JPH1046040A - Phthalocyanine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new phthalocyanine compound capable of providing a recording medium capable of being reactivated or record-regenerated by a laser beam having 620-690nm wave length and satisfying the condition that the recording medium has >=65% reflection rate by a light having 770-830nm wave length which is a standard for a recordable compact disk. SOLUTION: This phthalocyanine compound is represented by the formula I (R1 to R8 are each an alkyl, an alkoxyalkyl, an alkoxyalkoxyalkyl, etc., with the proviso that in the combination of R1 and R2 , R3 and R4 , R5 and R6 and R7 and R8 , each case that both Rs are alkyls or the one is an alkyl and the other is an alkoxyalkyl or an alkoxyalkoxyalkyl, is excluded; X is H, a halogen, etc.; M is two Hs, a divalent metal, etc.) The compound of formula I is obtained by reacting a new phthalonitrile compound of formula II (R9 and R10 are same as R1 and R2 , respectively) with a metal (derivative). 3,6-Bis(2-ethoxyethoxy) phthalonitrile is exemplified as the compound of formula II. The compound of formula II is obtained by reacting a compound of formula III with a compound of the formula R13 -D (R13 is same as R1 ; D is a halogen, tolyloxy, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel phthalocyanine compound and an optical recording medium using the same. In particular, an optical recording medium having a recording layer containing at least a dye and a reflective layer on a transparent substrate has a wavelength of 620 to 690 nm.
The present invention relates to an optical recording medium capable of reproducing or recording / reproducing with a laser beam having a wavelength selected from the group consisting of:
A recordable compact disc (hereinafter referred to as C) capable of reproducing or recording / reproducing with laser light having a wavelength selected from 830 nm
DR).

[0002]

2. Description of the Related Art A single-plate type recordable optical recording system in which a metal reflective layer is provided on a recording layer and a protective layer is further provided on the recording layer in order to use a dye as a recording layer and increase the reflectance. The medium is, for example, Optical Data Storage 1989, Technical Di
gest Series Vol. 145 (1989). Further, a medium using a cyanine dye or a phthalocyanine dye used in the present invention in the recording layer of such a medium is commercially available as a recordable compact disk medium (hereinafter, referred to as a CD-R medium). Such an optical recording medium basically has a recording layer, a reflective layer, and a protective layer formed in this order on a substrate. When a recording layer of this optical recording medium is irradiated with a laser beam such as a semiconductor laser at a high power, the recording layer undergoes a physical or chemical change, and information is recorded in the form of pits. The pit information can be reproduced by irradiating the formed pit with a low-power laser beam and detecting the reflected light.

[0003] The CD-R medium conforms to the Orange Book standard and has a wavelength (λ) selected from 770 to 830 nm.
It has a reflectance of 65% or more for the light of 1) and absorbs the light of λ1. Therefore, it is possible to record with a 780 nm semiconductor laser and a commercially available CD player or CD equipped with a 780 nm semiconductor laser.
-It has the feature that it can be played on a ROM player.

On the other hand, the current optical recording medium has a capacity of only 650 MB, and the recording time for recording large-capacity information such as digital moving pictures is as short as 15 minutes or less. In addition, as devices become smaller, the capacity becomes insufficient when the medium is made smaller with the conventional recording density.

[0005] Recently, a semiconductor laser having a wavelength (λ2) selected from 620 to 690 nm has been developed, and high-density recording and / or reproduction can be performed. Using this semiconductor laser, development of a high-density recording medium having a recording capacity of 5 to 8 times that of a conventional medium and a player compatible with a high-density recording medium capable of reproducing this high-density recording medium have been studied. I have. In particular, a system that can record movies digitally for 2 hours or more is a DVD (degital video disk).
The market for such playback-only media and playback players is imminent.

As one of such high-density recording media, there is a read-only medium in which pits are formed at the time of forming a substrate and an aluminum reflective layer is provided, like the conventional CD or CD-ROM medium. This read-only high-density recording medium has a reflectance of 70% or more. Therefore, a high-density compatible player capable of reproducing this high-density recording medium is designed to be able to reproduce the read-only medium having a high reflectance of 70% or more. Then, for example, a conventional CD, CD-ROM or C
It is desired that a medium such as a DR can be reproduced by the high density compatible player.

A conventional CD or CD-ROM medium is read-only, and its manufacturing method is the same as that of the read-only high-density recording medium. Reproduction is possible.

On the other hand, the CD-R medium currently on the market has a reflectance of 65% for light of about 780 nm.
It has the above and can be played on a commercially available CD or CD-ROM player, but has a wavelength (λ) selected from 620 to 690 nm.
In the case of reproducing with the light of 2), there is a problem that the reflectance is very small, 10% or less. Further, the degree of modulation is small, and the reflectance of the recorded portion is larger than that of the unrecorded portion.
This is a so-called low to high recording, and the normal C
The polarity is opposite to that of D or the like (high-to-low recording), which is not preferable. Further, a large distortion is observed in the recording waveform. Due to such a number of drawbacks, it has been difficult for conventional CD-R media to be played on a high-density player equipped with a laser having a wavelength (λ2) selected from 620 to 690 nm.

For example, US Pat. No. 5,099,0009 discloses a CD-R medium in which a recording layer containing a dye, a reflective layer, and a protective layer are sequentially laminated on a substrate, and between the substrate and the recording layer of the medium, A medium in which an interference layer is provided between a recording layer and a reflection layer is disclosed. Further, an optical constant and a film thickness of a recording layer for satisfying the CD standard (Red Book) and for enabling recording are disclosed. Certainly, the medium disclosed here absorbs a part of the 780 nm light used for the CD and has a reflectance of 70% or more.
Recording and reproduction can be performed with light of this wavelength. However,
It is not intended for recording and / or reproduction with light having a wavelength (λ2) selected from 620 to 690 nm, and has nothing to do with the reflectance for the light having the wavelength, the optical constant of the recording layer, and the optical path length of the interference layer. Not disclosed. The patent discloses many examples of a medium using an indodicarbocyanine dye for a recording layer and having no interference layer, and a medium having an interference layer made of an inorganic compound or a polymer. However, the medium using the indodicarbocyanine dye in the recording layer has a reflectance of 10% or less for light having a wavelength selected from 620 to 690 nm, and the reflectance of the recorded portion is larger than that of the unrecorded portion. This results in low to high recording, which is not preferable. The reason why the reflectivity is low is that CD
The dye used for the -R medium has a large wavelength dependence of optical characteristics, and the above-mentioned indodicarbocyanine dye has a very large absorption at 600 to 750 nm when measured on a recording film, and the CD-R medium has a wavelength of around 780 nm. Since the thickness and the optical constants (refractive index, extinction coefficient) of the recording layer are designed so that the reflectivity with respect to light increases, 620
The reflectance at -690 nm decreases. Further, Examples 8 and 14 of the patent disclose media having a recording layer made of a t-butyl-substituted phthalocyanine dye different from the phthalocyanine dye used in the recording layer of the present invention, and having an interference layer made of a polymer or an inorganic compound. ing. However, these media satisfy the CD standard in reflectivity and modulation degree, but have the same pulse width modulation (CD) as CD.
When the signal recorded in n) is reproduced with light having a wavelength (λ2) selected from 620 to 690 nm, a large distortion is observed in the reproduced waveform, and the error rate and jitter are large, so that a high density compatible player cannot reproduce. .

[0010] EP-19329 discloses a medium in which a VO-phthalocyanine dye is used as a recording layer and a 300 nm interference layer made of cellulose is provided on the recording layer.
However, the patent also aims to improve the reflectance and recording sensitivity for one specific wavelength,
As in the present invention, a wavelength selected from 770 to 830 nm (λ
1) Light and wavelength (λ2) selected from 620 to 690 nm
Are not optimized so that recording and reproduction can be performed with the two lights. Furthermore, this medium has the same pulse width modu as CD
When a signal recorded by lation is reproduced with light having a wavelength (λ2) selected from 620 to 690 nm, a large distortion is observed in a reproduced waveform, a large error rate and a large jitter, and cannot be reproduced by a high-density player.

US Pat. No. 5,124,067 discloses that
Many dyes similar to the dyes used in the recording layer of the invention and media using the dyes have been disclosed. However, for example, the media disclosed in Examples 98, 100, and 102 satisfy the CD standard, but have 620-69.
When reproduced with light having a wavelength (λ2) selected from 0 nm,
The recording mode is low to high, the reflectance is as small as 10% or less, and the pulse wi is the same as CD.
Distortion is observed in the reproduced waveform of the signal recorded by dth modulation, and the error rate and jitter are large.

Further, Japanese Patent Application Laid-Open No. 3-281287 discloses 78
It has a long wavelength side end of the absorption curve at 0 nm, and the imaginary part (ima) of the complex refractive index at 780 nm.
(A) having an absolute value of ginary part) of 0.2 or less
And a recording medium comprising a mixture of a trimethine cyanine dye (B) having a maximum absorption on a shorter wavelength side than the absorption maximum wavelength of the dye as a recording layer. This medium has excellent durability and satisfies the CD standard. However, 620
It is not optimized so that reproduction can be performed with light having a wavelength (λ2) selected from 〜690 nm. As is clear from the examples, the use ratio of the trimethine cyanine dye was 50 wt.
%, Pentamethine cyanine dye is 50 wt%,
The absorption of light having a wavelength (λ2) selected from 20 to 690 nm is too large, and the reflectance is less than 15%, which makes it difficult to reproduce by a high-density compatible player.

JP-A-6-336086 discloses a medium in which a recording layer is a mixture of a trimethine cyanine dye having a specific structure and a pentamethine cyanine dye. This medium is intended for recording and reproduction with light of 780 nm and 488 nm, and the ratio of trimethine cyanine dye to pentamethine cyanine dye is 1:10. Thus, when the use ratio of the pentamethine cyanine dye is large, 620 to 690
The absorption of light having a wavelength (λ2) selected from nm is too large, and the reflectance is less than 15%.

JP-A-6-40162 discloses a medium using a trimethine cyanine dye in a recording layer. This medium is intended for recording and reproduction with 630 nm light, and cannot record with 780 nm light because the recording layer has no absorption for 780 nm light.

JP-A-3-290835 discloses a medium in which an interference layer made of a low molecular organic substance is provided between a recording layer and a reflection layer made of an aluminum alloy. The medium is 78
In order to increase the reflectance at 0 nm to 70% or more, the reflection layer is provided with an interference layer using an aluminum alloy instead of expensive gold, and the reflectance at 780 nm is certainly 70%.
% Or more, but the reflectance for light having a wavelength (λ2) selected from 620 to 690 nm is small, and cannot be reproduced by a player supporting a high-density medium.

As described above, an optical recording medium having at least a recording layer containing a dye and a reflective layer is 770-83.
A reflectance of 65% or more for a laser beam having a wavelength (λ1) selected from 0 nm is obtained, high sensitivity, excellent recording characteristics, reproduction on a commercially available CD player or CD-ROM player, and 620 There is no medium that can be reproduced by a player compatible with a high-density recording medium equipped with a laser having a wavelength (λ2) selected from 〜690 nm.

[0017]

An object of the present invention is to provide a novel naphthalocyanine compound and a 620-containing naphthalocyanine compound.
Reproduction or recording / reproduction is possible with a laser beam having a wavelength selected from 690 nm to 690 nm, and the reflectance of light having a wavelength selected from the Orange Book (a wavelength selected from 770 to 830 nm), which is the standard for current CD-R media, is 65. % Or more, recording and reproduction can be performed with the light).

[0018]

Means for Solving the Problems The present inventors have conducted intensive studies for the purpose of solving the above-mentioned problems, and have completed the present invention. That is, the present invention provides: (1) a phthalocyanine compound represented by the general formula (I):

[0019]

Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are an alkyl group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group, or a substituent represented by the following general formula (II)) X represents a hydrogen atom, a halogen atom or an alkylthio group, M represents two hydrogen atoms, a divalent metal or a trivalent or tetravalent metal derivative, provided that a combination of R ₁ and R ₂ , In the combination of R ₃ and R _4, the combination of R ₅ and R ₆ , and the combination of R ₇ and R ₈ , when both are alkyl groups, one is an alkyl group and the other is an alkoxyalkyl group, Excluding the case where the other is an alkoxyalkoxyalkyl group in the alkyl group.)

[0020]

Embedded image (Wherein A represents an alkylene group, ring B represents an oxygen atom 1 to
A heterocyclic group having four is shown. )

(2) R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
R ₇ and R ₈ are an alkyl group having 1 to 15 carbon atoms, and a total of 2 to 2 carbon atoms.
The phthalocyanine compound of (1), which is an alkoxyalkyl group of 15 or a substituent represented by the following general formula (III), and wherein X is a hydrogen atom, a halogen atom or an alkylthio group having 1 to 10 carbon atoms.

[0022]

Embedded image (In the formula, A ′ represents an alkylene group having 1 to 4 carbon atoms, and ring B ′ represents a heterocyclic group having 3 to 10 carbon atoms and having 1 to 4 oxygen atoms.)

(3) The phthalocyanine compound of (2), wherein the substituent represented by the general formula (III) is a substituent of the following structural formula:

[0024]

Embedded image

(4) a phthalonitrile compound represented by the general formula (IV),

[0026]

Embedded image (In the formula, R ₉ and R ₁₀ represent an alkyl group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group or a substituent represented by the following general formula (II), and X represents a hydrogen atom, a halogen atom or an alkylthio group. , R ₉ and R ₁₀
, Except when both are alkyl groups, when one is an alkyl group and the other is an alkoxyalkyl group, when one is an alkyl group and the other is an alkoxyalkoxyalkyl group. )

[0027]

Embedded image (Wherein A represents an alkylene group, ring B represents an oxygen atom 1 to
A heterocyclic group having four is shown. )

(5) A method for producing a phthalocyanine compound of the general formula (I), comprising reacting a phthalonitrile compound represented by the general formula (IV) with a metal or a metal derivative;

(6) A phthalonitrile compound represented by the general formula (V) is reacted with a mercapto compound represented by the general formula (VI) in the presence of a base, wherein the compound is represented by the general formula (IV). Method for producing a phthalonitrile compound,

[0030]

Embedded image (In the formula, R ₉ and R ₁₀ are the same as those in the general formula (IV).) R ₁₁ —SH (VI) (In the formula, R ₁₁ represents an alkyl group.)

(7) The phthalonitrile compound represented by the general formula (VII) or (VIII) is reacted with the compound represented by the general formula (IX) in the presence of a base, IV) a method for producing a phthalonitrile compound represented by

[0032]

Embedded image (In the formula, X represents the same as in the general formula (I).)

[0033]

Embedded image (In the formula, X represents the same as in the general formula (I), and R ₁₂ represents the same as the alkyl group, the alkoxyalkyl group, the alkoxyalkoxyalkyl group or the substituent represented by the general formula (II).) ₁₃ -D (IX) (wherein, R ₁₃ is the same as R _{12 in} formula (VIII), and D is a halogen atom, a tolyloxy group or a mesyloxy group, provided that R ₁₂ and R ₁₃ Neither is an alkyl group at the same time, one is an alkyl group and the other is an alkoxyalkyl group, one is an alkyl group and the other is not an alkoxyalkoxyalkyl group.)

(8) An optical recording medium having at least a recording layer and a reflective layer on a substrate, wherein the recording layer contains the phthalocyanine compound described above. (9) The recording layer Wherein the phthalocyanine compound represented by the general formula (I) and a compound having an absorption maximum at a wavelength of less than 630 nm are contained in the optical recording medium of (8); An optical recording medium of (9) which is a complex, (11) a red laser having a reflectance of 15% or more measured from the substrate side with respect to light selected from a red laser having a wavelength of 620 to 690 nm, and a red laser having a wavelength of 620 to 690 nm; (12) a reflectance of at least 15% as measured from the substrate side with respect to light selected from a red laser having a wavelength of 620 to 690 nm; (11) The optical recording medium according to (11), which is recordable and reproducible with a red laser having a wavelength of 620 to 690 nm, and (13) has a reflectance of 65, measured from the substrate side, for light selected from near infrared lasers having a wavelength of 770 to 830 nm. % Or more, and at least reproducible with a near-infrared laser having a wavelength of 770 to 830 nm, (14) a near-infrared laser selected from wavelengths of 770 to 830 nm An optical recording medium according to (13), wherein the optical recording medium can be recorded and reproduced.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION The phthalocyanine compound represented by the general formula (I) of the present invention will be described below.

[0036]

Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are an alkyl group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group, or a substituent represented by the following general formula (II)) X represents a hydrogen atom, a halogen atom or an alkylthio group, M represents two hydrogen atoms, a divalent metal or a trivalent or tetravalent metal derivative, provided that a combination of R ₁ and R ₂ , In the combination of R ₃ and R _4, the combination of R ₅ and R ₆ , and the combination of R ₇ and R ₈ , when both are alkyl groups, one is an alkyl group and the other is an alkoxyalkyl group, Excluding the case where the other is an alkoxyalkoxyalkyl group in the alkyl group.)

[0037]

Embedded image (Wherein A represents an alkylene group, ring B represents an oxygen atom 1 to
A heterocyclic group having four is shown. )

In the phthalocyanine compound represented by the general formula (I), when R _{1 to} R ₈ are an alkyl group, a linear or branched alkyl group having 1 to 15 carbon atoms is preferable, and a linear chain having 1 to 8 carbon atoms is preferable. Or a branched alkyl group is particularly preferred. Examples are methyl, ethyl, n-propyl,
Isopropyl group, n-butyl group, isobutyl group, sec
-Butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, n-octyl group, 2-ethylhexyl group, 2-methyl-2-hexyl Group, 2, 4
-Dimethyl-3-pentyl group and the like.

When R _{1 to} R ₈ are alkoxyalkyl groups, alkoxyalkyl groups having 2 to 15 carbon atoms are preferred.
Particularly, an alkoxyalkyl group having 3 to 6 carbon atoms is preferable. Examples include methoxyethyl, methoxypropyl,
Methoxybutyl group, ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, n-propoxyethyl group, i
Examples thereof include a so-propoxyethyl group, a 1-methoxy-2-propyl group, and a 2-ethoxy-2-propyl group.

When R _{1 to} R ₈ are alkoxyalkoxyalkyl groups, alkoxyalkoxyalkyl groups having 3 to 15 carbon atoms in total are preferred. Examples are (2-methoxyethoxy) methyl, (2-ethoxyethoxy) methyl, 2
-(2-methoxyethoxy) ethyl group, 2- (1-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2-propoxyethoxy) ethyl group, 3- (2-methoxyethoxy) ) Propyl group, 3-
(2-ethoxyethoxy) propyl group and the like.

When R _{1 to} R ₈ are a substituent represented by the general formula (II), A is an alkylene group having 1 to 4 carbon atoms;
Ring B is preferably a heterocyclic group having 3 to 10 carbon atoms and having 1 to 4 oxygen atoms, which is represented by the following formula (III),

[0042]

Embedded image (In the formula, A ′ represents an alkylene group having 1 to 4 carbon atoms, and ring B ′ represents a heterocyclic group having 3 to 10 carbon atoms and having 1 to 4 oxygen atoms.) In particular, a substituent having the following structure Is preferred.

[0043]

Embedded image

In the combination of R ₁ and R ₂ , the combination of R ₃ and R ₄ , the combination of R ₅ and R ₆ , and the combination of R ₇ and R ₈ , a compound in which both are alkyl groups, one of which is an alkyl group A compound in which the other is an alkoxyalkyl group and a compound in which one is an alkyl group and the other is an alkoxyalkoxy group are used when forming a recording layer of an optical recording medium by a coating method, as compared with the compound of the present invention. Solubility in various solvents. Examples of these solvents include alcohol solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, cellosolve solvents, ketone solvents, and ester solvents. The solubility in alcoholic solvents decreases.

X is a hydrogen atom, a halogen atom, or an alkylthio group. Examples of X are a halogen atom, such as chlorine, bromine and bromine.

When X is an alkylthio group, it has 1 carbon atom
A straight-chain, branched or cyclic alkylthio group having 10 to 10 carbon atoms is preferred, and a straight-chain or branched alkylthio group having 1 to 4 carbon atoms is particularly preferred. Examples are methylthio, ethylthio, n-
Examples include a propylthio group, an iso-propylthio group, an n-butylthio group, a tert-butylthio group, an n-hexylthio group, a cyclohexylthio group, and an n-octylthio group.

M is a metal or a metal derivative, and when M is a divalent metal, Cu, Zn, Fe, Co,
Ni, Ru, Pb, Rh, Pd, Pt, Mn, Sn, P
b is preferable, and M is a metal chloride as a metal derivative;
Hydroxides and oxides are preferable, and trivalent or tetravalent metal derivatives include AlCl, InCl, FeCl, and MnO.
H, SiCl ₂ , SnCl ₂ , GeCl ₂ , Si (O
H) ₂ , Sn (OH) ₂ , Ge (OH) ₂ , VO, TiO
Is mentioned. M is Cu, Ni, Co,
FeCl, Zn, VO, Pd and MnOH are preferred.

Table 1 shows preferred specific examples of the phthalocyanine compound of the present invention. However, in Table 1, R ₁ =
(One of R ₃ and R ₄ ) = (one of R ₅ and R ₆ ) = (one of R ₇ and R ₈ ), and R ₂ =
(The other of R ₃ and R ₄ ) = (the other of R ₅ and R ₆ ) =
(The other of R ₇ and R ₈ ).

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

[Table 5]

[0054]

[Table 6]

The phthalocyanine compound represented by the general formula (I) of the present invention can be obtained by reacting the phthalonitrile compound of the general formula (IV) with a metal or a metal derivative, preferably in a solvent.

As the metal or metal derivative, Al, S
i, Ti, V, Mn, Fe, Co, Ni, Cu, Zn,
Ge, Ru, Rh, Pd, In, Sn, Pt, Pb and their halides, carboxylate, sulfate, nitrate, carbonyl compound, oxide, complex and the like are preferable. Particularly, a halide or a carboxylate of the above metal is preferable. Examples of these are copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate, iron chloride, zinc chloride,
Zinc bromide, zinc iodide, zinc acetate, vanadium chloride, vanadium oxytrichloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate,
Examples include acetylacetone manganese, manganese chloride, lead chloride, lead acetate, indium chloride, titanium chloride, tin chloride and the like.

The amount of the metal or metal derivative used is 0.2 to 0.6 times the mole of the phthalonitrile compound of the general formula (IV),
Preferably it is 0.25 to 0.4 times mol.

The reaction temperature is 80-300 ° C., preferably 1
00-250 ° C. When the reaction temperature is lower than 80 ° C., the reaction rate is extremely slow. When the reaction temperature is higher than 300 ° C., decomposition of the generated phthalocyanine compound is accelerated.

As the solvent, an organic solvent having a boiling point of 100 ° C. or higher, preferably 130 ° C. or higher is used. For example, n-
Amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 1-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol, ethoxyethanol, propoxyethanol Alcohol solvents such as butoxyethanol, dimethylaminoethanol and diethylaminoethanol; and high-boiling solvents such as trichlorobenzene, chloronaphthalene, sulfolane, nitrobenzene and urea.

The amount of the solvent used is 1 to 100 times by weight, preferably 5 to 100 times the weight of the phthalonitrile compound of the general formula (IV).
２０20 times by weight.

In the reaction, ammonium molybdate or DBU (1,8-diazabicyclo [5.4.0] -7-undecene), 1,4-diazabicyclo [2.2.2] octane, 1,5- Diazabicyclo [4.3.0] -5-nonene may be added. The amount of the catalyst to be added is 0.1 to 10 times, preferably 0.5 to 2 times, the mole of the phthalonitrile compound of the general formula (IV).

After the reaction, the solvent is distilled off from the reaction solution, or the reaction solution is discharged into a poor solvent for the phthalocyanine compound, and the precipitate is collected by filtration to obtain a crude product of the desired phthalocyanine compound. If necessary, the crude product may be purified by recrystallization or column chromatography to obtain a high-purity target product.

The phthalocyanine compound of the present invention has a high solubility in the above-mentioned solvent used when the recording layer of the recording medium is formed by a coating method, and particularly in an alcohol-based solvent such as 2,2,3,3-tetrafluoropropanol. High solubility.

The phthalonitrile compound represented by the general formula (IV) of the present invention will be described below.

[0065]

Embedded image (In the formula, R ₉ and R ₁₀ represent an alkyl group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group or a substituent represented by the following general formula (II), and X represents a hydrogen atom, a halogen atom or an alkylthio group. , R ₉ and R ₁₀
, Except when both are alkyl groups, when one is an alkyl group and the other is an alkoxyalkyl group, when one is an alkyl group and the other is an alkoxyalkoxyalkyl group. )

[0066]

Embedded image (Wherein A represents an alkylene group, ring B represents an oxygen atom 1 to
A heterocyclic group having four is shown. )

In the phthalonitrile compound represented by the general formula (IV), when R ₉ and R ₁₀ are alkyl groups, a linear or branched alkyl group having 1 to 15 carbon atoms is preferable.
A straight-chain or branched alkyl group having 1 to 8 carbon atoms is particularly preferred. Examples are methyl, ethyl, n-propyl,
Isopropyl group, n-butyl group, isobutyl group, sec
-Butyl group, n-pentyl group, isopentyl group, neopentyl group, n-heptyl group, isoheptyl group, sec-
Heptyl group, n-octyl group, 2-ethylhexyl group,
2-methyl-2-hexyl group, 2,4-dimethyl-3-
And a pentyl group.

When R ₉ and R ₁₀ are alkoxyalkyl groups, alkoxyalkyl groups having 2 to 15 carbon atoms are preferred, and alkoxyalkyl groups having 3 to 6 carbon atoms are particularly preferred. Examples include methoxyethyl, methoxypropyl, methoxybutyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, n-propoxyethyl, iso-propoxyethyl, 1-methoxy-2-
A propyl group, a 2-ethoxy-2-propyl group and the like.

When R ₉ and R ₁₀ are alkoxyalkoxyalkyl groups, alkoxyalkoxyalkyl groups having 3 to 15 carbon atoms in total are preferred. Examples are (2-methoxyethoxy) methyl, (2-ethoxyethoxy) methyl, 2
-(2-methoxyethoxy) ethyl group, 2- (1-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2-propoxyethoxy) ethyl group, 3- (2-methoxyethoxy) ) Propyl group, 3-
(2-ethoxyethoxy) propyl group and the like.

When R ₉ and R ₁₀ are the substituents represented by the following formula (II), A is an alkylene group having 1 to 4 carbon atoms, and ring B has 3 to 4 carbon atoms having 1 to 4 oxygen atoms. Preferred are those of the following formula (III), which is a heterocyclic group of 10 to 10,

[0071]

Embedded image (In the formula, A ′ represents an alkylene group having 1 to 4 carbon atoms, and ring B ′ represents a heterocyclic group having 3 to 10 carbon atoms and having 1 to 4 oxygen atoms.) In particular, a substituent having the following structure Is preferred.

[0072]

Embedded image

Preferred examples of the phthalonitrile compound of the present invention represented by the general formula (IV) are shown below. 3,6-bis (2-methoxyethoxy) phthalonitrile 4,5-dichloro-3,6-bis (2-methoxyethoxy) phthalonitrile 4,5-dimethylthio-3,6-bis (2-methoxyethoxy) phthalo The nitrile 4,5-di-tert-butylthio-3,6-bis (2
-Methoxyethoxy) phthalonitrile 4,5-di-n-octylthio-3,6-bis (2-methoxyethoxy) phthalonitrile 3,6-bis (3-methoxypropoxy) phthalonitrile 4,5-dichloro-3, 6-bis (3-methoxypropoxy) phthalonitrile 4,5-di-sec-butylthio-3,6-bis (3-
Methoxypropoxy) phthalonitrile 4,5-dicyclohexylthio-3,6-bis (3-methoxypropoxy) phthalonitrile

3,6-bis (3-methoxypropane-2
-Yloxy) phthalonitrile 4,5-dichloro-3,6-bis (3-methoxypropan-2-yloxy) phthalonitrile 4,5-dimethylthio-3,6-bis (3-methoxypropan-2-yloxy) phthalo The nitrile 4,5-di-tert-butylthio-3,6-bis (3
-Methoxypropan-2-yloxy) phthalonitrile 4,5-dioctylthio-3,6-bis (3-methoxypropan-2-yloxy) phthalonitrile 4,5-dichloro-3- (3-methoxypropane-2-
Yloxy) -6- (2-iso-propoxyethoxy) phthalonitrile 3- (3-methoxypropan-2-yloxy) -6
(2-iso-propoxyethoxy) phthalonitrile 4,5-dichloro-3,6-bis (3-methoxybutoxy) phthalonitrile 3,6-bis (3-methoxybutoxy) phthalonitrile 4,5-di-n- Propylthio-3,6-bis (3-methoxybutoxy) phthalonitrile 4,5-di-iso-hexylthio-3,6-bis (3
-Methoxybutoxy) phthalonitrile 3- (3-methoxybutoxy) -6- (3-methoxypropan-2-yloxy) phthalonitrile 4,5-dichloro-3- (3-methoxybutoxy) -6
-(3-methoxypropan-2-yloxy) phthalonitrile

3,6-bis (1-methoxybutane-2-
Yloxy) phthalonitrile 4,5-dichloro-3,6-bis (1-methoxybutan-2-yloxy) phthalonitrile 4,5-dimethylthio-3,6-bis (1-methoxybutan-2-yloxy) phthalonitrile 4,5-di-tert-butylthio-3,6-bis (1
-Methoxybutan-2-yloxy) phthalonitrile 4,5-dichloro-3,6-bis (2-ethoxyethoxy) phthalonitrile 3,6-bis (2-ethoxyethoxy) phthalonitrile 4,5-di-n- Hexylthio-3,6-bis (2-ethoxyethoxy) phthalonitrile 4,5-dicyclohexylthio-3,6-bis (2-ethoxyethoxy) phthalonitrile 4,5-dichloro-3,6-bis (3-ethoxy Propoxy) phthalonitrile 3,6-bis (3-ethoxypropoxy) phthalonitrile 4,5-di-sec-butylthio-3,6-bis (3-
Ethoxypropoxy) phthalonitrile 4,5-di-n-heptylthio-3,6-bis (3-ethoxypropoxy) phthalonitrile 4,5-dichloro-3,6-bis [2- (2-ethoxyethoxy) ethoxy] Phthalonitrile 3,6-bis [2- (2-ethoxyethoxy) ethoxy] phthalonitrile 4,5-diethylthio-3,6-bis [2- (2-ethoxyethoxy) ethoxy] phthalonitrile 4,5-dichloro- 3- (2-ethoxyethoxy) -6
-[2- (2-ethoxyethoxy) ethoxy] phthalonitrile 3- [2- (2-ethoxyethoxy) ethoxy] -6-
(3-methoxypropan-2-yloxy) phthalonitrile 4,5-dimethylthio-3- (2-iso-propoxyethoxy) -6- [2- (2-ethoxyethoxy) ethoxy] phthalonitrile 4,5-dichloro- 3,6-bis (2-iso-propoxyethoxy) phthalonitrile

3,6-bis (2-iso-propoxyethoxy) phthalonitrile 4,5-di-iso-hexylthio-3,6-bis (2
-Iso-propoxyethoxy) phthalonitrile 4,5-di-sec-butylthio-3,6-bis (2-
iso-propoxyethoxy) phthalonitrile 4,5-dichloro-3,6-bis (2,2-dimethyl-
1,3-dioxolan-4-ylmethoxy) phthalonitrile 3,6-bis (2,2-dimethyl-1,3-dioxolan-4-ylmethoxy) phthalonitrile 4,5-dimethylthio-3,6-bis (2 2-dimethyl-1,3-dioxolan-4-ylmethoxy) phthalonitrile 4,5-dichloro-3- (2,2-dimethyl-1,3-
Dioxolan-4-ylmethoxy) -6- (4-methylpentan-2-yloxy) phthalonitrile 4,5-dimethylthio-3- (2,2-dimethyl-1,
3-dioxolan-4-ylmethoxy) -6- (4-methylpentan-2-yloxy) phthalonitrile 4,5-dichloro-3- (2,2-dimethyl-1,3-
Dioxolan-4-ylmethoxy) -6- (3-methoxypropan-2-yloxy) phthalonitrile 4,5-dichloro-3- (2,2-dimethyl-1,3-
Dioxolan-4-ylmethoxy) -6- (2-iso
-Propoxyethoxy) phthalonitrile 4,5-dichloro-3,6-bis (1,3-dioxolan-2-ylmethoxy) phthalonitrile

3,6-bis (1,3-dioxolan-2
-Ylmethoxy) phthalonitrile 4,5-di-iso-pentylthio-3,6-bis (1,3-dioxolan-2-ylmethoxy) phthalonitrile 4,5-dichloro-3- (1,3-dioxolan-2-
Ilmethoxy) -6- (2,4-dimethylpentane-3
-Yloxy) phthalonitrile 3,6-bis [2- (1,3-dioxolan-2-yl) ethoxy] phthalonitrile 4,5-dichloro-3,6-bis [2- (1,3-dioxolan-2 -Yl) ethoxy] phthalonitrile 3,6- [2- (2-methyl-1,3-dioxolane-
2-yl) ethoxy] phthalonitrile 4,5-dichloro-3,6-bis [2- (2-methyl-
1,3-dioxolan-2-yl) ethoxy] phthalonitrile 3,6-bis [2- (1,3-dioxan-2-yl)
Ethoxy] phthalonitrile 4,5-dichloro-3,6-bis [2- (1,3-dioxan-2-yl) ethoxy] phthalonitrile 4,5-dichloro-3,6-bis (3-methyloxetane- 3-ylmethoxy) phthalonitrile 3,6-bis (3-methyloxetane-3-ylmethoxy) phthalonitrile 4,5-dichloro-3,6-bis (1,4-benzodioxan-2-ylmethoxy) phthalonitrile 3, 6-bis (1,4-benzodioxan-2-ylmethoxy) phthalonitrile

When X in the phthalonitrile compound represented by the general formula (IV) is an alkylthio group, the phthalonitrile compound represented by the general formula (V) and the mercapto compound represented by the general formula (VI) are reacted in the presence of a base. It can be produced by reacting.

[0079]

Embedded image (In the formula, R _9, R ₁₀ represents an alkyl group, an alkoxyalkyl group, a substituent represented by alkoxyalkoxyalkyl group or the following general formula (II). However, both of R ₉ and R _{1 0} are simultaneously alkyl group Wherein, when one is an alkyl group and the other is an alkoxyalkyl group, this excludes the case where one is an alkyl group and the other is an alkoxyalkoxyalkyl group.)

[0080]

Embedded image (Wherein A represents an alkylene group, ring B represents an oxygen atom 1 to
A heterocyclic group having four is shown. )

R ₁₁ -SH (VI) (In the formula, R ₁₁ represents an alkyl group.)

Examples of the mercapto compound include methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, iso-propyl mercaptan, n-butyl mercaptan, sec-butyl mercaptan, tert-butyl mercaptan, n-amyl mercaptan, iso-amyl mercaptan, and n-mercaptan. Hexyl mercaptan, cyclohexyl mercaptan, n-heptyl mercaptan, n
-Octyl mercaptan and the like are used.

The amount of the mercapto compound used is 2 to 3 moles, preferably 2 to 2.5 moles, per mole of the phthalonitrile compound of the formula (V).

As the base, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium acetate and the like are used. Particularly preferably, potassium carbonate or sodium carbonate is used. The amount of the base used is 2 to 3 moles, preferably 2 moles, per mole of the phthalonitrile compound of the formula (V).
It is about 2.5 times mol.

Examples of the solvent used in the reaction include alcoholic solvents such as methanol and ethanol, and aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, dimethylimidazolidinone and N-methylpyrrolidone. These can be used alone or in a mixed system with water.
% Or less is preferable. In a mixed system with water, ketone solvents such as acetone, diethyl ketone, and methyl ethyl ketone can also be used. The amount of the solvent used is 1 to 30 times the weight of the phthalonitrile compound of the general formula (V),
Preferably it is 2 to 15 times the weight.

The reaction temperature is from 0 ° C. to the reflux temperature of the solvent,
The temperature is preferably from 10C to the reflux temperature of the solvent.

The reaction time is preferably 30 minutes to 20 hours.

After the reaction, the reaction mixture is discharged into water, collected by filtration or extracted with an aromatic solvent such as toluene and concentrated to obtain the compound of the formula (IV)
To obtain a phthalonitrile compound. The crude product thus obtained may be further purified by recrystallization or column chromatography.

The phthalonitrile compound of the general formula (IV) is produced by reacting the phthalonitrile of the general formula (VII) or (VIII) with the compound of the general formula (IX) in the presence of a base. Can be.

[0090]

Embedded image (In the formula, X represents a hydrogen atom, a halogen atom or an alkylthio group.)

[0091]

Embedded image (Wherein, X represents a hydrogen atom, a halogen atom or an alkylthio group, R ₁₂ represents an alkyl group, an alkoxyalkyl group,
Alkoxyalkoxyalkyl group or the following general formula (II)
Represents a substituent represented by )

[0092]

Embedded image (Wherein A represents an alkylene group, ring B represents an oxygen atom 1 to
A heterocyclic group having four is shown. )

R ₁₃ -D (IX) (wherein, R ₁₃ is the same as R _{12 in} formula (VIII), and D is a halogen atom, a tolyloxy group or a mesyloxy group, provided that R ₁₂ And R ₁₃ are both alkyl groups at the same time, one is an alkyl group and the other is an alkoxyalkyl group, one is an alkyl group and the other is not an alkoxyalkoxyalkyl group.)

Examples of the compound represented by the general formula (IX) include alkyl halides and esters of p-toluenesulfonic acid or methanesulfonic acid.
As the alkyl halide, preferably, 1-iodomethane, 1-bromoethane, 1-iodoethane, 1-bromopropane, 2-bromopropane, 1-iodopropane, 1-chloropropane, 1-bromobutane, 2-bromobutane, 1-bromobutane, Bromopentane, 2-bromopentane,
1-bromo-3-methylbutane, 1-bromohexane,
2-bromohexane, 3-bromohexane, 1-bromoheptane, 3-bromoheptane, 2-bromoethyl methyl ether, 2-bromoethyl ethyl ether, 3-bromopropyl ethyl ether, 2-bromomethyl-1,
3-dioxolan, 2- (2-bromoethyl) -1,3
-Dioxolan, 2- (2-bromoethyl) -2-methyl-1,3-dioxolan, 2-chloromethyl-1,4
-Benzodioxane is preferably an ester of p-toluenesulfonic acid or methanesulfonic acid, preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, se
c-butanol, n-pentanol, isopentanol n-hexanol, sec-hexanol, n-octanol, 2-ethylhexanol, 2,4-dimethyl-
3-pentanol, 2-methoxyethanol, 3-methoxypropanol, 3-methoxy-2-propanol,
3-methoxy-2-butanol, 2-methoxy-1-butanol, 2-ethoxyethanol, 2-ethoxy2-
Propanol, 2-ethoxy-1-propanol, 2-
Iso-propoxyethanol, 2- (2-ethoxyethoxy) ethanol, 2,2-dimethyl-1,3-dioxolan-4-methanol, 3-methyl-3-oxetanemethanol and p-toluenesulfonic acid or methanesulfonic acid Esters are mentioned.

The amount of the compound of the general formula (IX) used in the reaction is 0.5 to 20 times, preferably 1.0 mol, based on the phthalonitrile compound of the general formula (VII) or (VIII). ５5.0-fold molar.

Examples of the base include potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, sodium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate,
Sodium acetate and the like.

The amount of the base used is represented by the general formula (VII) or (VII)
It is 0.5 to 20 times mol, preferably 1.0 to 5.0 times mol for the phthalonitrile compound of I).

Examples of the solvent used for producing the phthalonitrile of the general formula (IV) include dimethylacetamide (DMAC), dimethylformamide (DMF), dimethylsulfoxide (DMSO), and 1,3-dimethyl-2.
-Aprotic polar solvents such as imidazolidinone (DMI); and alcoholic solvents such as methanol and ethanol.

The amount of the solvent used is determined by the formula (VII) or (V
It is 1 to 30 times, preferably 2 to 15 times the weight of the phthalonitrile compound of III).

The reaction temperature ranges from 0 ° C. to the reflux temperature of the reaction solvent, preferably from 15 to 90 ° C.

After the reaction, the reaction mixture is discharged into water, collected by filtration or extracted and concentrated with an aromatic solvent such as toluene and the like.
To obtain a phthalonitrile compound. The crude product thus obtained may be further purified by recrystallization or column chromatography.

The optical recording medium containing the phthalocyanine compound of the formula (I) in the recording layer of the present invention will be described below.

The optical recording medium of the present invention has a recording layer and a reflective layer on a substrate. An optical recording medium is a read-only optical read-only medium on which information is recorded in advance, and an optical recording medium capable of recording and reproducing information, particularly a recording layer, a reflective layer and a protective layer on a substrate in this order. The optical recording medium formed by the method will be described. This optical recording medium has a four-layer structure as shown in FIG. That is, a recording layer 2 is formed on a substrate 1, a reflective layer 3 is provided in close contact with the recording layer 2, and a protective layer 4 further covers the reflective layer 3.

The substrate may be made of any material as long as it is transparent at the wavelength of the recording light and the reproducing light. For example, an acrylic resin such as a polycarbonate resin, a vinyl chloride resin and polymethyl methacrylate, a polymer material such as a polystyrene resin and an epoxy resin, and an inorganic material such as glass are used. These substrate materials are formed into a substrate on a disk by an injection molding method or the like. If necessary, a groove may be formed on the substrate surface.

In the present invention, the recording layer has the general formula (I)
630 contained together with the phthalocyanine compound
Examples of the compound having an absorption maximum below nm include a pentamethine cyanine dye, a squarylium dye, an anthraquinone dye, an indophenol dye, a porphyrin dye, and an azo dye. Above all, wavelength 63
A compound having an absorption maximum at less than 0 nm is preferably an azo compound represented by the general formula (X) and an azo metal complex compound with a metal.

[0106]

Embedded image Wherein E represents a residue that forms a heterocycle with the nitrogen and carbon atoms to which it is attached, and F is
It represents a residue that forms an aromatic ring together with the two carbon atoms to which it is attached, and Z represents a group having an active hydrogen. )

In the above formula, E is a thiazole ring, a benzothiazole ring, or a specific example of a residue which forms a heterocyclic ring together with the nitrogen atom and carbon atom to which it is bonded.
Residues forming a pyridobenzothiazole ring, a benzopyridothiazole ring, a pyridothiazole ring, a pyridine ring, a quinoline ring, a thiadiazole ring, an imidazole ring, and the like can be given. These nitrogen-containing heterocycles may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, an aralkyl group, an aryl group, a halogen atom, a cyano group, a nitro group, and an ester group. Carbamoyl group, acyl group, acylamino group, sulfamoyl group, sulfonamide group, amino group, hydroxyl group, phenylazo group, pyridinoazo group, vinyl group, etc., and these substituents may further have a substituent. . Preferred among the substituents on the nitrogen-containing heterocyclic ring are an alkyl group having 1 to 25 carbon atoms that may have a substituent, an alkoxy group having 1 to 25 carbon atoms that may have a substituent, Halogen atom, cyano group, nitro group, optionally substituted alkylsulfamoyl group having 1 to 25 carbon atoms, optionally substituted phenylazo group, optionally substituted pyridinoazo group An ester group having 2 to 26 carbon atoms, 2 to 26 carbon atoms
Examples include a carbamoyl group having 26, an acyl group having 2 to 26 carbon atoms, an acylamino group having 1 to 25 carbon atoms, a sulfonamide group having 1 to 25 carbon atoms, and a hydroxyl group.

Specific examples of the residue of F, which forms an aromatic ring together with the two carbon atoms to which it is bonded, include a benzene ring, a naphthalene ring, a pyridine ring, a pyridone ring, and a tetrahydroquinoline ring. Or a residue forming a pyrazole ring or the like. These aromatic rings or heterocyclic rings may have a substituent, and examples of such a substituent include an alkyl group, an alkoxy group, an aryloxy group, an aralkyl group, an aryl group, a halogen atom, a cyano group, a nitro group, and an ester. Group, a carbamoyl group, an acyl group, an acylamino group, a sulfamoyl group, a sulfonamide group, an amino group, a hydroxyl group, a phenylazo group, a pyridinoazo group, a vinyl group, and the like.These substituents may further have a substituent. Good. Among the substituents on the nitrogen-containing heterocycle, preferred are those having 1 to 2 carbon atoms which may have a substituent.
5 alkyl groups, 1 to 25 carbon atoms which may have a substituent
An alkoxy group, a halogen atom, a cyano group, a nitro group,
An alkylsulfamoyl group having 1 to 25 carbon atoms which may have a substituent, a phenylazo group which may have a substituent, a pyridinoazo group which may have a substituent, and an ester group having 2 to 26 carbon atoms A carbamoyl group having 2 to 26 carbon atoms, an acyl group having 2 to 26 carbon atoms, an acylamino group having 1 to 25 carbon atoms, a sulfonamide group having 1 to 25 carbon atoms, a hydroxyl group, and the like.

The Z is not particularly limited as long as it is a group having an active hydrogen. Preferred examples include a hydroxy group, a carboxyl group and a sulfonic acid group.

The metal that forms a complex compound with the azo compound is not particularly limited as long as it is a metal that forms a complex compound with the azo compound. Nickel, cobalt, iron, ruthenium, rhodium, palladium, Transition metals such as copper, osmium, iridium and platinum are preferred.

Among the azo compound metal complexes used in the present invention, particularly preferred specific examples include the following azo compound metal complexes.

[0112]

Embedded image In the above formula (a), a complex of the following metal having a substituent and the following metal.

[0113]

[Table 7]

[0114]

Embedded image In the above formula (b), a complex of the following compound having a substituent and the following metal.

[0115]

[Table 8]

When it is required to improve the durability of the recording layer of the present invention, additives such as a quencher and an ultraviolet absorber may be mixed. It is also possible to introduce a functional group exhibiting such an effect into the compound of the formula (I) as a substituent and use it. Examples of the additive include those represented by the following general formulas (1) to (5).

[0117]

Embedded image

In these formulas, G and G 'are benzene
Ring or substituted benzene ring, or
Atoms forming a ring or substituted naphthalene ring,
They may be the same or different, and these rings
Represents a halogen atom, an alkyl group, an alkoxy group,
Si group, carboxyl group, allyl group, alkyl carboxy
Group, alkylalkoxyl group, aralkyl group, alk
Sulfonate group bonded to carbonyl group and metal ion
Alkyl, nitro, amino, alkylamino,
Substituted with a substituent such as phenyl or phenylethylene
May be. R ₁₆~ R₂₈Is a halogen atom, substituted or
Unsubstituted alkyl, alkoxy, hydroxy,
Ruboxyl group, allyl group, alkylcarboxyl group,
Alkylalkoxyl group, aralkyl group, alkylcarbo
Nyl group, sulfonate alkyl bonded to metal ion
Group, nitro group, amino group, alkylamino group, phenyl
And a phenylethylene group. Q is Ni, Co,
Represents a transition metal such as Mn, Cu, Pd and Pt;
It may have a load and take a salt structure with a cation. a 'is a
It represents the number of charges in the ON-form and is a positive integer including 0. d is
A ′ = b ′ × c ′, where a ′ = 0
When b ′ × c ′ = 0, d does not exist and the compound is non-ionic
Sex.

The recording layer containing these dyes is formed on a substrate by a coating method such as a spin coating method or a casting method, a sputtering method, a chemical vapor deposition method, a vacuum vapor deposition method or the like.
nm, preferably 100-150 nm. In particular, in the coating method, a coating solvent in which a dye is dissolved or dispersed is used. In this case, it is preferable to select a solvent that does not damage the substrate. For example, alcohol solvents such as methanol, aliphatic hydrocarbon solvents such as hexane and octane, cyclic hydrocarbon solvents such as cyclohexane, aromatic hydrocarbon solvents such as benzene, halogenated hydrocarbon solvents such as chloroform, One or a mixture of ether solvents such as dioxane, cellosolve solvents such as methyl cellosolve, ketone solvents such as acetone, and ester solvents such as ethyl acetate is used. The recording layer may be formed not only of one layer but also of a plurality of dyes in a multilayer, or the dyes may be dispersed in a polymer thin film or the like, for example, preferably at about 50% or more. When a solvent that does not damage the substrate cannot be selected, a sputtering method, a chemical vapor deposition method, a vacuum vapor deposition method, or the like is effective.

Next, on the recording layer, a thickness of 50 to 300 n
m, preferably a reflective layer having a thickness of 100 to 150 nm. As a material of the reflection layer, one having a sufficiently high reflectance at the wavelength of the reproduction light, for example, Au, Al, Cu, Ti, Cr,
The metals Ni, Pt, Ta and Pd can be used alone or as an alloy. Among them, Au and Al have high reflectivity and high reflectivity and are suitable as a material for the reflective layer. In addition, the following may be included. For example, Mg, Se, Hf, V, Nb, RuW, Mn, R
e, Fe, Co, Rh, Ir, Cu, Zn, Cd, G
a, In, Si, Ge, Te, Pb, Po, Sn, Bi
And metal and semimetal. Further, those containing Au as a main component are preferable because a reflection layer having high reflectance can be easily obtained. Here, the main component means a component having a content of 50% or more. It is also possible to form a multilayer film by alternately stacking low-refractive-index thin films and high-refractive-index thin films with a material other than a metal and use it as a reflective layer.

As a method of forming the reflection layer, for example,
Examples include a sputtering method, a chemical vapor deposition method, and a vacuum vapor deposition method.
In addition, a reflection amplification layer and an adhesive layer may be provided between the recording layer and the reflection layer in order to increase the reflectance and improve the adhesion.

The optical recording medium of the present invention thus obtained is a medium having a recording layer and a reflective layer formed on a substrate.
The reflectance from the substrate side to light having a wavelength selected from the range of 620 to 690 nm, preferably 630 to 690 nm is 15% or more, preferably 20% or more, and more preferably 40% or more. Further, the reflectance from the substrate side to light having a wavelength selected from the range of 770 to 830 nm is 65%.
As described above, it is preferably 70% or more, which satisfies the reflectance of the Red Book (CD) standard and the Orange Book (CD-R) standard. If these standards are satisfied, it is possible to satisfactorily reproduce even a commercially available CD player.

Further, in the optical recording medium of the present invention, a protective layer can be formed on the reflective layer. The material of the protective layer is not particularly limited as long as it protects the reflective layer from external force. Examples of the organic substance include a thermoplastic resin, a thermosetting resin, and a UV-curable resin. Among them, a UV-curable resin is preferable. Examples of the inorganic substance include SiO ₂ , SiN ₄ , MgF ₂ , and SnO ₂ . A protective layer can be formed by dissolving a thermoplastic resin, a thermosetting resin, or the like in an appropriate solvent to form a coating solution, applying the coating solution, and drying. The UV-curable resin can be used as it is or after dissolving in a suitable solvent to prepare a coating solution, and then applying the coating solution and irradiating with UV light to cure it, thereby forming a protective layer. As the UV-curable resin, for example, acrylate resins such as urethane acrylate, epoxy acrylate, and polyester acrylate can be used. These materials may be used alone or as a mixture, and may be used not only as a single layer but also as a multilayer film.

As a method of forming the protective layer, a coating method such as a spin coating method or a casting method, a sputtering method or a chemical vapor deposition method is used as in the case of the recording layer. Is preferred.

The optical recording medium of the present invention has a wavelength of 620 to 69.
At least reproduction is possible with a red laser of 0 nm, and reproduction or recording / reproduction is possible. Furthermore, 770-
At least reproduction is possible with near infrared laser selected from 830 nm, and reproduction or recording / reproduction is possible. As the red laser, any laser having a wavelength of 620 to 690 nm may be used. For example, a dye laser capable of selecting a wavelength in a wide range of the visible region, a helium neon laser having a wavelength of 633 nm, and a recently developed wavelength of 635 n
Although there are high-power semiconductor lasers of m and 680 nm, a semiconductor laser is preferable in consideration of mounting on a device. Further, as a near infrared laser, 770 to 830 n
Any laser having a wavelength of m may be used, and a semiconductor laser used in a commercially available CD player or CD recorder is suitable.

[0126]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to the examples.

Example 1 Synthesis of 3,6-bis (3-methoxypropan-2-yloxy) phthalonitrile In a nitrogen stream, 3,6 bis (3-methoxypropan-2-yloxy) phthalonitrile was added to 100 mL of dimethylacetamide.
-Dihydroxyphthalonitrile (8.0 g) was dissolved, potassium carbonate (27.6 g) was added, and the temperature was raised to 60 ° C. To this solution was added methanesulfonic acid- (3-methoxypropane-2).
-Yl) ester at an internal temperature of 60 to 70 ° C.
The mixture was added dropwise over a period of minutes, and then stirred at 75 to 80 ° C for 20 hours. After cooling, the reaction solution was discharged into 1000 mL of water, and extracted with 1000 mL of toluene. Separate the toluene layer,
After washing with water and filtration, the solvent was distilled off. An 80% aqueous IPA solution was added to the residue, and the precipitated crystals were collected by filtration and dried to obtain 5.9 g of white crystals. The melting point of the obtained compound is 90.2-9.
1.7 ° C. It was confirmed to be the target substance from the following analysis results. FIG. 2 shows the IR spectrum of the obtained compound.

[0128]

[Table 9] MS (m / e): 304 (M ⁺ )

Example 2 4,5-Dichloro-3,6-
Synthesis of bis (3-methoxypropan-2-yloxy) phthalonitrile 4,5 to 500 mL of dimethylacetamide under a nitrogen stream
-Dichloro-3,6-dihydroxyphthalonitrile 5
7.3 g was dissolved, 138.2 g of potassium carbonate was added, and the temperature was raised to 60 ° C. To this solution was added p-toluenesulfonic acid- (3-methoxypropan-2-yl) ester 13
4.4 g was added dropwise at an internal temperature of 60 to 70 ° C over 25 minutes, followed by stirring at 75 to 80 ° C for 27 hours. After cooling,
The reaction solution was discharged into 3000 mL of water, and toluene 1000 m
L. The toluene layer was separated, washed with water, filtered, and the solvent was distilled off. The residue was powdered by adding 400 mL of n-hexane, collected by filtration and dried to obtain 32.7 g of a white powder.
The melting point of the obtained compound was 105.8 to 106.3 ° C. It was confirmed to be the target substance from the following analysis results.
FIG. 3 shows the IR spectrum of the obtained compound.

[0130]

[Table 10] MS (m / e): 373 (M ⁺ )

Example 3 Synthesis of 3,6-bis (2,2-dimethyl-1,3-dioxolan-4-ylmethoxy) phthalonitrile Under a nitrogen stream, 3,6-bis (2,2-dimethyl-1,3-dioxolan-4-ylmethoxy) phthalonitrile was added to 50 mL of dimethylacetamide in a nitrogen stream.
10.0 g of dihydroxyphthalonitrile, 21.6 g of potassium carbonate and p-toluenesulfonic acid- (2,2-
48.2 g of dimethyl-1,3-dioxolan-4-yl) methyl ester was added, and the mixture was stirred at 70 to 75 ° C. for 25 hours. After cooling, the reaction solution was discharged into 300 mL of water, and the precipitate was collected by filtration, washed with water, washed successively with 100 mL of toluene and 100 mL of an 80% aqueous isopropyl alcohol solution, and dried to obtain 16.3 g of white crystals. The melting point of the obtained compound was 173 to 174.5 ° C. It was confirmed to be the target substance from the following analysis results. FIG. 4 shows the IR spectrum of the obtained compound.

[0132]

[Table 11] MS (m / e): 388 (M ^<+> )

Example 4 4,5-Dichloro-3,6-
Bis (2,2-dimethyl-1,3-dioxolan-4-
Synthesis of ylmethoxy) phthalonitrile In a nitrogen stream, 4,5
-Dichloro-3,6-dihydroxyphthalonitrile 5
0.0 g, 75.4 g of potassium carbonate and 163.4 g of p-toluenesulfonic acid- (2,2-dimethyl-1,3-dioxolan-4-yl) methyl ester were added to give 8
Stirred at 0-85 ° C for 25 hours. After cooling, add 5%
NaOH aqueous solution is discharged to 1000 mL, and toluene 800
Extracted in mL. The toluene layer is separated, washed with water, filtered,
The solvent was distilled off. The residue was purified by column chromatography (silica gel / (ethanol: toluene = 2: 100)) to obtain 31.9 g of white crystals. The melting point of the obtained compound was 115 to 123.5 ° C.

From the following analysis results, the product was confirmed to be the target product. FIG. 5 shows the IR spectrum of the obtained compound.

[0135]

[Table 12] MS (m / e): 457 (M ⁺ )

Example 5 4,5-dimethylthio-3,
6-bis (2,2-dimethyl-1,3-dioxolane-
Synthesis of 4-ylmethoxy) phthalonitrile 4,80-dichloro-
3,6-bis (2,2-dimethyl-1,3-dioxolan-4-ylmethoxy) phthalonitrile 8.0 g, 15
20% to 25 ° C.
For 1 hour. The reaction solution was prepared as a 20% saline 1000m
The mixture was discharged to L and extracted with 300 mL of toluene. The toluene layer was separated, washed with water, filtered, and the solvent was distilled off. The residue was subjected to column chromatography (silica gel / (ethanol:
(Toluene = 1: 100)) and purified by 8.1 g of white crystals.
I got The melting point of the obtained compound is 74.5-79.5 ° C.
Met. It was confirmed to be the target substance from the following analysis results. FIG. 6 shows the IR spectrum of the obtained compound.

[0137]

[Table 13] MS (m / e): 480 (M ⁺ )

Example 6 4,5-Dichloro-3- (4
-Methylpentan-2-yloxy) -6- (2,2-
Dimethyl-1,3-dioxolan-4-ylmethoxy)
Synthesis of phthalonitrile In a nitrogen stream, 4,5-
10.0 g of dichloro-3- (4-methylpentan-2-yloxy) -6-hydroxyphthalonitrile and 5.3 g of potassium carbonate were added, and the temperature was raised to 70 ° C. To this solution was added p-toluenesulfonic acid- (2,2-dimethyl-
1,3-dioxolan-4-yl) methyl ester 11
g was added and stirred at 70-80 ° C for 150 hours. After cooling, the reaction solution was discharged into 300 mL of water, and 300 m
L. The toluene layer was separated, washed with water, filtered, and the solvent was distilled off. The residue was purified by column chromatography (silica gel / toluene) to obtain 9.0 g of a pale yellow oil. It was confirmed to be the target substance from the following analysis results.
FIG. 7 shows the IR spectrum of the obtained compound.

[0139]

[Table 14] MS (m / e): 427 (M ^<+> )

Example 7 Synthesis of phthalocyanine compound 19.5 g of 3,6-bis (3-methoxypropan-2-yloxy) phthalonitrile, palladium (II) chloride
After mixing 4.3 g, 14.3 g of DBU and 175 mL of n-octyl alcohol, the mixture was stirred at 180 to 185 ° C for 22 hours. After cooling, n-octyl alcohol was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel / (methanol: toluene = 5: 100)) to obtain 7.4 g of a green powder of a phthalocyanine compound represented by the following structural formula (I-1).

[0141]

Embedded image

From the results of the following analysis, it was confirmed that the target compound was obtained. In addition, in this example and the following examples, the atomic absorption method was used to confirm metals.

[0143]

[Table 15] The compound thus obtained shows a maximum absorption at 724 nm in a toluene solution, and the gram extinction coefficient is 1.
It was 35 × 10 ⁵ mL / g · cm.

Example 8 Synthesis of Phthalocyanine Compound 7.2 g of 4,5-dichloro-3,6-bis (3-methoxypropan-2-yloxy) phthalonitrile, 1.3 g of palladium (II) chloride, DBU4. After mixing 3 g and 50 mL of n-pentyl alcohol, 135 to 138 ° C.
For 18 hours. After cooling, n-pentyl alcohol was distilled off under reduced pressure. The residue was subjected to column chromatography (silica gel / (methanol: toluene = 5: 10)
0)) and 2.3 g of green powder of the following structural formula (I)
A phthalocyanine compound represented by -2) was obtained.

[0145]

Embedded image It was confirmed to be the target substance from the following analysis results.

[0146]

[Table 16]

The compound thus obtained exhibited a maximum absorption at 729 nm in a toluene solution, and had a gram extinction coefficient of 1.14 × 10 ⁵ mL / g · cm.

Example 9 Synthesis of phthalocyanine compound 7.0 g of 3,6-bis (2,2-dimethyl-1,3-dioxolan-4-ylmethoxy) phthalonitrile, 0.8 g of palladium (II) chloride, DBU4 After mixing 1 g and 35 mL of n-pentyl alcohol, 135 to 138
Stirred at C for 21 hours. After cooling, n-pentyl alcohol was distilled off under reduced pressure. The residue was subjected to column chromatography (silica gel / (ethanol: toluene = 2: 10
0)), and 1.9 g of green powder represented by the following structural formula (I)
A phthalocyanine compound represented by -3) was obtained.

[0149]

Embedded image

From the following analysis results, the product was confirmed to be the target product. FIG. 8 shows the IR spectrum of the obtained compound.

[0151]

[Table 17]

The compound thus obtained exhibited a maximum absorption at 720 nm in a toluene solution, and had a gram extinction coefficient of 1.28 × 10 ⁵ mL / g · cm.

Example 10 Synthesis of phthalocyanine compound 4,5-dichloro-3,6-bis (2,2-dimethyl-
9.0 g of 1,3-dioxolan-4-ylmethoxy) phthalonitrile, 1.1 g of palladium (II) chloride, DBU
After mixing 3.0 g and 35 mL of n-pentyl alcohol, the mixture was stirred at 135 to 138 ° C. for 1.5 hours. After cooling, n-pentyl alcohol was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel / (dioxane: toluene = 2: 100)) to obtain 2.4 g of a green powder of a phthalocyanine compound represented by the following structural formula (I-4).

[0154]

Embedded image

From the results of the following analysis, the product was confirmed to be the target compound. FIG. 9 shows the IR spectrum of the obtained compound.

[0156]

[Table 18]

The compound thus obtained exhibited a maximum absorption at 719 nm in a toluene solution, and had a gram extinction coefficient of 1.19 × 10 ⁵ mL / g · cm.

Example 11 Synthesis of phthalocyanine compound 7.8 g of 4,5-dimethylthio-3,6-bis (2,2-dimethyl-1,3-dioxolan-4-ylmethoxy) phthalonitrile, palladium chloride (II) ) 0.9 g, D
After mixing BU2.5g and n-pentyl alcohol 40mL, it stirred at 135-138 degreeC for 15 hours. After cooling, n-pentyl alcohol was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel / (dioxane: toluene = 4: 100)) to obtain 3.0 g of a green powder of a phthalocyanine compound represented by the following structural formula (I-5).

[0159]

Embedded image

From the following analysis results, the product was confirmed to be the target product. FIG. 10 shows the IR spectrum of the obtained compound.

[0161]

[Table 19]

The compound thus obtained showed a maximum absorption at 746 nm in a toluene solution, and had a gram extinction coefficient of 1.04 × 10 ⁵ mL / g · cm.

Example 12 Synthesis of phthalocyanine 5,6-dichloro-4- (4-methylpentan-2-yloxy) -7- (2,2-dimethyl-1,3-dioxolan-4-ylmethoxy) phthalo 2.1 g of nitrile,
0.3 g of palladium (II) chloride, 0.8 g of DBU, n-
After mixing 20 mL of pentyl alcohol, 135-1
The mixture was stirred at 38 ° C for 28 hours. After cooling, n-pentyl alcohol was distilled off under reduced pressure. The residue was subjected to column chromatography (silica gel / (ethyl acetate: toluene = 5: 9
5), and 0.8 g of green powder represented by the following structural formula (I-
A phthalocyanine compound represented by 6) and its isomer were obtained.

[0164]

Embedded image It was confirmed to be the target substance from the following analysis results.

[0165]

[Table 20]

The compound thus obtained showed a maximum absorption at 719 nm in a toluene solution, and the gram extinction coefficient was 9.53 × 10 ⁴ mL / g · cm.

Example 13 Among the phthalocyanine compounds represented by the general formula (I), a 2,2,3,3-tetrafluoropropanol solution of the phthalocyanine compound represented by the structural formula (I-3) (10 g / L) ) Was prepared.

As the substrate, a disc-shaped substrate (made of polycarbonate resin) having a continuous guide groove (track pitch: 1.6 μm) and a diameter of 120 mmφ and a thickness of 1.2 mm was used.
Using. On this substrate, the dye solution is rotated at 1000 rpm.
m, and dried at 70 ° C. for 2 hours to form a recording layer. Au is sputtered on this recording layer using a sputtering apparatus (CDI-900) manufactured by Balzers Co., Ltd.
A reflective layer having a thickness of 100 nm was formed. The sputtering was performed at a sputtering gas pressure of 1.0 × 10 ⁻² Torr.

Further, an ultraviolet curable resin SD is provided on the reflective layer.
-17 (manufactured by Dainippon Ink and Chemicals, Inc.), spin-coated, and irradiated with ultraviolet light to form a protective layer having a thickness of 6 μm.
-R medium was produced.

The medium has a reflectance of 71% (775-79).
0 nm), and an EFM signal could be written with a power of 5.5 mW at a linear velocity of 1.3 m / s using a 780 nm semiconductor laser, and the error rate at that time was less than 10.

Example 14 Among the phthalocyanine compounds represented by the general formula (I), 0.2 g of the phthalocyanine compound represented by the structural formula (I-4) and a metal complex (a-1) of an azo compound (0.2 g) were added. 02 g was dissolved in 2,2,3,3-tetrafluoropropanol (10 mL) to prepare a dye solution.

As the substrate, a disc-shaped substrate (made of polycarbonate resin) having a continuous guide groove (track pitch: 1.6 μm) and a diameter of 120 mmφ and a thickness of 1.2 mm was used.
Using.

The dye solution was placed on the substrate at a rotational speed of 1500.
Spin coating was performed at rpm and dried at 70 ° C. for 2 hours to form a recording layer. Au was sputtered on this recording layer using a sputtering apparatus (CDI-900, manufactured by Balzers) to form a reflective layer having a thickness of 100 nm. The sputtering was performed at a sputtering gas pressure of 1.0 × 10 ⁻² Torr.

Further, an ultraviolet curable resin SD is provided on the reflective layer.
After spin coating with -17 (manufactured by Dainippon Ink and Chemicals, Inc.), the layer was irradiated with ultraviolet rays to form a 6 μm thick protective layer. Using a Philips writer (CD-521) equipped with a 780 nm semiconductor laser head, this optical recording medium was subjected to FEM at a linear velocity of 2.8 m / s and a laser power of 8 mW.
The signal was recorded. After recording, a commercially available CD player (YAM
AHA CDX-1050, laser wavelength 786nm)
The signal was reproduced by using, and the reflectance, the error rate, and the modulation were measured. All showed good values satisfying the Orange Book standard. Next, the recorded medium is set at 680 nm.
And optical disc evaluation device (DDU-100) manufactured by Pulstic Industrial equipped with a 635 nm red semiconductor laser head.
The signal was reproduced using 0), and the reflectance, the error rate, and the modulation were measured. All exhibited good values.

Next, this medium was used as an optical disk evaluation device (DDU-1000) manufactured by Pulstic Industrial and equipped with a 680 nm red semiconductor laser head, and an EF manufactured by KENWOOD.
Recording was performed at a linear velocity of 5.6 m / s and a laser power of 10 mW using an M encoder. After recording, 680 nm and 6
The signal was reproduced using an evaluation device equipped with a 35 nm red semiconductor laser head, and the reflectance, the error rate, and the modulation were measured. All exhibited good values. This recorded medium is used as a commercially available CD player (YAMAHACDX-
1050, laser wavelength 786 nm)
A signal recorded by an 80 nm drive (DDU-1000) was reproduced, and the reflectance, the error rate, and the modulation were measured. All were good values satisfying the Orange Book standard.

As described above, this medium was able to perform recording and reproduction favorably with a plurality of laser wavelengths.

The error rate was measured using a Kenwood CD decoder (DR3552), and the modulation was determined by the following equation. Modulation degree = {(maximum signal strength)-(minimum signal strength)}
/ (Maximum signal strength)

[Examples 15 to 24] Optical recording media were produced in the same manner as in Example 14, except that a phthalocyanine compound and a metal complex of an azo compound were used in combination.

The prepared medium was converted to 780 in the same manner as in Example 14.
Philips writer equipped with a 6.8 nm semiconductor laser head and an optical disc evaluation device (DDU-1) manufactured by Pulstic Industrial equipped with a 680 nm red semiconductor laser head.
000) and KENWOOD EFM encoder. After recording, the same measurement as in Example 16 was performed. As a result, good recording characteristics were shown.

Tables 2 and 3 show the reflectance, error rate, and modulation factor at the time of reproduction at 786, 680, and 635 nm in each of the cases where the above media were recorded at 780 and 680 nm.
Are shown together.

Comparative Example 1 An optical recording medium was produced in the same manner as in Example 14, except that only the metal complex (a-1) of an azo compound was used in the recording layer.

The prepared medium was converted to 780 in the same manner as in Example 14.
Philips writer equipped with a 6.8 nm semiconductor laser head and an optical disc evaluation device (DDU-1) manufactured by Pulstic Industrial equipped with a 680 nm red semiconductor laser head.
000) and KENWOOD EFM encoder, but recording was not possible at 780 nm, and the sensitivity was low at 680 nm, making it impossible to record clearly.

Comparative Example 2 The procedure of Example 14 was repeated, except that an n-octane solution of a phthalocyanine compound having the following structure disclosed in Example 98 of US Pat. No. 5,124,067 was used for the recording layer. An optical recording medium was manufactured.

[0184]

Embedded image

The prepared medium was used in the same manner as in Example 16 to obtain a 780
Philips writer equipped with a 6.8 nm semiconductor laser head and an optical disc evaluation device (DDU-1) manufactured by Pulstic Industrial equipped with a 680 nm red semiconductor laser head.
000) and KENWOOD EFM encoder. After recording, the same measurement as in Example 16 was performed. As a result, the waveform was distorted, and the reflectance at 635 and 680 nm was low.

Table 2 summarizes the reflectance, error rate, and degree of modulation at the time of reproduction at 786, 680, and 635 nm in each of the cases where the above media were recorded at 780 and 680 nm.

[0187]

[Table 21]

[0188]

[Table 22]

[0189]

According to the present invention, reproduction or recording / reproduction can be performed with a laser beam having a wavelength selected from 620 to 690 nm, and furthermore, the Orange Book (770 to 830 nm), which is the standard for current CD-R media, is used. And a phthalocyanine compound suitably used for the optical recording medium which satisfies the condition that the reflectance with respect to the light having a wavelength selected from the above is not less than 65% and recording / reproducing is possible with the light.

[Brief description of the drawings]

FIG. 1 is a sectional structural view illustrating an embodiment of an optical recording medium of the present invention.

FIG. 2 is an infrared absorption spectrum of 3,6-bis (3-methoxypropan-2-yloxy) phthalonitrile synthesized in Example 1.

FIG. 3 shows 4,5-dichloro-3,6 synthesized in Example 2.
3 is an infrared absorption spectrum of -bis (3-methoxypropan-2-yloxy) phthalonitrile.

FIG. 4 is an infrared absorption spectrum of 3,6-bis (2,2-dimethyl-1,3-dioxolan-4-yloxy) phthalonitrile synthesized in Example 3.

FIG. 5 shows 4,5-dichloro-3,6 synthesized in Example 4.
-Bis (2,2-dimethyl-1,3-dioxolan-4
3 is an infrared absorption spectrum of-(yloxy) phthalonitrile.

FIG. 6 shows 4,5-dimethylthio-synthesized in Example 5.
3 is an infrared absorption spectrum of 3,6-bis (2,2-dimethyl-1,3-dioxolan-4-yloxy) phthalonitrile.

FIG. 7 shows 4,5-dichloro-3-synthesized in Example 6.
(4-methylpentan-2-yloxy) -6- (2,
It is an infrared absorption spectrum of 2-dimethyl-1,3-dioxolan-4-yloxy) phthalonitrile.

FIG. 8 is an infrared absorption spectrum of the phthalocyanine compound synthesized in Example 9.

FIG. 9 is an infrared absorption spectrum of the phthalocyanine compound synthesized in Example 10.

FIG. 10 is an infrared absorption spectrum of the phthalocyanine compound synthesized in Example 11.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C07D 487/22 C09B 47/20 C09B 47/20 8721-5D G11B 7/24 G11B 7/24 8721- 5D 516 516 B41M 5/26 Y (72) Inventor Nobuaki Sasaki 1-43, Yugecho Minami, Yao City, Osaka Prefecture Inside Yamamoto Kasei Co., Ltd. (72) Inventor Shigeo Fujita 1-43, Yugecho Minami, Yao City, Osaka Prefecture Yamamoto Chemicals In-house (72) Inventor Yojiro Kumagai 1-443 Minami Yuge-cho, Yao-shi, Osaka Yamamoto Kasei Co., Ltd. (72) Inventor Denmi Misawa 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Prefecture Mitsui Toatsu Chemical Co., Ltd. (72 Inventor Keisuke Takuma 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals Co., Ltd.

Claims (14)

[Claims] 1. A phthalocyanine compound represented by the general formula (I). Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are an alkyl group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group, or a substituent represented by the following general formula (II)) X represents a hydrogen atom, a halogen atom or an alkylthio group, M represents two hydrogen atoms, a divalent metal or a trivalent or tetravalent metal derivative, provided that a combination of R ₁ and R ₂ , In the combination of R ₃ and R _4, the combination of R ₅ and R ₆ , and the combination of R ₇ and R ₈ , when both are alkyl groups, one is an alkyl group and the other is an alkoxyalkyl group, (Excluding the case where the other is an alkoxyalkoxyalkyl group in the alkyl group.) (Wherein A represents an alkylene group, ring B represents an oxygen atom 1 to
A heterocyclic group having four is shown. ) 2. The method of claim ₁ , wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ ,
R ₈ is an alkyl group having 1 to 15 carbon atoms, a total of 2 to 15 carbon atoms
The phthalocyanine compound according to claim 1, wherein X is a hydrogen atom, a halogen atom or an alkylthio group having 1 to 10 carbon atoms, or an alkoxyalkyl group represented by the following formula (III): Embedded image (In the formula, A ′ represents an alkylene group having 1 to 4 carbon atoms, and ring B ′ represents a heterocyclic group having 3 to 10 carbon atoms and having 1 to 4 oxygen atoms.) 3. The substituent represented by the general formula (III) is
The phthalocyanine compound according to claim 2, which is a substituent having the following structural formula. Embedded image 4. A phthalonitrile compound represented by the general formula (IV). Embedded image (In the formula, R ₉ and R ₁₀ represent an alkyl group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group or a substituent represented by the following general formula (II), and X represents a hydrogen atom, a halogen atom or an alkylthio group. , R ₉ and R ₁₀
, Except when both are alkyl groups, when one is an alkyl group and the other is an alkoxyalkyl group, when one is an alkyl group and the other is an alkoxyalkoxyalkyl group. ) (Wherein A represents an alkylene group, ring B represents an oxygen atom 1 to
A heterocyclic group having four is shown. ) 5. The method for producing a phthalocyanine compound according to claim 1, wherein the phthalonitrile compound according to claim 4 is reacted with a metal or a metal derivative. 6. The method for producing a phthalonitrile compound according to claim 4, wherein the phthalonitrile compound represented by the general formula (V) and the mercapto compound represented by the general formula (VI) are reacted in the presence of a base. Method. Embedded image (In the formula, R _9, R ₁₀ represents an alkyl group, an alkoxyalkyl group, a substituent represented by alkoxyalkoxyalkyl group or the following general formula (II). However, both of R ₉ and R _{1 0} are simultaneously alkyl group Wherein, when one is an alkyl group and the other is an alkoxyalkyl group, this excludes the case where one is an alkyl group and the other is an alkoxyalkoxyalkyl group.) (Wherein A represents an alkylene group, ring B represents an oxygen atom 1 to
A heterocyclic group having four is shown. R ₁₁ -SH (VI) (wherein, R ₁₁ represents an alkyl group.) 7. A method comprising reacting a phthalonitrile compound represented by the general formula (VII) or (VIII) with a compound represented by the general formula (IX) in the presence of a base.
A method for producing a phthalonitrile compound according to claim 4. Embedded image (In the formula, X represents a hydrogen atom, a halogen atom or an alkylthio group.) (Wherein, X represents a hydrogen atom, a halogen atom or an alkylthio group, R ₁₂ represents an alkyl group, an alkoxyalkyl group,
Alkoxyalkoxyalkyl group or the following general formula (II)
Represents a substituent represented by ) (Wherein A represents an alkylene group, ring B represents an oxygen atom 1 to
A heterocyclic group having four is shown. R ₁₃ -D (IX) (wherein, R ₁₃ is the same as R _{12 in} formula (VIII), and D is a halogen atom, a tolyloxy group or a mesyloxy group, provided that R ₁₂ and R Both of ₁₃ are simultaneously alkyl groups, one is an alkyl group and the other is an alkoxyalkyl group, one is an alkyl group and the other is not an alkoxyalkoxyalkyl group.) 8. An optical recording medium having at least a recording layer and a reflective layer on a substrate, wherein the recording layer comprises
An optical recording medium comprising the phthalocyanine compound according to any one of claims 1 to 3. 9. The optical recording medium according to claim 8, wherein the recording layer contains a phthalocyanine compound represented by the general formula (I) and a compound having an absorption maximum at a wavelength of less than 630 nm. 10. The optical recording medium according to claim 9, wherein the compound having an absorption maximum at less than 630 nm is a metal complex of an azo compound. 11. The red laser having a wavelength of 620 to 690 nm has a reflectance of 15% or more measured from the substrate side with respect to light selected from a red laser having a wavelength of 620 to 690 nm, and is at least reproducible by a red laser having a wavelength of 620 to 690 nm. 11. The optical recording medium according to any one of 10). 12. The method according to claim 11, wherein a reflectance of light selected from a red laser having a wavelength of 620 to 690 nm measured from the substrate side is 15% or more, and recording / reproduction is possible with the red laser having a wavelength of 620 to 690 nm. Optical recording medium. 13. A near infrared laser with a wavelength of 770 to 830 nm has a reflectance measured from the substrate side of 65% or more for light selected from near infrared lasers, and is at least reproducible with a near infrared laser with a wavelength of 770 to 830 nm. The optical recording medium according to claim 11. 14. The optical recording medium according to claim 13, wherein recording and reproduction can be performed with a near-infrared laser having a wavelength of 770 to 830 nm.