimethyl-heptyl group, n-octyl group, n
-Nonyl group, 2,5-dimethyl-heptyl group, 2-methyl-hexyl group, 5-methyl-hexyl group and the like.

The halogen atom represented by X includes chlorine, bromine and iodine.

Further, in the formula (1), a divalent metal represented by M
Examples of Cu, Zn, Co, Ni, Pd, Pt,
Examples include Mn, Sn, Mg, Ti, Ca
Examples of trivalent metals include Al-F, Al-Cl, Al-
Br, Al-I, Ga-F, Ga-Cl, Ga-Br,
Ga-I, In-F, In-Cl, In-Br, In-
I, Tl-F, Tl-Cl, Tl-Br, Tl-I, A
l-C₆H_Five, Al-C ₆H_Four(CH₃), In-C₆H_Five,
In-C₆H_Four(CH₃), Mn (OH), Mn (OC₆H
_Five), Mn [OSi (CH₃)₃], Fe-Cl, Ru-
Cl and the like, and examples of the di-substituted tetravalent metal include C
rCl₂, SiF₂, SiCl₂, SiBr₂, SiI₂,
SnF₂, SnCl₂, SnBr₂, ZrCl₂, Ge
F₂, GeCl₂, GeBr₂, GeI₂, TiF₂, Ti
Cl₂, TiBr₂, Si (OH)₂, Sn (OH)₂, G
e (OH)₂, Zr (OH)₂, Mn (OH)₂, Ti
A₂, CrA₂, SiA₂, SnA₂, GeA₂[A is Al
Shows the kill group, phenyl group, naphthyl group and its derivatives.
], Si (OA ')₂, Sn (OA ')₂, Ge (O
A ')₂, Ti (OA ')₂, Cr (OA ')₂[A ’is
Alkyl group, phenyl group, naphthyl group, trialkyl group
Ryl group, dialkylalkoxysilyl group and derivatives thereof
Represents the body], Si (SA ”)₂, Sn (SA ")₂, Ge
(SA ”)₂[A] is an alkyl group, a phenyl group, a naphthyl group
Group and its derivatives] and the like, and oxygold
Examples of the genus include VO, MnO, TiO, and the like.
It Particularly preferable examples are Cu, Ni, Co and M.
g, Zn, Pd, Pt, VO, etc.

The synthetic method of the phthalocyanine compound represented by the general formula (1) includes the following formula (3) or (4)

[0023]

[Chemical 6] [In the formulas (3) and (4), OR ¹ and R ² are represented by the general formula (2)
Means the same as. ] The compound represented by
A metal derivative is heated and reacted in alcohol in the presence of 8-diazabicyclo [5,4,0] -7-undecene (DBU). Alternatively, a metal derivative and chlornaphthalene,
A phthalocyanine compound having an alkoxy group and an alkyl group was synthesized by heating and reacting in a solvent with a high boiling point such as bromnaphthalene or trichlorobenzene. It can be obtained by a method of reacting with a halogenating agent such as

The compound represented by the general formula (3) or (4) can be produced by the route shown below.

[0025]

[Chemical 7]

Alkoxyphthalonitrile (B) is obtained by reacting commercially available 3-nitrophthalonitrile (A) with an allyl alcohol derivative represented by R ³ OH in the presence of a base. Further, after Claisen rearrangement reaction of (B), in the presence of a base, R ¹ X [R ¹ represents an alkyl group corresponding to the alkoxy group represented by OR ¹ of the general formula (1), and X represents a halogen atom. . ] It reacts with the alkyl halide derivative represented by these, and 3-alkoxy-4-alkenyl- phthalonitrile (C) is obtained. This is reduced with hydrogen gas in the presence of a transition metal catalyst to obtain 3-alkoxy-4-alkyl-phthalonitrile (3). The compound represented by (4) can be obtained by reacting (3) with ammonia in alcohol using sodium methylate as a catalyst.

In the method for producing an optical recording medium using the phthalocyanine compound of the present invention, 1 to 3 compounds including the phthalocyanine compound of the present invention are coated or vapor-deposited on a transparent substrate in one layer or two layers. There is a method, and the coating method is 20% by weight or less of the binder resin, preferably 0%.
%, And the phthalocyanine compound of the present invention is 0.05 to 20% by weight, preferably 0.5 to 20% by weight, dissolved in a solvent and applied by a spin coater. The vapor deposition method is 10 ^-5 to 10 ^-7 torr, 100 to
There is a method of depositing a phthalocyanine compound on a substrate at 300 ° C.

The substrate may be any optically transparent resin. Examples thereof include acrylic resin, polyethylene resin, vinyl chloride resin, vinylidene chloride resin, polycarbonate resin, polyolefin copolymer resin, vinyl chloride copolymer resin, vinylidene chloride copolymer resin, and styrene copolymer resin. The substrate may be subjected to a surface treatment with a thermosetting resin or an ultraviolet curable resin.

When manufacturing an optical recording medium (optical disk, optical card, etc.), a polyacrylate substrate or a polycarbonate substrate is used as the substrate and it is applied by a spin coating method in terms of cost and handling by the user. preferable.

Due to the solvent resistance of the substrate, the solvent used for spin coating is a halogenated hydrocarbon (eg, dichloromethane, chloroform, carbon tetrachloride, tetrachloroethylene, dichlorodifluoroethane, etc.), ethers (eg, tetrahydrofuran, diethyl ether, diether). Propyl ether, dibutyl ether, dioxane, etc.), alcohols (eg, methanol, ethanol, propanol, etc.), cellosolves (eg, methyl cellosolve,
Ethyl cellosolve, etc.), hydrocarbons (eg, hexane, cyclohexane, ethylcyclohexane, cyclooctane, dimethylcyclohexane, octane, benzene, toluene, xylene, etc.), or a mixed solvent thereof is preferably used.

In order to process it as a recording medium, it is covered with a substrate as described above, or a substrate provided with two recording layers is laminated with air gaps facing each other, or a reflective layer is formed on the recording layer. (Aluminum or gold) is provided, and a protective layer of thermosetting or photocurable resin is laminated. As a protective layer, Al ₂ O ₃ , SiO ₂ , S
iO, may be used an inorganic compound of SnO ₂ or the like.

[0032]

EXAMPLES The present invention will be specifically described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 In a container equipped with a stirrer, a reflux condenser and a nitrogen introducing tube,
Structural formula (3-1) below

[0034]

Embedded image 2- (2-pentoxy) -4-propylphthalonitrile of 25.6 g (0.1 mol), DBU15.
2 g (0.1 mol), and n-amyl alcohol 15
0 g was charged and the temperature was raised to 100 ° C. under a nitrogen atmosphere. Next, at the same temperature, 5.3 g of palladium chloride (0.03
mol) was added, and the mixture was reacted at 95 to 100 ° C. for 15 hours. After completion of the reaction, the mixture was cooled and the insoluble matter was filtered off. After the filtrate was concentrated under reduced pressure to recover the solvent, column purification (silica gel 500 g, solvent toluene) was performed, and the palladium tetra [α- (2-pentoxy) -β-propyl] phthalocyanine compound 18 of the following structural formula (1-1) was used. 0.1 g (yield 64%)
I got

[0035]

[Chemical 9] The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 693 nm ε _g = 2.7 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

5.1 g of the above phthalocyanine compound (4.
5 mmol) was dissolved in 25 g of 1,1,2-trichloroethane, and 10 g of water was added. Then 2.9 g (18
mmol) and 3 g of 1,1,2-trichloroethane were added dropwise at 50 to 55 ° C. in 30 minutes, and the same temperature was applied for 1 hour to complete the process. 15% sodium bisulfite aqueous solution 5
g and washed. 80 g of methanol was added dropwise to the organic layer, and the precipitated crystals were filtered and purified by column (silica gel 1
(00 g, toluene) to obtain 6.5 g of a brominated phthalocyanine compound represented by the following structural formula (1-2). Elemental analysis revealed that 3.5 bromine atoms were substituted.

[0038]

[Chemical 10] The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 707 nm ε _g = 1.7 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

A solution of the phthalocyanine compound of structural formula (1-1) above in ethylcyclohexane (10 g / l) was added to
It was applied onto a polycarbonate substrate for an optical card by a spin coater, and subsequently a protective layer was formed using a UV curable resin to prepare an optical card. When a 780 nm semiconductor laser was used to record on this medium at a linear velocity of 2.0 m / s and a power of 4.0 mW, the CN ratio was 60 dB. Further, a dimethylcyclohexane (10 g / l) solution of the brominated phthalocyanine compound represented by the structural formula (1-2) was added to a spiral groove (pitch: 1.6 μm, groove width: 0.6 μm, groove depth: 0.18 μm), an outer shape of 120 mm, and a thickness. 1.2 mm
500-100 on the polycarbonate substrate for CD-R
A spin coat film was formed at 0 rpm. A 30 nm gold layer was sputter-deposited thereon to form a reflective layer, and then a protective layer was formed by overcoating with a photo-curing polyacrylic resin and then photo-curing to form a CD-R type medium. When an EFM signal was written in this medium at a linear velocity of 1.4 m / s and a power of 6.0 mW using a semiconductor laser having a wavelength of 780 nm, the error rate was less than 0.2%, and the linear velocity was 5.6 m. The error rate was less than 0.2% even at 4 × speed recording of / s. Also, linear velocity 2m / s, 0.8m
There was no change in recording even after reproducing 10 ⁵ times with W laser light.

Example 2 5.1 g (4.5 mmol) of palladium tetra [α- (2-pentoxy) -β-propyl] phthalocyanine compound of the structural formula (1-1) synthesized in Example 1 was added to 1,1,1. Two
Dissolved in 25 g of trichloroethane and added 10 g of water. Then, a mixed solution of 6.1 g (45 mmol) of sulfuryl chloride and 6 g of 1,1,2-trichloroethane was added to 50
The mixture was added dropwise at -55 ° C over 30 minutes and reacted at the same temperature for 1 hour.
After the completion, 45 g of a 10% aqueous sodium hydroxide solution was added to neutralize. 80 g of methanol was added dropwise to the organic layer, and the precipitated crystals were filtered and dried, followed by column purification (silica gel 100).
g, solvent toluene) to obtain 6.5 g of a chlorinated phthalocyanine compound represented by the following structural formula (1-3). From elemental analysis, it was found that 6.2 chlorine was substituted.

[0042]

[Chemical 11] The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 700 nm ε _g = 1.5 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

A solution of the above chlorinated phthalocyanine compound in ethylcyclohexane (10 g / l) was applied onto a polycarbonate substrate for CD-R by a spin coater as in Example 1, and gold was sputter-deposited on the substrate. U
A protective layer was formed using a V-curable resin to prepare a CD-R type medium. When an EFM signal was written on this medium at a linear velocity of 1.4 m / s and a power of 6.0 mW using a semiconductor laser of 780 nm, the error rate was less than 0.2%, and the linear velocity was 5.6 m / s. The error rate was less than 0.2% even at 4 × speed recording. There was no change even after reproducing 1 million times with reproducing light of 0.5 mW. 80 ° C / 85
There was no problem in recording and reproducing even after 1000 hours under the condition of%.

Example 3 3.0 g (0.03 mo) of copper chloride was added to the metal chloride of Example 1.
The following structural formula (1-4) was carried out in the same manner except that l) was used.
Copper tetra [α- (2-pentoxy) -β-propyl]
23.1 g (yield 85%) of the phthalocyanine compound was obtained. The results of visible absorption spectrum and elemental analysis were as follows.

[0046]

[Chemical 12] Visible absorption: λ _max = 705 nm ε _g = 2.2 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

4.9 g of the above phthalocyanine compound (4.
5 mmol) was dissolved in 30 g of 1,1,2-trichloroethane, and 10 g of water was added. Next, 3.2 g of bromine (20 g
mmol) and 3 g of 1,1,2-trichloroethane were added dropwise at 50 to 55 ° C. in 30 minutes, and the same temperature was applied for 1 hour to complete the process. 15% sodium bisulfite aqueous solution 5
g and washed. 100 g of methanol was added dropwise to the organic layer, and the precipitated crystals were filtered and dried, and then column purified (silica gel 100 g, solvent toluene), and the following structural formula (1-
6.2 g of the brominated phthalocyanine compound of 5) was obtained. From elemental analysis, it was found that 3.8 bromine atoms were substituted.

[0048]

[Chemical 13] The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 728 nm ε _g = 1.8 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

A dibutyl ether solution (10 g / l) of the brominated phthalocyanine compound represented by the structural formula (1-5) was applied onto a polycarbonate substrate for CD-R by a spin coater in the same manner as in Example 1, and then applied. Gold is sputter-deposited on the C, then a protective layer is formed using a UV curable resin, and C
A D-R type medium was produced. When an EFM signal was written on this medium with a power of 6.0 mW at a linear velocity of 1.4 m / s using a semiconductor laser of 780 nm, the error rate was less than 0.2%. There was no change even after reproducing 1 million times with reproducing light of 0.5 mW. .

Example 4 The following structural formula (3-2) was placed in the same container as in Example 1.

[0052]

Embedded image 2-Pentoxy-4-propylphthalonitrile of 25.6 g (0.1 mol), DBU 15.2 g
(0.1 mol) and n-amyl alcohol 150 g
Was charged and the temperature was raised to 100 ° C. under a nitrogen atmosphere. Next, 4.1 g (0.03 mol) of zinc chloride was added at the same temperature, and the mixture was reacted at 95 to 100 ° C. for 25 hours. After completion of the reaction, the mixture was cooled and the insoluble matter was filtered off. After the filtrate was concentrated under reduced pressure to recover the solvent, column purification (silica gel 500 g, solvent toluene) was performed, and 18.5 g of a zinc tetra [α-pentoxy-β-propyl] phthalocyanine compound represented by the following structural formula (1-6) (collection: Rate 68%).

[0053]

[Chemical 15] The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 688 nm ε _g = 2.5 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

4.9 g of the above phthalocyanine compound (4.
5 mmol) was dissolved in 30 g of 1,1,2-trichloroethane, and 10 g of water was added. Next, 3.2 g of bromine (20 g
mmol) and 3 g of 1,1,2-trichloroethane were added dropwise at 50 to 55 ° C. in 30 minutes, and the same temperature was applied for 1 hour to complete the process. 15% sodium bisulfite aqueous solution 5
g and washed. 100 g of methanol was added dropwise to the organic layer, and the precipitated crystals were filtered and dried, and then column purified (silica gel 100 g, solvent toluene), and the following structural formula (1-
5.9 g of the brominated phthalocyanine compound of 7) was obtained. From elemental analysis, it was found that 3.7 bromine atoms were substituted.

[0056]

Embedded image The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 704 nm ε _g = 1.8 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

A solution of the brominated phthalocyanine compound of the above structural formula (1-7) in ethylcyclohexane (10 g /
1) was applied onto a polycarbonate substrate for an optical card by a spin coater, and then a protective layer was formed using a UV curable resin to prepare an optical card. 780 nm on this medium
4.0m at a linear velocity of 2.0m / s using the semiconductor laser of
When recorded at a power of W, the CN ratio was 60 dB. In addition, there was no change even after reproducing 1 million times with reproducing light of 0.5 mW.

Example 5 In a container similar to that of Example 1, 15.2 g (0.1 m) of DBU was added.
ol) and 150 g of n-octyl alcohol are charged and the temperature is raised to 150 ° C. under a nitrogen atmosphere. to this,
Structural formula (4-1) below

[0060]

[Chemical 17] And a mixture of 27.3 g (0.1 mol) of 3-pentoxy-4-propyl-diiminoisoindoline represented by and 5.3 g (0.03 mol) of palladium chloride was prepared.
Add at 0 ° C. The reaction is carried out at 150 to 160 ° C. for 5 hours, and after the reaction is completed, it is cooled. After discharging into 500 g of methanol, filtering and drying, column purification (silica gel 500 g, solvent toluene) was performed, and 23.2 g of palladium tetra [α-pentoxy-β-propyl] phthalocyanine compound represented by the following structural formula (1-8) (yield 82%).

[0061]

Embedded image The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 691 nm ε _g = 2.3 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

5.1 g of the above phthalocyanine compound (4.
5 mmol) was dissolved in 30 g of 1,1,2-trichloroethane, and 10 g of water was added. Next, sulfuryl chloride 6.
A mixed solution of 1 g (45 mmol) and 6 g of 1,1,2-trichloroethane was added dropwise at 50 to 55 ° C over 30 minutes, and the mixture was reacted at the same temperature for 1 hour. After the completion, 45 g of a 10% aqueous sodium hydroxide solution was added to neutralize. 80 g of methanol was added dropwise to the organic layer, and the precipitated crystals were filtered and dried, followed by column purification (silica gel 100 g, solvent toluene) to obtain 6.0 g of a chlorinated phthalocyanine compound represented by the following structural formula (1-9). From elemental analysis, it was found that 7.2 chlorine was substituted.

[0064]

[Chemical 19] The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 705 nm ε _g = 1.6 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

A solution of the above chlorinated phthalocyanine compound of structural formula (1-9) in ethylcyclohexane (10 g /
1) was subjected to CD-R by a spin coater as in Example 1.
Was coated on a polycarbonate substrate for gold, and gold was sputter-deposited on the substrate, and then a protective layer was formed using a UV curable resin to prepare a CD-R type medium. 780 nm on this medium
5.5m at a linear velocity of 1.4m / s using the semiconductor laser of
There was no change even after recording with a power of W and reproducing 1 million times with a reproducing light of 0.5 mW. Further, the error rate was less than 0.2% when recording (high-density recording) with a power of 5.5 mW at a linear velocity of 1.2 m / s. And 80 ° C / 85
There was no problem in recording and reproducing even after 1000 hours under the condition of%.

Example 6 The following structural formula (3-3) was placed in the same container as in Example 1.

[0068]

Embedded image 2-butoxy-4- (4-methyl-pentyl) phthalonitrile represented by 28.4 g (0.1 mol), DB
U (15.2 g, 0.1 mol) and n-amyl alcohol (150 g) were charged, and the temperature was raised to 100 ° C. under a nitrogen atmosphere. Next, at the same temperature, 3.9 g of nickel chloride (0.
(03 mol) was added and reacted at 120 to 130 ° C. for 10 hours. After completion of the reaction, the mixture was cooled and the insoluble matter was filtered off. After the filtrate was concentrated under reduced pressure to recover the solvent, column purification (silica gel 500 g, solvent toluene) was performed, and the following structural formula (1-
21.5 g of nickel tetra [α-butoxy-β- (4-methyl-pentyl)] phthalocyanine compound of 10)
(Yield 72%) was obtained.

[0069]

[Chemical 21] The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 687 nm ε _g = 2.2 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

5.5 g of the above-mentioned phthalocyanine compound (4.
5 mmol) was dissolved in 30 g of 1,1,2-trichloroethane, and 10 g of water was added. Next, 4.3 g of bromine (27
mmol) and 3 g of 1,1,2-trichloroethane were added dropwise at 50 to 55 ° C. in 30 minutes, and the same temperature was applied for 1 hour to complete the process. 15% sodium bisulfite aqueous solution 5
g and washed. 100 g of methanol was added dropwise to the organic layer, and the precipitated crystals were filtered and dried, and then column purified (silica gel 100 g, solvent toluene), and the following structural formula (1-
5.9 g of the brominated phthalocyanine compound of 11) was obtained.
It was found from elemental analysis that 5.5 bromine atoms were substituted.

[0072]

[Chemical formula 22] The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 711 nm ε _g = 1.4 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

The above-mentioned brominated phthalo of the structural formula (1-11)
Ethylcyclohexane solution of cyanine compound (10 g /
l) spin coater for polycarbonate for optical card
The protective layer is applied on the substrate using UV curable resin.
To form an optical card. 780 nm on this medium
4.0m at a linear velocity of 2.0m / s using the semiconductor laser of
The CN ratio when recorded with the power of W was 65 dB.
Was. With a laser beam of 0.8 mW at a linear velocity of 2.0 m / s
It was reproducible, and when the reproduction light stability was investigated, it was 10 ^FiveTimes
It was possible to reproduce.

Example 7 4.7 g of vanadium trichloride was added to the metal chloride of Example 6.
(0.03 mol) except that vanadyl tetra [α- (2-pentoxy) -β-propyl] phthalocyanine compound 18.4 having the following structural formula (1-12) was used.
g (yield 61%) was obtained. The results of visible absorption spectrum and elemental analysis were as follows.

[0076]

[Chemical formula 23] Visible absorption: λ _max = 728 nm ε _g = 2.0 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

5.4 g of the above phthalocyanine compound (4.
5 mmol) was dissolved in 40 g of 1,1,2-trichloroethane, and 20 g of water was added. Next, 1.6 g (10
mmol) and 3 g of 1,1,2-trichloroethane were added dropwise at 50 to 55 ° C. in 30 minutes, and the same temperature was applied for 1 hour to complete the process. 15% sodium bisulfite aqueous solution 5
g and washed. 100 g of methanol was added dropwise to the organic layer, and the precipitated crystals were filtered and dried, and then column purified (silica gel 100 g, solvent toluene), and the following structural formula (1-
6.2 g of the brominated phthalocyanine compound of 13) was obtained.
From elemental analysis, it was found that 1.5 bromine atoms were substituted.

[0078]

[Chemical formula 24] The results of visible absorption spectrum and elemental analysis were as follows.

Visible absorption: λ _max = 735 nm ε _g = 1.5 × 10 ⁵ cm ² g ^-1 (solvent: toluene)

A solution of the brominated phthalocyanine compound represented by the structural formula (1-13) in dibutyl ether (10 g / l)
Was applied onto a polycarbonate substrate for an optical card by a spin coater, and subsequently, a protective layer was formed using a UV curable resin to prepare an optical card. When a 780 nm semiconductor laser was used to record on this medium at a linear velocity of 2.0 m / s and a power of 4.0 mW, the CN ratio was 60 dB.
There was no change even after reproducing 1 million times with reproducing light of 0.2 mW.

Examples 8 to 15 Phthalocyanine compounds were synthesized in the same manner as in Example 1. The laser power (mW) required to measure the visible absorption spectrum and prepare a CD-R medium in the same manner as in Example 1 and write an EFM signal at a linear velocity of 1.4 m / sec using a semiconductor laser of 780 nm. The measurement was performed and the error rate at that time was evaluated. As an evaluation of error rate,
○ indicates an error rate of less than 10, and × indicates an error rate of 10.
The above is shown. Further, as a comparative example, JP-A-3-62878 (USP 51) represented by the following structural formula (A) is shown.
24067) was used to prepare a CD-R medium,
It evaluated similarly. The results are shown in Table 1 below.

[0082]

[Chemical 25]

[0083]

[Table 1]

[0084]

[Table 2]

[0085]

[Table 3]

[0086]

INDUSTRIAL APPLICABILITY Since the phthalocyanine compound of the present invention has an alkyl group and an alkoxy group substituted on the phthalocyanine ring, it has improved solubility in a solvent and can be applied to a substrate by a spin coating method. In addition, the halogen atom substituting the phthalocyanine ring allows the signal at the time of optical recording to be correctly written in the optical recording medium using this compound. Even in high-speed recording or high-density recording, the effect is improved in sensitivity and recording characteristics.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Taizo Nishimoto 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Takeshi Tsuda 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Keisuke Soma, 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (4)

[Claims] 1. The following general formula (1): [In the formula (1), M is two hydrogen atoms, a divalent metal atom,
Represents a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxymetal atom, and L ¹ is represented by the formula (2): (In the formula (2), OR ¹ represents a linear or branched alkoxy group having 1 to 10 carbon atoms, R ² represents a linear or branched alkyl group having 3 to 10 carbon atoms, and X represents halogen. Represents an atom, and n represents a number of 0 to 2). ] The phthalocyanine compound shown by these. 2. In the general formula (1), the central metal represented by Met is Pd, Cu, Pt, Ni, Co, Zn,
Mg, VO, TiO, Si (Y) ₂ , Sn (Y) ₂ (Y is a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a hydroxy group, an alkyl group, an aryl group,
It represents an alkylthio group, an arylthio group, a trialkylsilyloxy group, a trialkyltinoxy group, or a trialkylgermaniumoxy group. ) The phthalocyanine compound according to claim 1. 3. An optical recording medium containing the phthalocyanine compound according to claim 1 or 2. 4. A structure in which a recording layer containing the phthalocyanine compound according to claim 1 or 2 on a substrate, a reflective layer made of gold or aluminum thereon, and a protective layer further laminated thereon. 3. The optical recording medium according to 3.