JPH07116371B2 - Halogenated alkoxyphthalocyanine for recording / storing material, method for producing the same, and optical recording medium using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is, record-memory material, particularly useful halogenated alkoxyphthalocyanine analogue as a recording material for the write-once compact disk, a method of manufacturing the same
And an optical recording medium containing the same.

[0002]

2. Description of the Related Art A technique for using phthalocyanine in an optical recording medium is disclosed in US Pat. No. 4,298,975 and European Patent 35.
3394, U.S. Pat. No. 4,769,307,
It is described in JP-A-3-62878. The phthalocyanines disclosed in these patents are insufficient as phthalocyanines for optical recording media in terms of sensitivity and refractive index.

[0003]

DISCLOSURE OF THE INVENTION As a result of investigations, the present inventors have found the following. That is, since the write-once compact disc (CD-WO) uses laser light in the vicinity of 780 nm for writing and reading of recording, it is important to control the absorption coefficient, refractive index, and reflectance of the recording material in the vicinity of 780 nm. Therefore, the structural stability is high and 78
It is necessary to develop phthalocyanine as a recording material for CD-WO which has a high refractive index, a high decomposition property, and a high sensitivity when exposed to light near 0 nm. Secondly, when forming the recording layer, it was to develop a dye having a solubility of 30 g / l or more in a solvent capable of coating, according to the shape of the groove carved on the substrate.

[0004]

Means for Solving the Problems The inventors of the present invention have made earnest studies to solve the above-mentioned problems, and as a result, the following formulas (1) to
It has been found that a halogenated alkoxyphthalocyanine substituted with an alkoxy group having 2 to 4 secondary to quaternary carbon atoms represented by (4) is preferable as a dye for a recording / memory material .

[0005]

[Chemical 3] [In Formulas (1) to (4), R ^{1 to} R ⁴ are each independently a second
Represents an alkyl group having 2 to 4 primary, tertiary or quaternary carbon atoms and having a total carbon number of 6 to 9, Met being 2
The valent metal atom, the trivalent mono-substituted metal atom or the tetravalent di-substituted metal atom X represents a halogen atom, and n represents the number of substitutions of X and is 1 to 4. That is, the increase in steric hindrance of the alkoxy group lowers the decomposition temperature and increases the melting point. Therefore, it is possible to write with a small laser power, and the shape of the written signal is good.

Among the halogenated alkoxyphthalocyanines of formulas (1) to (4), the substituents represented by R ^{1 to} R ⁴ are 1-iso-propyl-2-methylbutyl group and 1-t-butyl-2-
1 selected from the group consisting of methylpropyl group, 1-iso-propyl-2-methylpropyl group, 1,2-dimethylbutyl group, 1-iso-propylpropyl group, 1-iso-propylbutyl group
The central metal Met is one species selected from the group of divalent metal atoms consisting of iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium and platinum, and the halogen atom is a bromine atom. Yes, the number is 1
It has been found that four halogenated alkoxyphthalocyanine compounds are particularly suitable compounds for solving the above problems.

Japanese Unexamined Patent Publication (Kokai) No. 3-62878 discloses a phthalocyanine having a branched alkoxy group and a substituent, but Examples 93 to 100 have no halogen atom and therefore have a refractive index at 780 nm. Was as low as less than 2. Further, the compounds of Examples 101 to 103 had low solubility in a coating solvent and were about 10 g / l. Therefore, a CD-WO optical recording medium could not be manufactured industrially.

Therefore, as a result of earnest studies, the present inventors have found that
The phthalocyanine having 2 to 4 secondary, tertiary or quaternary carbon atoms and having a total carbon number of 6 to 9 and a combination with a bromine atom has solubility, refractive index, The inventors have found that the sensitivity (the compound is easily thermally decomposed, that is, the decomposition initiation temperature is low) and the recording characteristics are good, and the present invention has been completed. Among them, when the symmetry of the molecule is low,
For example, the formulas (2), (3) and (4), and the formulas (1-3), (1-4) (1-5) (1-6) (1-
7) Compounds such as (1-8) have excellent solubility in coating solvents.

In producing the compound of the present invention, preferred compounds as raw materials are the following general formulas (5) and (6)

[0010]

[Chemical 4] [In formula (5) or (6), R has 2 to 4 secondary, tertiary or quaternary carbon atoms, and has a total carbon number of 6 to
9 represents an alkyl group, X represents a halogen atom, and 4
It is attached to position 6 or 6. n represents 0 or 1. ] 1 to 4 types of alkoxyphthalonitrile or alkoxydiiminoisoindoline represented by the above formula, and at least one type has a substituent X.

As a particularly preferable raw material, in the formula (5) or (6), R is a 1-iso-propyl-2-methylbutyl group, 1
-t-butyl-2-methylpropyl group, 1-iso-propyl-2-methylpropyl group, 1,2-dimethylbutyl group, 1-iso-propylpropyl group, 1-iso-propylbutyl group It is a compound selected from the group in which X is bromine.

The metal or metal compound which is the other raw material of the present invention includes aluminum, silicon, titanium, vanadium, chromium, manganese, iron, cobalt, nickel,
Examples thereof include copper, zinc, gallium, germanium, ruthenium, rhodium, palladium, indium, tin, platinum, and chlorides, bromides, iodides, acetates, and oxides thereof. Particularly preferred are iron chloride, iron bromide, iron acetate, cobalt chloride, cobalt bromide, cobalt acetate, nickel chloride, nickel bromide, nickel acetate, copper chloride, copper bromide, copper iodide, copper acetate, chloride. Zinc, zinc bromide, zinc acetate, ruthenium chloride, rhodium chloride, rhodium bromide, palladium chloride, palladium bromide, palladium acetate, platinum chloride, platinum bromide.

The conditions for synthesizing the phthalocyanine ring are that 1 to 4 kinds of the raw material alkoxyphthalonitrile or alkoxydiiminoisoindoline are heated and reacted at 10 to 300 ° C. in a solvent, preferably alcohol. When the raw material is the alkoxyphthalonitrile represented by the formula (5), the reaction temperature is preferably 80 to 160 ° C. Further, when the raw material is alkoxydiiminoisoindoline represented by the formula (6), the temperature is preferably 140 to 200 ° C. Further, as a catalyst for the ring forming reaction, diazabicycloundecene (DBU), diazabicyclononene (D
An auxiliary agent such as BN) may be added.

The alkoxyphthalonitrile (5) or diiminoisoindoline (6) used in the present invention was synthesized by the method of the following formula.

[0015]

[Chemical 5] 3-Nitrophthalonitrile was obtained from Tokyo Chemical Industry Co., Ltd. NOUVEAU JOURNALDE CHIMIE is used to synthesize alkoxyphthalonitrile (b) from nitrophthalonitrile (a).
It was produced by the method described in VOL.6 No.12, pages 653-58 (1982). That is, the alcohol was converted to sodium alkoxide with sodium hydride and subsequently reacted with nitrophthalonitrile at 0 to 100 ° C. to give alkoxyphthalonitrile.

The synthesis of halogenated alkoxyphthalonitrile (c) is described by IT Harrison and S. Harrison in "COMPENDIUM OF ORGANIC SYNTHETIC METHODS", Volumes 1-6.
The alkoxyphthalonitrile was halogenated by the method described in "WILEY-INTERSCIENCE". Then, it was separated and purified by column chromatography. Examples of the halogenating agent that can be used for the above halogenation include chlorine, bromine, iodine, sulfuryl chloride, thionyl chloride, antimony chloride, ICl ₃ , and FeC.
l ₃ , phosphorus pentachloride, phosphorus oxychloride, t-butyl hypochlorite, N-chlorosuccinimide, cupric bromide, quaternary ammonium bromide, N-bromosuccinimide, iodochloride, quaternary ammonium iodide Dyad, potassium iodide and the like are preferred. The amount of the halogenating agent used is appropriately 1 to 2 molar ratio with respect to the alkoxyphthalonitrile.

The alkoxydiiminoisoindoline (d) is synthesized from the alkoxyphthalonitrile (b), and the halogenated alkoxydiiminoisoindoline (e) is synthesized from the halogenated alkoxyphthalonitrile (c) by reaction with ammonia. To be done. (E) is (d)
Can also be synthesized by halogenating the above.

A recording medium suitable for the compound of the present invention has a structure in which a substrate, a recording layer, a reflective layer and a protective layer are laminated in this order.

The resin used as the basis of the present invention is
It should be optically transparent. For example, polyacrylic resin, polyolefin resin, polycarbonate resin, polyester resin, etc. may be mentioned. The surface of the base may be covered with a photocurable resin or a thermosetting resin.

As a method for producing the recording layer, a coating liquid containing the compound of the present invention and 20% by weight or less of the binder resin is coated on a substrate by using a spin coater.
The concentration of the coating liquid is preferably 5 to 100 g / l. The coating solvent may be any solvent that does not attack the substrate.
Preferably, n-hexane, cyclohexane, n-octane, ethylcyclohexane, dimethylcyclohexane, cyclooctane, tetrachloroethane, carbon tetrachloride, dichloromethane, chloroform, THF, dioxane, or a mixed solvent thereof may be used. The thickness of the recording layer is preferably 50 to 300 nm.

Further, as the reflective layer, aluminum, gold,
A metal such as silver can be used. The reflective layer is obtained by sputtering metal. The thickness of the reflective layer is 20 to
200 nm is preferred.

The resin used for the protective layer is
A thermosetting resin or a photocurable resin, for example, an acrylic / urethane resin is used. The thickness of the protective layer is 1 μm to 1 mm
Is preferred. The manufacturing method is that a thermosetting resin or a photo-curing resin is applied on the reflective layer by spin coating, and a film is formed and cured.

[0023]

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

Example 1 10 parts of phthalonitrile represented by the following formula (5-1), 2 parts of palladium chloride, 4 parts of DBU and n-amyl alcohol 2
00 parts were mixed and reacted at 95 ° C. for 24 hours.

[0025]

[Chemical 6] The reaction mixture was discharged into 1 liter of methanol, and the precipitated tar was separated and purified by column chromatography to obtain the following formula (1-
1) 2 parts, (2-1) 2 parts, (3-1) 0.5 part, (4
-1) 0.5 part was obtained. The physical properties of each were as shown in the table below.

[0026]

[Chemical 7]

[0027]

[Chemical 8]

[0028]

[Chemical 9]

[0029]

[Chemical 10]

[0030]

[Table 1] Example 2 Diiminoisoindoline 1 represented by the following formula (6-1)
0 parts, 2 parts of palladium chloride, 4 parts of DBU and 200 parts of n-octyl alcohol were mixed and reacted under reflux for 4 hours.

[0031]

[Chemical 11] The reaction mixture was discharged into 1 liter of methanol, and the precipitated tar was separated and purified by column chromatography to obtain the following formula (1-
2) 0.5 parts, (2-2) 0.1 parts, (3-2) 5.1
Parts, (4-2) 0.5 parts were obtained. The physical properties of each were as shown in the table below.

[0032]

[Chemical 12]

[0033]

[Chemical 13]

[0034]

[Chemical 14]

[0035]

[Chemical 15]

[0036]

[Table 2] Example 3 5 parts of phthalonitrile represented by the formula (5-1), 5 parts of phthalonitrile represented by the following formula (5-2), 2 parts of palladium chloride, 4 parts of DBU and 200 parts of n-amyl alcohol were mixed. And reacted at 95 ° C. for 4 hours.

[0037]

[Chemical 16] The reaction mixture was discharged into 1 liter of methanol, and the precipitated tar was separated and purified by column chromatography to obtain the following formula (1-
3) 0.1 part, (1-4) 0.1 part, (1-5) 0.5
Parts, (1-6) 0.3 parts were obtained. The physical properties of each were as shown in the table below.

[0038]

[Chemical 17]

[0039]

[Chemical 18]

[0040]

[Chemical 19]

[0041]

[Chemical 20]

[0042]

[Table 3] Example 4 8 parts of phthalonitrile represented by the formula (5-1), 2 parts of phthalonitrile represented by the following formula (5-3), 2 parts of palladium chloride, 4 parts of DBU and 300 parts of n-amyl alcohol were mixed. And reacted at 95 ° C. for 24 hours.

[0043]

[Chemical 21] The reaction mixture was discharged into 1 liter of methanol, and the precipitated tar was separated and purified by column chromatography, and the following formula (3-
3) 0.2 parts, (1-7) 0.3 parts, (3-4) 0.5
Part, (3-5) 0.3 part, (1-8) 0.2 part, (1-
1) 0.2 parts and (3-1) 0.2 parts were obtained. The physical properties of each were as shown in the table below.

[0044]

[Chemical formula 22]

[0045]

[Chemical formula 23]

[0046]

[Chemical formula 24]

[0047]

[Chemical 25]

[0048]

[Chemical formula 26]

[0049]

[Table 4] Example 5 Diiminoisoindoline 7 represented by the formula (6-1)
Parts, 3 parts of diiminoisoindoline represented by the following formula (6-2), 2 parts of palladium chloride, 4 parts of DBU and 300 parts of n-octyl alcohol were mixed and reacted under reflux for 4 hours.

[0050]

[Chemical 27] The reaction mixture was discharged into 1 liter of methanol, and the precipitated tar was separated and purified by column chromatography, and the following formula (3-
6) 0.4 parts, (1-9) 0.3 parts, (3-7) 0.2
Part, (3-8) 0.2 part, (1-10) 0.2 part, (3
-9) 0.1 part, (1-11) 0.2 part, (3-2)
0.2 part and (1-2) 0.2 part were obtained. The physical properties of each were as shown in the table below.

[0051]

[Chemical 28]

[0052]

[Chemical 29]

[0053]

[Chemical 30]

[0054]

[Chemical 31]

[0055]

[Chemical 32]

[0056]

[Chemical 33]

[0057]

[Chemical 34]

[0058]

[Table 5] Example 6 Diiminoisoindoline 7 represented by the following formula (6-3)
Parts, 3 parts of diiminoisoindoline represented by the following formula (6-4), 2 parts of palladium chloride, 4 parts of DBU and 300 parts of n-octyl alcohol were mixed and reacted at 175 ° C. for 12 hours.

[0059]

[Chemical 35]

[0060]

[Chemical 36] The reaction mixture was discharged into 1 liter of methanol, and the precipitated tar was separated and purified by column chromatography to obtain the following formula (1-
12) 0.3 part, (4-3) 0.4 part, (3-10)
0.2 part, (3-11) 0.2 part, (4-4) 0.2
Part, (1-13) 0.1 part, (4-5) 0.2 part, (3
-12) 0.2 parts and (4-6) 0.2 parts were obtained. The physical properties of each were as shown in the table below.

[0061]

[Chemical 37]

[0062]

[Chemical 38]

[0063]

[Chemical Formula 39]

[0064]

[Chemical 40]

[0065]

[Chemical 41]

[0066]

[Chemical 42]

[0067]

[Chemical 43]

[0068]

[Chemical 44]

[0069]

[Chemical formula 45]

[0070]

[Table 6] Example 7 Diiminoisoindoline 7 represented by the following formula (6-5)
Parts, 3 parts of diiminoisoindoline represented by the following formula (6-7), 2 parts of palladium chloride, 4 parts of DBU and 300 parts of n-octyl alcohol were mixed and reacted at 175 ° C. for 12 hours.

[0071]

[Chemical formula 46]

[0072]

[Chemical 47] The reaction mixture was discharged into 1 liter of methanol, and the precipitated tar was separated and purified by column chromatography to obtain the following formula (1-
14) 0.2 parts, (1-15) 0.4 parts, (4-7)
0.1 part, (4-8) 0.1 part, (3-13) 0.2
Part, (3-14) 0.1 part, (4-9) 0.2 part, (1
-16) 0.2 parts and (3-15) 0.2 parts were obtained. The physical properties of each were as shown in the table below.

[0073]

[Chemical 48]

[0074]

[Chemical 49]

[0075]

[Chemical 50]

[0076]

[Chemical 51]

[0077]

[Chemical 52]

[0078]

[Chemical 53]

[0079]

[Chemical 54]

[0080]

[Chemical 55]

[0081]

[Chemical 56]

[0082]

[Table 7] Example 8 A solution prepared by dissolving 30 g of the compound represented by the formula (1-3) in 1 liter of dimethylcyclohexane was spin-coated on a polycarbonate substrate provided with a groove to obtain 120 n.
m was applied. Next, gold was sputtered to a thickness of 100 nm. Then spin coat UV curable resin,
It was cured by UV light. Its thickness was 6 μm.
The CD-WO optical recording medium manufactured in this manner is 60 dB recording when recorded at a linear velocity of 1.4 m / sec, a 780 nm laser beam and an optimum power (8 mW), and has recording characteristics (signal symmetry, jitter). , Crosstalk) was also excellent. The reflectance was 69%. The refractive index of this recording layer was 2.12 at 780 nm.

Examples 9 to 16 CD-WO optical recording media were prepared in the same manner as in Example 8 using the compounds obtained in the above Examples. The obtained optical recording medium was examined for optimum power, recording sensitivity, symmetry, jitter, and crosstalk. The results are shown in the table below. The reflectances were all between 65 and 72%.

[0084]

[Table 8] Comparative Examples 1 to 6 CD-W was prepared by using the exemplified compounds (I-98) to (I-103) of JP-A-3-62878 in the same manner as in Example 7.
An O optical recording medium was produced. The respective recording characteristics are shown in the table below. The structures of the exemplified compounds (I-98) to (I-103) are as follows.

[0085]

[Chemical 57]

[0086]

[Chemical 58]

[0087]

[Chemical 59]

[0088]

[Chemical 60]

[0089]

[Chemical formula 61]

[0090]

[Chemical formula 62]

[0091]

[Table 9]

[0092]

The phthalocyanine compound of the present invention is
-Recording of an optical recording medium having excellent solubility in a solvent, having a refractive index and sensitivity by having 2 to 4 quaternary carbon atoms and having an alkoxy group having a total carbon number of 6 to 9 and a halogen atom It is useful as a layer forming compound.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location G11B 7/24 516 7215-5D (72) Inventor Kenichi Sugimoto 1190 Kasamacho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Shin Aihara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (56) Reference JP-A-3-62878 (JP, A)

Claims (10)

[Claims] 1. A compound represented by the following general formulas (1) to (4):
Halogenated alkoxy phthalocyanine compound for recording and memory materials . [Chemical 1] [In Formulas (1) to (4), R ^{1 to} R ⁴ are each independently a second
Represents an alkyl group having 2 to 4 primary, tertiary or quaternary carbon atoms and having a total carbon number of 6 to 9, Met being 2
The valent metal atom, the trivalent mono-substituted metal atom or the tetravalent di-substituted metal atom X represents a halogen atom, and n represents the number of substitutions of X and is 1 to 4. ] 2. The substituent X of the halogenated alkoxyphthalocyanine is a bromine atom, and the substituents R ^{1 to} R ⁴ are 1-iso-
Propyl-2-methylbutyl group, 1-t-butyl-2-methylpropyl group, 1-iso-propyl-2-methylpropyl group, 1,2-dimethylbutyl group, 1-iso-propylpropyl group, 1-iso The compound according to claim 1, which is one selected from the group consisting of -propylbutyl group. 3. The central metal Met of the halogenated alkoxyphthalocyanine is one selected from the group of divalent metal atoms consisting of iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium and platinum. Item 2
Compound of. 4. A method for producing a halogenated alkoxyphthalocyanine for a recording / memory material according to claim 1, which comprises the following formula (5) or (6): [In formula (5) or (6), R has 2 to 4 secondary, tertiary or quaternary carbon atoms, and has a total carbon number of 6 to
9 represents an alkyl group, X represents a halogen atom, and 4
It is attached to position 6 or 6. n represents 0 or 1. ] The compound which has 1 to 4 types, and at least 1 type of substituent X is selected from the alkoxy phthalonitrile or the alkoxy diimino isoindoline shown by these, and it reacts with a metal or a metal compound. 5. The substituent R is 1-iso-propyl-2-methylbutyl group, 1-t-butyl-2-methylpropyl group, 1-iso-propyl-2-methylpropyl group, 1,2-dimethyl. Butyl group, 1
It is one selected from the group consisting of -iso-propylpropyl group and 1-iso-propylbutyl group, and the metal or metal compound is iron chloride, iron bromide, iron acetate, cobalt chloride, cobalt bromide, cobalt acetate. , Nickel chloride, nickel bromide,
Nickel acetate, copper chloride, copper bromide, copper iodide, copper acetate, zinc chloride, zinc bromide, zinc acetate, ruthenium chloride, rhodium chloride, rhodium bromide, palladium chloride, palladium bromide, palladium acetate, platinum chloride, The production method according to claim 4, which is one selected from the group of platinum bromide. 6. The production method according to claim 5, wherein the reaction is carried out at a reaction temperature of 10 to 300 ° C. using an alcohol solvent. 7. The material according to claim 6, wherein the raw material is phthalonitrile represented by the formula (5) and the reaction temperature is 80 to 1
The manufacturing method which is 60 ° C. 8. The production method according to claim 6, wherein the raw material is diiminoisoindoline represented by the formula (6) and the reaction temperature is 140 to 200 ° C. 9. An optical recording medium containing the halogenated alkoxy phthalocyanine according to claim 1 . 10. The medium structure comprises a substrate, a recording layer, a reflective layer,
The protective layer, and the recording layer according to any one of claims 1 to 3.
An optical recording medium containing a halogenated alkoxyphthalocyanine compound described therein .