JPH08291261A - Phthalocyanine derivative and optical recording medium using the derivative - Google Patents

Abstract

PURPOSE: To obtain the subject new compound having strong absorption bands in visible to far IR light regions, excellent in light resistance, heat resistance, record-regenerating characteristics, and coatability to resin substrates, substantially not causing a thermal change in the wavelengths of the absorption bands, and useful for optical recording media. CONSTITUTION: A compound of formula I X is a group of the formula: O(CH2 CH2 O)n CH2 Y [Y is a (substituted) dioxorane ring; (n) is 0-3]; A is a (halogen or oxygen-bound) metal}. For example, a compound of formula II. The compound of formula I is obtained by heating a compound of formula III together with a metal (compound) such as the halide of magnesium, zinc or copper in quinoline or chloronaphthalene solvent at 200-250 deg.C for 1-5hrs, or together with a basic catalyst such as 1,8-diazabicyclo[5,4,0]-7-undecene in a high boiling alcohol such as n-pentanol at 70-120 deg.C for 1-20hrs.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phthalocyanine derivative and an optical recording medium containing the derivative as a light absorbing substance in a recording layer.

[0002]

2. Description of the Related Art An optical recording medium using a laser, especially a semiconductor laser, is a technique which has been particularly desired in recent years because it enables high density information recording and storage and reproduction thereof. An example of such an optical recording medium is an optical disc. Generally, an optical disc is one in which a thin recording layer provided on a circular substrate is irradiated with a laser beam focused to about 1 μm to record information at high density.

Recently, among the optical discs, one that has been attracting attention is a writable compact disc (CD Wri).
te Once disc). This disc has the same shape as the compact disc. The user can record the music and information only once using the recording device, and can reproduce the recorded music and information by using the existing CD player or CD ROM drive.

This disc is usually constructed by sequentially laminating a recording layer containing a dye as a main component, a metal reflection film, and a protective film on a plastic substrate having guide grooves. Information is recorded by irradiating a laser beam (usually having a wavelength of 780 nm) to decompose and evaporate the recording layer and the substrate at that location.
Reproduction of information generated and recorded by a thermal change such as melting is performed by reading a difference in reflectance between a portion where a change has occurred and a portion where no change has occurred, with a laser beam.

Therefore, it is important for the optical recording medium that the recording sensitivity to the laser light used for recording is high and the reflectance to the laser light used for reproduction is low in the recorded portion and high in the unrecorded portion. In order to reproduce by a compact disc player, it is necessary that the reflectance of the unrecorded portion with respect to the laser beam (usually 780 nm) used for the reproduction is 65% or more and the reflectance of the recording portion is 45% or less.

[0006] Such a CD Write Once
As a dye to be used in the recording layer of a disc, a dye using a cyanine dye has been conventionally proposed, but a dye using a cyanine dye has a drawback that it is weak against sunlight and other light. In addition, as an optical recording medium using an organic dye, one using a squarylium dye, a naphthoquinone dye, a phthalocyanine dye, a naphthalocyanine dye, or the like has been proposed.

Of the above-mentioned dyes, phthalocyanine dyes and naphthalocyanine dyes are generally preferable because they have excellent weather resistance, but those having no substituents on the benzene ring or naphthalene ring have solubility in a solvent. Since it is extremely low, there is a problem that the recording layer cannot be formed by coating. On the other hand, Japanese Patent Application No. 6-0817
In No. 42, the present inventors proposed to introduce a tetrahydrofurfuryloxy group or the like into the benzene ring in the phthalocyanine dye. However, these phthalocyanine derivatives have a problem that recording sensitivity is not always high when used as a dye for a recording layer of a CD Write Once disc.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel phthalocyanine derivative which can solve the above-mentioned conventional problems and an optical recording medium using the derivative.

[0009]

The inventors of the present invention have arrived at the present invention as a result of intensive studies to achieve the above object. That is, the present invention provides a phthalocyanine derivative represented by the general formula [I]

[0010]

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(In the formula, X is —O (CH ₂ CH ₂ O) nC.
H ₂ Y (wherein Y represents a dioxolane ring which may have a substituent, and n is an integer of 0 to 3), and A
Represents a halogen atom or a metal atom to which an oxygen atom may be bonded), and a recording layer on the substrate, and the recording layer is a phthalocyanine derivative represented by the general formula [I] shown above as a light absorbing substance. The gist of the present invention is an optical recording material characterized by containing.

Each of the phthalocyanine derivatives of the present invention has absorption in the near infrared region near 600 to 800 nm,
It has excellent light resistance and heat resistance and is very useful as a light absorbing substance for an optical recording medium as described later. Among them, in the following general formula [II], one of D and E is -O (CH
Represents ₂ CH ₂ O) nCH ₂ Y group, and the other one represents a hydrogen atom, a Y is di 2,2-methyl-1,3-dioxolane ring, n is 0, A is Cu atoms A phthalocyanine derivative in the case of is preferable.

Further, the optical recording medium of the present invention uses the phthalocyanine derivative of the present invention as a light absorbing substance to solve the above-mentioned problems of the conventional optical recording medium and develop its function. Is. The phthalocyanine derivative represented by the above general formula [I] used as a light absorbing substance in the optical recording medium of the present invention has the following general formula [III] (wherein X is —O (CH ₂ CH ₂ O) nCH ₂ Y).
(Wherein Y represents a dioxolane ring which may have a substituent, and n is an integer of 0 to 3) and the metal or metal compound in a quinoline or chloronaphthalene solvent. 1 to 5 hours, 2
Heat to 00-250 ° C or DBU (1,8-
Diazobicyclo [5.4.0] -7-undecene) and a high boiling alcohol such as n-pentanol or n-hexanol together with a basic catalyst such as n-pentanol or n-hexanol for 1 hour to 20 minutes.
It can also be synthesized by heating to about 70 to 120 ° C. for about an hour.

The metals and metal compounds used are IB
Group, Group IIA, Group IIB, Group IIIA, Group IVA, Group VB, VIB
Although various compounds of Group VIII and Group VIII can be mentioned, copper, magnesium, zinc, titanium, aluminum, indium, in view of easiness of synthesis and performance of the obtained compound,
Tin, lead, vanadium, chromium, iron, cobalt, nickel, ruthenium, palladium and oxides, halides and acetates thereof are preferable, and halides of magnesium, zinc and copper are particularly preferable.

Further, the phthalocyanine derivative represented by the general formula [I] shown above is represented by the following general formula [IV] (wherein X is -O).
(CH ₂ CH ₂ O) nCH ₂ Y (where Y represents a dioxolane ring which may have a substituent, and n is 0 to 3).
Phthalic acid derivative represented by the formula) and a metal or a metal compound in the presence of urea in a quinoline or chloronaphthalene solvent for about 1 to 5 hours for about 200 to 2
It can be synthesized by heating to 50 ° C. Metals and metal compounds used include IB group, IIA group, II
Examples thereof include Group B, Group IIIA, Group IVA, Group VB, Group VIB and Group VIII. Magnesium, zinc, vanadium, nickel, cobalt and copper oxides or halides and acetates Particularly preferred. Furthermore, when nickel, cobalt, and copper halides are used, it is preferable to add a small amount of ammonium molybdate as a catalyst because the yield increases.

[0016]

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The optical recording medium of the present invention basically comprises a substrate and a recording layer. If necessary, an undercoat layer may be provided on the substrate, and a reflective layer and a protective layer may be provided on the recording layer. Can be provided. As the substrate in the present invention,
It may be transparent or opaque to the laser light used. As the material of the substrate, a support for a recording medium of this type such as glass, plastic, paper, plate-shaped or foil-shaped metal can be generally used, but plastic is preferable from various viewpoints. Examples of the plastic include acrylic resin, methacrylic resin, vinyl acetate resin,
Examples thereof include vinyl chloride resin, nitrocellulose, polyethylene, polypropylene, polycarbonate, polyimide, polysulfone and the like.

In the optical recording medium of the present invention, the thickness of the information recording layer containing a light absorbing substance is 100Å.
˜5 μm, preferably 500 Å to 3 μm. In the present invention, as a method for forming such a recording layer on the substrate surface, a coating method is preferable. As a film forming method by coating, the above-mentioned general formula [I] used as a light absorbing substance is used.
The phthalocyanine derivative of the present invention shown in, a solution or dispersion of a solvent or a mixture of a solvent and a binder, a method of spin coating, a method of spray coating and the like, the binder in such cases, polyimide, polyamide , Polystyrene, acrylic resin, polyester, polycarbonate, cellulose and the like.

At this time, the ratio of the light absorbing substance to the resin is preferably 10% by weight or more. The solvent in such a case includes dimethylformamide, methyl ethyl ketone,
Various substances such as methyl cellosolve, ethyl alcohol, tetrahydrofuran, dichloromethane and chlorobenzene can be used. When a polycarbonate substrate or a methacrylic resin substrate manufactured by injection molding is used as the substrate, the solvent is preferably ethyl cellosolve, ethyl alcohol, octafluoropentanol or the like.

The recording layer of the optical recording medium of the present invention may be provided on both sides of the substrate, or may be provided on only one side. Recording on the optical recording medium obtained as described above is performed by irradiating a recording layer provided on both sides or one side of the substrate with a laser beam converged to about 1 μm, preferably a semiconductor laser beam. In the part where the laser light is irradiated,
Due to the absorption of laser energy, thermal deformation of the recording layer such as decomposition, evaporation and melting occurs.

The recorded information is reproduced by using a laser beam to read the difference in reflectance between the portion where thermal deformation has occurred and the portion where thermal deformation has not occurred. As a light source, H
Various lasers such as an e-Ne laser, an argon laser, and a semiconductor laser can be used, but the semiconductor laser is particularly preferable in terms of cost and size.

As the semiconductor laser, a laser having a central wavelength of 830 nm and a central wavelength of 780 n which are currently used.
m lasers and shorter wavelength lasers can also be used. Further, the phthalocyanine derivative of the present invention can be used for applications other than optical recording media such as coloring of various materials such as plastic and paper, dyeing of various fibers, coloring of optical filters.

[0023]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples. In addition, "%" is "% by weight" unless otherwise specified. Example 1

Synthesis of 2,2-dimethyl-4-[(2,3-dicyanophenoxy) methyl] -1,3-dioxolane 2.8 g of sodium hydroxide was dispersed in 100 ml of tetrahydrofuran previously dehydrated by molecular sieves. , 2,2-dimethyl-at 5-10 ° C with stirring
9.24 g of 1,3-dioxolane-4-methanol was added to 3
It was added dropwise in 0 minutes. After stirring at 5-10 ° C for 1 hour, 5
A solution of 8.65 g of 3-nitrophthalonitrile dissolved in 100 ml of tetrahydrofuran was added dropwise at -10 ° C over 1 hour. This was stirred at 5 to 10 ° C. for 5 hours, then allowed to stand overnight, and added to 500 g of ice water. The precipitate formed was filtered off, washed with water and dried to give pale yellow crystals 8.8.
g was obtained. This product was dissolved in 100 ml of ethyl acetate and chromatographed on a silica gel column (filler: Wakogel C-200, manufactured by Wako Pure Chemical Industries, developing solvent: ethyl acetate) to give 2,2-represented by the following structural formula [V]. Dimethyl
4-[(2,3-dicyanophenoxy) methyl] -1,
5.1 g of a purified product of 3-dioxolane was obtained. The structure is NM
It was confirmed by the R spectrum (shown in FIG. 1).

Synthesis of Phthalocyanine Derivative 2,2-Dimethyl-4-obtained as described above
[(2,3-Dicyanophenoxy) methyl] -1,3-
2.58 g of dioxolane was added to 10 ml of α-chloronaphthalene together with 0.37 g of anhydrous copper chloride and 0.2 g of ammonium molybdate, and the mixture was stirred at 180 ° C. to 200 ° C. for 4 hours. After allowing to cool, 30 ml of n-hexane was added, and the obtained crystals were separated by filtration to obtain 1.5 g of a green substance. This product was dissolved in 30 ml of chloroform and chromatographed on a silica gel column (filler: Wakogel C-200, manufactured by Wako Pure Chemical Industries, developing solvent: chloroform, methyl alcohol mixed system) to give 0.72 g of a green compound.
I got The obtained substance (crystal) is considered to include isomers, and its typical structure is represented by the following formula [VI].
Λmax of this substance in chloroform solution is 698n
m, the molecular extinction coefficient was 19.5 × 10 ⁴ .

[0026]

[Chemical 4]

Example 2 2,2-Dimethyl-4-[(2,3-dicyanophenoxy) methyl] -1,3-dioxolane 2.58 g, anhydrous magnesium chloride 0.29 g, DBU (1,8-diazabicyclo [ 4.3.0] -7-undecene) 1.52 g
Was added to 10 ml of n-amyl alcohol to generate nitrogen gas stream,
The mixture was stirred at 90 ° C to 100 ° C for 3.5 hours. The n-amyl alcohol was distilled off under reduced pressure to obtain 0.45 g of a green product.
This product was dissolved in 20 ml of chloroform and a silica gel column (filler: Wakogel C-200, manufactured by Wako Pure Chemical Industries,
Chromatographic purification with a developing solvent: chloroform-methanol mixed system) gave 0.14 g of a green compound. The obtained substance (crystal) is considered to include isomers, and its typical structure is represented by the following formula [VII]. This substance had a λmax of 701 nm in a chloroform solution and a molecular extinction coefficient of 23.2 × 10 ⁴ .

[0028]

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Examples 3 to 8 According to Example 1, in Example 3, 2,2-dimethyl-4 was used.
-[(2,3-Dicyanophenoxy) methyl] -1,3
-Dioxolane and cobalt chloride, in Example 4, 2,
2-dimethyl-4-[(2,3-dicyanophenoxy)
Methyl] -1,3-dioxolane and nickel chloride, and in Example 5, 2,2-dimethyl-4-[(2,3-dicyanophenoxy) methyl] -1,3-dioxolane and ruthenium chloride (RuCl ₃ ). The phthalocyanine derivative of the present invention was synthesized by reacting each of these.

According to the second embodiment, in the sixth embodiment,
2-dimethyl-4-[(2,3-dicyanophenoxy)
Methyl] -1,3-dioxolane and ferrous chloride, in Example 7, 2,2-dimethyl-4-[(2,3-dicyanophenoxy) methyl] -1,3-dioxolane and palladium chloride, In Example 8, 2,2-dimethyl-4-
[(2,3-Dicyanophenoxy) methyl] -1,3-
The phthalocyanine derivative of the present invention was synthesized by reacting dioxolane with zinc chloride.
As a result, each of the obtained substances (crystals) is considered to contain an isomer, but as a typical structure thereof, the substances of Examples 3 to 8 can be respectively represented by the following general formula [VIII]. .

[0031]

[Chemical 6]

Further, the structures of the substances (substituents A and R in the general formula (VIII)) obtained in Examples 3 to 8, λmax in a chloroform solution, and the measurement results of the molecular extinction coefficient were measured as described above. The measurement results of Examples 1 and 2 are collectively shown in Table 1 below.

[0033]

[Table 1]

Examples 9 to 11 General formula [IX] (A and R in the formula are shown in Table 2 below)
Three kinds of phthalocyanine derivatives of the present invention represented by are synthesized according to Example 1. Table 2 below shows the λmax and molecular extinction coefficient of each of the obtained substances in a chloroform solution.

[0035]

[Chemical 7]

[0036]

[Table 2]

Example 12 A 1.7% octafluoropentanol solution of the phthalocyanine derivative of the present invention represented by the structural formula [VI] synthesized on the basis of Example 1 was prepared and spin-coated (rotation speed 500 rpm). Was applied onto a polycarbonate substrate having a diameter of 120 mm and a plate thickness of 1.2 mm. Gold was vapor-deposited on the dye thin film to form a reflective layer, and a protective layer made of an ultraviolet curable resin was provided on the reflective layer to prepare an optical recording medium. 775 nm of the unrecorded part of the obtained optical recording medium
The reflectance was 74%.

A linear velocity of 1.2 m /
While rotating at s, a semiconductor laser beam having a central wavelength of 775 nm was irradiated at an output of 9.3 mW to record an EFM signal. Next, when the recording portion was reproduced with a CD player having a semiconductor laser having a central wavelength of 780 nm, a good reproduced signal was obtained. In addition, light resistance (xenon fade meter acceleration test; 60 hours) and storage stability (70
As a result of a test conducted at 85 ° C. and 85% RH for 100 hours, no deterioration in sensitivity and reproduction signal was observed as compared with the initial stage, and it was an extremely excellent optical recording medium.

Comparative Example A compound represented by the following structural formula [X] was synthesized according to Example 1 of Japanese Patent Application No. 6-081742.

[0040]

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Synthesis of 3-tetrahydrofurfuryloxyphthalic anhydride 3-hydroxyphthalic acid (melting point 200-204 ° C.) 10
0 g was dispersed in methyl alcohol 21, 5% 97% sulfuric acid was added, and the mixture was stirred under reflux for 24 hours. After allowing to cool, it is added to ice water 51, and the precipitated crystals are separated by filtration, washed with water and dried,
85 g of crystals of dimethyl 3-hydroxyphthalate were obtained.
The structure was confirmed by mass spectrum.

15 g of dimethyl 3-hydroxyphthalate,
Paratoluenesulfonic acid tetrahydrofurfuryl ester 2 previously synthesized from paratoluenesulfonyl chloride and tetrahydrofurfuryl alcohol according to a conventional method
Chlorobenzene 2 with 5.8 g and potassium carbonate 7.5 g
It was added to 00 ml and stirred under reflux for 10 hours. Then
After cooling, the precipitated crystals were separated by filtration and chlorobenzene was removed from the filtrate by distillation under reduced pressure to give a pale brown tar-like substance 1
3 g were obtained.

This tar-like substance was dispersed in 500 ml of a 5% aqueous sodium hydroxide solution, and the mixture was stirred under reflux for 8 hours. After cooling, concentrated hydrochloric acid was added dropwise with ice cooling to adjust the pH to 3, and the precipitate was separated by filtration and dried to obtain 9.5 g of pale yellow crystals. The crystals were recrystallized from glacial acetic acid to obtain 3-tetrahydrofurfuryloxyphthalic anhydride. The structure was confirmed by mass spectrum.

Synthesis of Phthalocyanine Derivatives 6.2 g of 3-tetrahydrofurfuryloxyphthalic anhydride thus obtained and 12.5 g of urea were crushed and mixed in a mortar, and then at 150 ° C. to 180 ° C. for 30 minutes. The reaction was carried out with stirring. Then, after cooling to about 100 ° C,
2.0 g of vanadium trichloride and 10 ml of quinoline were added and heated, and the mixture was stirred at 200 ° C to 220 ° C for 2 hours. After cooling to room temperature, 200 ml of methyl alcohol was added and the mixture was stirred under reflux for 1 hour.

Crystals obtained by hot filtration of this product were
% Aqueous sodium hydroxide solution (200 ml) and ethyl alcohol (200 ml) and the mixture was stirred under reflux for 2 hours. This product was hot filtered, washed with ethyl alcohol and dried to obtain 5.3 g of dark green crystals. The crystals were dispersed in 30 ml of chloroform, insoluble materials were filtered off, and chloroform was distilled off from the filtrate under reduced pressure. Methyl alcohol was added to the obtained green substance, and the obtained crystals were filtered to obtain 0.93 g of a green substance.

The obtained substance (crystal) is considered to include isomers, and its typical structure is represented by the above general formula [X]. The λmax of this substance in a chloroform solution was 700 nm, and the molecular extinction coefficient was 13.8 × 10 ⁴ . An optical recording medium was produced using the obtained compound under substantially the same conditions as in Example 12. The reflectance of the unrecorded portion of the obtained optical recording medium at 775 nm was 71%.

A linear velocity of 1.2 m / s was applied to the produced optical recording material.
The semiconductor laser beam having a central wavelength of 775 nm was irradiated at an output of 10.0 mW while rotating the optical disc to record an EFM signal. Next, when the recording portion was reproduced with a CD player having a semiconductor laser having a central wavelength of 780 nm, a good reproduced signal was obtained. Next, this optical recording medium was subjected to a linear velocity of 1.
While rotating at 2 m / s, a semiconductor laser beam having a central wavelength of 775 nm was emitted at an output of 9.3 mW to try to record an EFM signal. When this recording part was reproduced with a CD player having a semiconductor laser with a central wavelength of 780 nm,
The reproduced signal obtained was noisy.

[0048]

The phthalocyanine derivative of the present invention is 600
Has strong absorption in the visible to near-infrared region around ~ 800 nm, has good light resistance and heat resistance, does not easily change the absorption wavelength due to heating, and is easy to apply to the plastic substrate of the optical recording medium. That is, it has a significant effect with industrial value. Further, since the optical recording medium of the present invention contains such a phthalocyanine derivative as the light absorbing substance of the recording layer, it exhibits a remarkable effect that it is excellent in light resistance and heat resistance and has good recording and reproducing characteristics. is there.

[Brief description of drawings]

1 is the 2,2-dimethyl-4-prepared in Example 1.
[(2,3-Dicyanophenoxy) methyl] -1,3-
It is a figure which shows the NMR spectrum of dioxolane.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akiko Nozawa 1000 Kamoshida-cho, Aoba-ku, Yokohama, Kanagawa Mitsubishi Chemical Corporation Yokohama Research Institute (72) Inventor Takako Tsukahara 1000, Kamoshida-cho, Aoba-ku, Yokohama, Kanagawa Mitsubishi Chemical Co., Ltd. Yokohama Research Institute

Claims (2)

[Claims] 1. A phthalocyanine derivative represented by the following general formula [I]. Embedded image (In the formula, X is —O (CH ₂ CH ₂ O) _n CH ₂ Y (wherein Y represents a dioxolane ring which may have a substituent, and n is an integer of 0 to 3)). Represents, and A represents a metal atom to which a halogen atom or an oxygen atom may be bonded.) 2. An optical recording medium having a recording layer on a substrate, the recording layer containing the phthalocyanine derivative according to claim 1 as a light absorbing substance.