JP3016649B2 - α-Alkoxyphthalocyanine compound and optical recording medium using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an .alpha.-alkoxyphthalocyanine compound (hereinafter referred to as .alpha.-APc) which is useful as a near-infrared absorber which plays an important role in optoelectronics such as information recording, display sensors and safety glasses. And an optical recording medium such as an optical disk and an optical card containing the same in a recording layer.

[0002]

2. Description of the Related Art A technique using a phthalocyanine dye, particularly an alkoxyphthalocyanine, in a recording layer of an optical recording medium such as an optical disk or an optical card is disclosed in Japanese Patent Application Laid-Open No. 61-154888 (EP 1).
No. 86404), No. 61-197280, No. 61-246091, No. 62
JP-39286-A (USP 4769307), JP-A-63-37991, JP-A-63-37991
Although it is widely known from JP 39888 and the like, phthalocyanines are not easily absorbed due to easy association. Therefore, in an optical recording medium using it, 78
The reflectivity at 0 to 830 nm was low, and it was hard to say that it had sufficient performance in sensitivity and recording characteristics.

[0003]

SUMMARY OF THE INVENTION Phthalocyanines are
Sensitivity (C / N ratio, optimum recording power),
In addition to the recording characteristics (jitter, deviation), it is difficult to prepare a coating film without defects, and it has poor solubility in organic solvents, etc., and it is not possible to form a thin film by solution coating. Therefore, there is a problem that a large-scale facility is required, and the processing cost is also increased.

Accordingly, an object of the present invention is to provide a novel phthalocyanine compound which does not have the above-mentioned disadvantages.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the problems described in the preceding paragraph, and as a result, have found a novel phthalocyanine compound meeting the above-mentioned object, and have completed the present invention.

That is, the present invention provides a compound represented by the general formula (1)

[0007]

Embedded image [In the formula (1), the R group represents the following formula;

[0008]

Embedded image 1-alkoxy-3-dialkyl , wherein in the R group, X, X 'and Y are linear or branched alkyl groups having 1 to 4 carbon atoms.
Represents an amino- isopropyl group. The substitution position of the OR group represents the 1- or 4-position, the 5- or 8-position, the 9- or 12-position, the 13- or 16-position. Met represents Cu or Pd. Α-APc represented by the formula: and an optical recording medium containing the same in a recording layer.

The α-APc of the present invention has a sharp absorption at 650 to 900 nm, a high molecular extinction coefficient of 150,000 or more, and an optical recording medium using a semiconductor laser (optical disc,
Optical card, etc.).

Further, the α-APc of the present invention utilizes the steric hindrance by introducing an alkoxy group represented by R in the general formula (1) to reduce the association of phthalocyanine, It is a phthalocyanine compound having good solubility and compatibility with a resin.Moreover, by the nitrogen atom in the alkoxy group, the adhesion to the metal layer which is a reflective layer when used as an optical recording medium is improved, and the alkylamino group It is a compound having excellent sensitivity, recording characteristics and durability due to its effect.

Hereinafter, preferred embodiments of the present invention will be described in detail.

In the general formula (1), as a specific example of the group represented by R, the steric hindrance of the alkoxy group is large, the phthalocyanine ring is easily extended in the vertical direction, and the light per unit weight of the near infrared absorbing agent is As a group capable of increasing the absorption amount of the compound, an effective group for improving the sensitivity when used as an optical recording medium, and a group effective for improving the solubility in a spin coat solvent, an alkylamino group is located at the 3- position of the isopropyl group. Substituted 1-n-butoxy-3-diisobutyryl
Mino-isopropyl group, 1-methoxy-3-diisobutyi
L-amino-isopropyl group, 1-isopropoxy-3-
And a diethylamino-isopropyl group.

As a method for synthesizing the phthalocyanine compound represented by the general formula (1), the following formula (2)

[0014]

Embedded image [In the formula (2), the R group represents the same group as in the general formula (1). And 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) in the presence of
Heat reaction with metal derivative in alcohol. Or,
A method in which a metal derivative is heated and reacted in a high-boiling solvent such as chloronaphthalene, bromonaphthalene, or trichlorobenzene may be used.

As a method for producing an optical recording medium using the phthalocyanine of the present invention, there is a method of coating or vapor-depositing one or two layers of one to three compounds containing the phthalocyanine of the present invention on a transparent substrate. As a coating method, the binder resin is 20% by weight or less, preferably 0%, and the phthalocyanine of the present invention is 0.05 to 20% by weight, preferably 0.1% by weight.
For example, there is a method of dissolving in a solvent so as to have a concentration of 5 to 20% by weight and applying by a spin coater. In addition, as the vapor deposition method, 1
There is a method of depositing on a substrate at 0 ^-5 to 10 ^-7 torr at 100 to 300 ° C.

The substrate may be any optically transparent resin. Examples include acrylic resin, polyethylene resin, vinyl chloride resin, vinylidene chloride resin, polycarbonate resin, ethylene 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 the substrate is applied by a spin coating method from the viewpoint of cost and handling by the user. preferable.

From the viewpoint of the solvent resistance of the substrate, solvents used for spin coating include halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride, tetrachloroethylene, dichlorodifluoroethane, etc.), and ethers (eg, tetrahydrofuran, diethyl ether, Propyl ether, dibutyl ether, dioxane, etc.), alcohols (eg, methanol, ethanol, propanol, etc.), cellosolves (eg, methyl cellosolve,
Ethyl cellosolve and the like, and hydrocarbons (eg, hexane, cyclohexane, ethylcyclohexane, cyclooctane, dimethylcyclohexane, octane, benzene, toluene, xylene and the like) are preferably used.

To process as a recording medium, the substrate is covered with a substrate as described above, or bonded to a substrate provided with two recording layers with an air gap provided therebetween, or a reflective layer is formed on the recording layer. (Aluminum or gold), and a method of laminating a protective layer of a thermosetting (photosetting) resin.

[0021]

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

Example 1 In a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube,
3- (1'-n-butoxy-3'-diisobutylamino
-Isopropoxy ) phthalonitrile 38.5 g (0.1
Mol), 15.2 g (0.1 mol) of DBU, and n-
125 g of amyl alcohol is charged, and under a nitrogen atmosphere,
The temperature was raised to 110 ° C. Next, at the same temperature, 5.3 g (0.03 mol) of palladium chloride was added, and
Incubate at 8 ° C for 8 hours. After completion of the reaction, the mixture was cooled and insolubles were removed by filtration. After concentrating the filtrate under reduced pressure and evaporating the solvent,
Column purification (silica gel 500 g, solvent toluene) gave a dark green oily substance of the desired α-alkoxyphthalocyanine palladium compound.

The yield was 25.0 g (61%). The result of purity measurement by high performance liquid chromatography was 99.0%. The results of the visible absorption spectrum and the elemental analysis are as follows. Visible absorption: λmax = 686 nm, εg = 1.5 × 10
⁵ ml / g. Cm (solvent: toluene) Elemental analysis: C ₉₂ H ₁₄₀ N ₁₂ O ₈ Pd

[0024]

[Table 1] N-octane solution of the above phthalocyanine compound (10 g
/ L) was applied on a polycarbonate substrate to produce an optical disk having gold as a reflective layer. The reflectance of this optical disk is 70% (at 780 to 830 nm), and the rotation speed is 1800.
It exhibited a sensitivity of 60 dB in reflection of 780 nm laser light (substrate surface) at 7 mW at rpm.

Example 2 In the same container as in Example 1 , 3- (1'-methoxy-3 '
-Diisobutylamino-isopropoxy) phthalonitrile
Le 34.3 g (0.1 mol), DBU15.2g (0.
1 mol) and 120 g of n-amyl alcohol, and heated to 110 ° C. under a nitrogen atmosphere. Next, 5.3 g (0.03 mol) of palladium chloride was added at the same temperature and reacted at 120 ° C. for 12 hours. After finishing, cool down,
The mixture was filtered to remove insolubles. The filtrate was concentrated under reduced pressure, and the solvent was recovered, followed by column purification (silica gel 500 g, solvent toluene).
Thus, a dark green oily substance of the desired α-alkoxyphthalocyanine palladium compound was obtained. Yield 21g
(56.8% yield). Purity was 99.6%.

The results of the spectrum and elemental analysis are as follows. Visible absorption λmax = 686 nm, εg = 1.6 × 10 ⁵
ml / g. Cm (solvent: toluene) Elemental analysis: C ₈₀ H ₁₁₆ N ₁₂ O ₈ Pd

[0027]

[Table 2] The phthalocyanine compound is dissolved in n-octane (10
g / l) and spin-coated on the substrate to produce an optical recording medium. When recording was performed using a 780 nm semiconductor laser, a CN ratio of 60 dB was obtained at 8 mW, and there was no change even when reproduction was performed a million times with a reproduction light of 0.5 mW. 80 ℃
There was no problem in recording / reproducing even after 1000 hours under the condition of / 80%.

Example 3 In the same container as in Example 1, 3- (1'-isopropoxy) was added.
-3'-Diethylamino-isopropoxy) phthalonite
31.5 g (0.1 mol) of ril , DBU (0.1 mol) and 120 g of n-amyl alcohol are charged, and the temperature is raised to 110 ° C. under a nitrogen atmosphere. At the same temperature, 5.3 g (0.03 mol) of palladium chloride was added and 12
The reaction was performed at 0 ° C. for 10 hours.

After the completion of the reaction, the mixture was cooled and insolubles were removed by filtration. The filtrate was concentrated under reduced pressure and then purified by column (silica gel 300 g, solvent: toluene) to obtain a dark green oily substance of the target α-alkoxyphthalocyanine palladium compound. The yield is 19.5 g (57.1% yield).
And the purity was 99.9%.

The results of the visible absorption spectrum and the elemental analysis are as follows. Visible absorption: λmax = 688.5 nm, εg = 1.6 ×
10 ⁵ ml / g. Cm (solvent: toluene) Elemental analysis: C ₇₂ H ₁₀₀ N ₁₂ O ₈ Pd

[0031]

[Table 3] 10 g of the above phthalocyanine compound was added to dibutyl ether 1
The solution dissolved in 000 g was coated on a polycarbonate optical card substrate, and a protective layer was provided on the coated surface to produce an optical card. This optical card was capable of recording with a semiconductor laser beam having a linear velocity of 2 m / sec and 4 mW, and the CN ratio at that time was 55 dB. In addition, linear velocity 2m / se
c, can be reproduced by a laser beam of 0.8 mW, it was possible to 10 ^five regeneration was examined reproduction light stability.
Further, this optical card had good storage stability.

Example 4 In the same container as in Example 1, 3- (1'-n-butoxy-
3'-diisobutylamino-isopropoxy) phthaloni
Tolyl 38.5g (0.1 mol), DBU15.2
(0.1 mol), and 125 g of n-amyl alcohol, and heated to 110 ° C. under a nitrogen atmosphere. At the same temperature, 3.0 g (0.03 mol) of copper chloride was added, and 12
The reaction was completed at 0 ° C. for 10 hours. After cooling, insolubles are removed by filtration. The filtrate was concentrated under reduced pressure to recover the solvent, and then subjected to column purification (500 g of silica gel, chloroform solvent) to obtain the desired α-alkoxyphthalocyanine copper compound as a bluish green oil. The yield was 28 g (68.8% yield). Purity was 99.2%.
The results of the visible absorption spectrum and the elemental analysis were as follows.

Visible absorption: λmax = 704 nm, εg =
1.6 × 10 ⁵ ml / g. Cm (solvent: toluene) Elemental analysis: C ₉₂ H ₁₄₀ N ₁₂ O ₈ Cu

[0034]

[Table 4] 1 g of the obtained phthalocyanine compound was added to 100 g of benzene.
, And spin-coated on a substrate to produce an optical recording medium. The sensitivity was good at a CN ratio of 60 dB.

[0035]

The phthalocyanine compound of the present invention has a high reflectivity and is excellent in sensitivity and recording characteristics in an optical recording medium using the same, due to the effect of an alkoxy group, particularly an alkylamino group, in the molecule. It has excellent reproduction light stability and storage stability, and can be used for a long period of time. Further, it is a compound having good solubility in an organic solvent and good compatibility with a resin, and it is possible to easily mass-produce an optical recording medium by a coating method.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shin Aihara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Naoto Ito 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical (56) References JP-A-2-265788 (JP, A) JP-A-3-62878 (JP, A) JP-A-3-31247 (JP, A) JP-A-4-15263 (JP, A) A) JP-A-63-37991 (JP, A) JP-A-61-197280 (JP, A) JP-A-61-246091 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) C09B 47/18 G11B 7/24 516

Claims (2)

(57) [Claims] [Claim 1] The following general formula (1) [In the formula (1), the R group represents the following formula: 1-alkoxy-3-dialkyl , wherein in the R group, X, X 'and Y are linear or branched alkyl groups having 1 to 4 carbon atoms.
Represents an amino- isopropyl group. The substitution position of the OR group represents the 1- or 4-position, the 5- or 8-position, the 9- or 12-position, the 13- or 16-position. Met represents Cu or Pd. An α-alkoxyphthalocyanine compound represented by the formula: 2. An optical recording medium comprising the α-alkoxyphthalocyanine compound according to claim 1 in a recording layer.