JPH08225751A - New phthalocyanine compound, its production and optical recording medium using the same - Google Patents

Abstract

PURPOSE: To obtain the subject compound having excellent absorbing properties, solubility, light resistance and economical efficiency and useful for a near- infrared absorbing pigment, especially for an addition-type optical recording medium by position-selectively introducing a substituting group to a phthalocyanine skeleton. CONSTITUTION: The objective compound is obtained by reacting (A) a phthalonitrile compound of formula I (COOR is a carboxylic acid ester having a heterocycle; X is a halogen, etc.; m is an integer of 0-3; n is an integer of 0-4) with (B) a metallic compound and expressed by (C) the formula II in which 1-8 pieces of benzene nuclei in 16 substitutable positions in a phthalocyanine skeleton are substituted with phenoxy and the phenoxy is substituted with a carboxylic acid ester having more than one heterocycles (M is a metal, a metal oxide or a metal halide). The objective optical recording medium is obtained by adding the compound to a recording medium placed on a substrate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel phthalocyanine compound, a method for producing the same, and a near-infrared absorbing material having absorption in the near-infrared region, particularly to an optical recording medium. The novel phthalocyanine compound according to the present invention is 6
A near-infrared absorbing dye for writing or reading in an optical recording medium using a semiconductor laser, a liquid crystal display device, an optical character reader, etc., because it has absorption in the near-infrared region of 0 to 1000 nm and has excellent solubility Near-infrared sensitizer, thermal transfer, photothermal conversion agent such as thermal paper and thermal stencil, near-infrared absorption filter, eye fatigue preventive, near-infrared absorbing material used as photoconductive material, or used for imaging tube Excellent for use in color separation filters, liquid crystal display devices, color cathode ray tube selective absorption filters, color toners, inkjet inks, tampering prevention barcode inks, microbial inactivating agents, photosensitive dyes for tumor treatment, etc. Be effective. In particular, it is extremely effective as a near-infrared absorbing dye for use in a write-once type optical recording medium compatible with compact discs.

[0002]

2. Description of the Related Art In recent years, development of optical recording media such as compact discs, laser discs, optical memory discs and optical cards using a semiconductor laser as a light source has been active. In particular, CD, PHOTO-CD or CD-RO
M is used as a large-capacity, high-speed access digital recording medium for mass storage and reproduction of voice, image, code data and the like. All of these systems require so-called near-infrared absorbing dyes that are sensitive to semiconductor lasers, and those dyes having good characteristics are required.

Among them, many studies have been conducted on phthalocyanine compounds which are stable to light, heat, temperature and the like and have excellent fastness.

The characteristics required for use in a write-once type optical recording medium compatible with compact discs are: (1) The maximum absorption wavelength of the thin film is controlled to 700 to 730 nm. (There are few peaks due to association, which results in high absorbance and sharp peaks.) (2) A solvent that can be applied onto a substrate by a simple and highly productive method such as spin coating and that does not attack the substrate It has excellent solubility in.

(3) The reflectance is high.

(4) Good heat resistance and light resistance.

(5) High sensitivity.

(6) It is a compound excellent in economy in the production method and the like.

And the like.

For example, Japanese Patent Application Laid-Open No. 58-56892 discloses that
A method using a perfluorophthalocyanine compound has been proposed. However, these compounds have poor solubility in organic solvents and cannot be controlled to a satisfactory absorption wavelength.

JP-A-61-2192780, JP-A-61-61
-246091, JP-A-63-37991, JP-A-64-42283, JP-A-2-276677, JP-A-2-91360, JP-A-2-265788, JP-A-3-215466, JP-A-3-215466. No. 4-226390 proposes that a substituent is introduced into the benzene ring of the phthalocyanine skeleton through oxygen. However, these compounds have poor light resistance depending on the type, number and position of the substituents of the dye, have a low reflectance, and are not dissolved in a solvent that can be directly applied to a substrate such as commonly used polycarbonate such as polycarbonate. Or there is a problem in controlling the absorption wavelength.

As a solution to those drawbacks, Japanese Patent Application Laid-Open No. 5-1272 proposes a method in which four alkoxy groups are introduced at the α-position of phthalocyanine and a halogen compound or the like is partially introduced into the residue. Has been done. However, those having a substituent introduced at the α-position have problems in terms of economy, such as poor productivity from phthalonitrile as a raw material. Further, such a phthalocyanine compound does not necessarily have to satisfy all the properties, and thus further excellent properties are desired.

However, the phthalocyanine compounds proposed so far do not satisfy all the above characteristics.

[0014]

SUMMARY OF THE INVENTION The present invention has been made in consideration of the above circumstances of the prior art. That is, the object of the present invention is to enable absorption control according to the purpose in the absorption wavelength range of 600 to 1000 nm, and to have excellent solubility in a solvent suitable for the application, such as an alcohol solvent, and heat resistance, It is intended to provide a novel phthalocyanine compound having high light resistance.

Another object of the present invention is to provide a method for efficiently producing a phthalocyanine compound with high purity.

Still another object of the present invention is an optical recording medium,
In particular, it is to provide a phthalocyanine compound that exhibits excellent effects in solubility, absorption wavelength, sensitivity, reflectance, and light resistance, which are properties required for them when used as an optical recording medium for compact discs.

[0017]

Means for Solving the Problems The above-mentioned objects are as follows: 1 to 8 out of 16 substitutable positions of a benzene nucleus of a phthalocyanine skeleton are substituted with a phenoxy group, and the phenoxy group has at least one phenoxy group. And a novel phthalocyanine compound characterized by being substituted with a carboxylic acid ester group having a heterocycle represented by COOR.

The present invention also relates to the following general formula (1)

[0019]

[Chemical 4]

[Wherein, COOR represents a carboxylic acid ester group having a heterocycle, X represents a halogen atom,
It represents at least one selected from the group consisting of an alkyl group which may be substituted with a halogen atom, an alkoxy group and a carboxylic acid ester group, m represents an integer of 0 to 3, and n represents an integer of 0 to 4. M represents a metal, a metal oxide, or a metal halide. ] It is also achieved by the novel phthalocyanine compound represented by

The present invention also provides the following general formula (2):

[0022]

Embedded image

[Wherein, COOR represents a carboxylic acid ester group having a heterocycle, X represents a halogen atom,
It represents at least one selected from the group consisting of an alkyl group which may be substituted with a halogen atom, an alkoxy group and a carboxylic acid ester group, n represents an integer of 0 to 4, M represents a metal, a metal oxide or a halogen. Represents a metal oxide. ] It is also achieved by the novel phthalocyanine compound represented by

The present invention is further achieved by the above novel phthalocyanine compound in which the carboxylic acid ester group having a heterocycle is at the 2-position of the phenoxy group.

The present invention is further achieved by the above novel phthalocyanine compound in which the hetero ring is a carboxylic acid ester group having an oxygen atom.

The present invention is also achieved by the above novel phthalocyanine compound in which one of Xs in the general formula (1) is at the 6-position of the phenoxy group.

The present invention further provides the novel phthalocyanine represented by the general formula (1), wherein one of X is an alkyl group having 1 to 4 carbon atoms, which may be substituted with a halogen atom, an alkoxy group or a carboxylic acid ester group. It is also achieved by compounds.

The above objects are to provide a phthalonitrile compound substituted with a phenoxy group which is substituted with one or more carboxylic acid ester groups having a heterocycle represented by COOR, or a phthalonitrile which is not substituted with the phenoxy group. It is also achieved by the method for producing a novel phthalocyanine compound, which comprises reacting a mixture of the above with a metal compound.

The present invention also provides the following general formula (3):

[0030]

[Chemical 6]

[Wherein, COOR represents a carboxylic acid ester group having a heterocycle, X represents a halogen atom,
It represents at least one selected from the group consisting of an alkyl group which may be substituted with a halogen atom, an alkoxy group and a carboxylic acid ester group, m represents an integer of 0 to 3, and n represents an integer of 0 to 4. Represent ] It is also achieved by the above-mentioned method for producing a novel phthalocyanine compound, which comprises reacting a phthalonitrile compound and a metal compound.

The above objects can also be achieved by an optical recording medium containing the novel phthalocyanine compound in a recording layer provided on a substrate.

The present invention also provides a write-once type optical recording medium for a compact disc, which has a recording layer and a metallic reflecting layer provided on a transparent resin substrate, wherein the recording layer is the above-mentioned recording layer. It is also achieved by the medium.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION The phthalocyanine compound according to the present invention has 1 to 8 of the 16 substitutable positions of the benzene nucleus of the phthalocyanine skeleton substituted with a phenoxy group, and the phenoxy group has one phenoxy group. It is a novel phthalocyanine compound characterized by being substituted with a carboxylic acid ester group having a heterocycle represented by COOR. Here, the carboxylic acid ester group having a heterocycle represented by COOR is a group having a heterocycle unit in the ester portion. The heterocycle may be directly bonded to the carboxylic acid or may be bonded via an alkylene group. The thermal decomposition temperature is lower in the case of interposing an alkylene group. Examples of the hetero atom in the hetero ring include oxygen, nitrogen, sulfur, selenium, tellurium and the like. Of these, oxygen or nitrogen is preferable, and oxygen is particularly preferable. Also,
The heterocycle is preferably between 4 and 8 membered rings, especially 5 to 6 membered rings. Specifically, tetrahydrofurfuryloxycarbonyl group, pyranoxycarbonyl group, piperidinooxycarbonyl group, piperidinoethoxycarbonyl group, tetrahydropyrroleoxycarbonyl group, tetrahydropyranmethoxycarbonyl group, tetrahydrothiopheneoxycarbonyl group, cyclohexyloxy A carbonyl group and the like are shown. Preferred among these novel phthalocyanine compounds are those represented by the above general formula (1), which will be described in detail below.

First, in the general formula (1) as well, COOR
With regard to the above, it has already been described above.

Next, in the general formula (1), M is a metal,
It is a metal oxide or a metal halide. Specific examples of the central metal of the phthalocyanine compound represented by M include iron,
Magnesium, nickel, cobalt, copper, palladium,
Zinc, aluminum chloride, indium chloride, germanium chloride, tin chloride, silicon chloride, titanyl, vanadyl and the like, in terms of good light resistance, cobalt, copper, zinc, tin chloride or vanadyl is preferable, and vanadyl is particularly preferable. preferable.

Further, in the general formula (1), the substituent on the phenoxy group represented by X represents a halogen atom, an alkyl group which may be substituted with a halogen atom, an alkoxy group or a carboxylic acid ester group.

Here, the halogen atom is fluorine, chlorine, bromine and iodine, of which fluorine or chlorine is preferable, and fluorine is particularly preferable.

The alkyl group which may be substituted with a halogen atom is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms and these alkyl groups. Is a halogenated alkyl group substituted with a halogen atom. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, tert-butyl group, n-penter group, n
-Hexyl group, cyclohexyl group, n-octyl group, 2
-Ethylhexyl group, n-decyl group, lauryl group, stearyl group, methyl chloride group, methyl bromide group, ethyl chloride group, ethyl bromide group and the like are shown.

The alkoxy group is a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 8 carbon atoms. Specifically, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-octyl group. An oxy group, a 2-ethylhexyloxy group, an n-decyloxy group and the like are shown.

The carboxylic acid ester group is an alkyl ester having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, which may contain a hetero atom in the ester portion, or 3 to 8, preferably 5 carbon atoms, which may contain a hetero atom. 8 represents a cyclic alkyl ester of Further, the carboxylic acid ester group is C
It may be the same as the carboxylic acid ester group containing a heterocycle represented by OOR. Specifically, methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, methoxyethoxycarbonyl group. , Ethoxyethoxycarbonyl group, butoxyethoxycarbonyl group, diethylaminoethoxycarbonyl group, methylthioethoxycarbonyl group, methoxypropyloxycarbonyl group, (3,6,6
9-oxa) decyloxycarbonyl group, tetrahydrofurfuryloxycarbonyl group, pyranoxycarbonyl group, piperidinooxycarbonyl group, piperidinoethoxycarbonyl group, tetrahydropyrroleoxycarbonyl group, tetrahydropyranmethoxycarbonyl group, tetrahydrothiophenoxy A carbonyl group, a cyclohexyloxycarbonyl group and the like are shown.

The substitution position of X on the phenoxy group is not particularly limited, but it is more preferable that one of them is at the 6-position of the phenoxy group.

Furthermore, in the general formula (1), m is an integer of 0 to 3, preferably 3, and n is an integer of 0 to 4, preferably 1 to 2.

Specific examples of the phthalocyanine compound used in the present invention include the following compounds.

General formula (4)

[0046]

[Chemical 7]

In the above, A is a compound (M: VO) represented by the following formula: Compound 1: tetrakis (2- (2-tetrahydrofurfuryloxy) carbonylphenoxy) dodecafluorovanadyl phthalocyanine,

[0048]

Embedded image

Similarly, in the general formula (4), A is a compound represented by the following formula: Compound 2: tetrakis (2- (2-tetrahydrofurfuryloxy) carbonyl-6-methylphenoxy) dodecafluorovanadyl Phthalocyanine,

[0050]

[Chemical 9]

Compound 3: Tetrakis (2- (2-tetrahydrofurfuryloxy) carbonyl-6-ethylphenoxy) dodecafluorozinc phthalocyanine,

[0052]

[Chemical 10]

Compound 4: tetrakis (4- (2-tetrahydrofurfuryloxy) carbonylphenoxy) dodecafluoro (dichlorotin) phthalocyanine,

[0054]

[Chemical 11]

Compound 5: tetrakis (2- (2-tetrahydrofurfuryloxy) carbonyl-6-ethoxyphenoxy) dodecafluorovanadyl phthalocyanine,

[0056]

[Chemical 12]

Compound 6: tetrakis (2- (2-tetrahydrofurfuryloxy) carbonyl-6-tertbutylphenoxy) dodecafluorovanadyl phthalocyanine,

[0058]

[Chemical 13]

Compound 7: Tetrakis (2,3,5,6-
Tetrafluoro-4- (2-tetrahydrofurfuryloxy) carbonylphenoxy) dodecafluorozinc phthalocyanine,

[0060]

Embedded image

Compound 8: tetrakis (2- (2-tetrahydrofurfuryloxy) carbonyl-4,6-dimethylphenoxy) dodecafluorotitanyl phthalocyanine,

[0062]

[Chemical 15]

Compound 9: tetrakis (2- (2-tetrahydrofurfuryloxy) carbonyl-4-methyl-6
-Methoxyphenoxy) dodecafluorovanadyl phthalocyanine,

[0064]

Embedded image

Compound 10: tetrakis (2- (2-tetrahydrofurfuryloxy) carbonyl-4-methoxy-6-chlorophenoxy) dodecafluoro (dichlorotin) phthalocyanine,

[0066]

[Chemical 17]

Compound 11: tetrakis (2- (2-tetrahydrofurfuryloxy) carbonyl-6-bromomethylphenoxy) dodecafluorovanadyl phthalocyanine,

[0068]

Embedded image

Compound 12: tetrakis (2- (2-tetrahydrofurfuryloxy) carbonyl-4,6-dibromomethylphenoxy) dodecafluorocopper phthalocyanine,

[0070]

[Chemical 19]

Compound 13: tetrakis (2,6-dimethoxy-4- (2-tetrahydrofurfuryloxy) carbonylphenoxy) dodecafluoropalladium phthalocyanine,

[0072]

Embedded image

Compound 14: tetrakis (2-propyloxy-5- (2-tetrahydrofurfuryloxy) carbonylphenoxy) dodecafluoroiron phthalocyanine,

[0074]

[Chemical 21]

Compound 15: tetrakis (2- (2-tetrahydrofurfuryloxy) carbonyl-5- (2-methoxyethoxy) carbonylphenoxy) dodecafluoronickel phthalocyanine,

[0076]

[Chemical formula 22]

Compound 16: Tetrakis (2,6-di (2
-Tetrahydrofurfuryloxy) carbonylphenoxy) dodecafluorovanadyl phthalocyanine,

[0078]

[Chemical formula 23]

Compound 17: Tetrakis (2,6-di (2
-Tetrahydrofurfuryloxy) carbonyl-4-methoxyphenoxy) dodecafluorovanadyl phthalocyanine,

[0080]

[Chemical formula 24]

Compound 18: tetrakis (4- (2-tetrahydrofuranoxy) carbonylphenoxy) dodecafluorocobalt phthalocyanine,

[0082]

[Chemical 25]

Compound 19: tetrakis (2- (3-tetrahydrofuranoxy) carbonyl-6-methylphenoxy) dodecafluorovanadyl phthalocyanine,

[0084]

[Chemical formula 26]

Compound 20: tetrakis (2- (3-tetrahydrofuranoxy) carbonyl-6-ethoxyphenoxy) dodecafluorozinc phthalocyanine,

[0086]

[Chemical 27]

Compound 21: tetrakis (3- (2-tetrahydropyranylmethoxy) carbonylphenoxy) dodecafluoro (chloroindium) phthalocyanine,

[0088]

[Chemical 28]

Compound 22: Tetrakis (2- (2-tetrahydropyranylmethoxy) carbonyl-6-ethoxycarbonylphenoxy) dodecafluorozinc phthalocyanine,

[0090]

[Chemical 29]

Compound 23: tetrakis (2- (2-tetrahydropyranylmethoxy) carbonyl-6-methylphenoxy) dodecafluorovanadyl phthalocyanine,

[0092]

Embedded image

Compound 24: tetrakis (2- (1-morpholinyl-2-ethoxy) carbonylphenoxy) dodecafluorovanadyl phthalocyanine,

[0094]

[Chemical 31]

Compound 25: Tetrakis (2-methoxy-
4- (2-pyrazolidinyloxy) carbonylphenoxy) dodecafluoro (chlorogallium) phthalocyanine,

[0096]

Embedded image

Compound 26: Tetrakis (2- (2-piperidylmethoxy) carbonyl-4-chlorophenoxy)
Dodecafluorovanadyl phthalocyanine,

[0098]

[Chemical 33]

Compound 27: tetrakis (2- (2-pyrazolidinylmethoxy) carbonyl-6-methylphenoxy) dodecafluoro (dichlorogermanium) phthalocyanine,

[0100]

Embedded image

Compound 28: tetrakis (4- (2-tetrahydrothienylmethoxy) carbonylphenoxy) dodecafluoro (dichlorotin) phthalocyanine,

[0102]

Embedded image

Compound 29: tetrakis (2- (2-tetrahydrothienylmethoxy) carbonyl-6-methylphenoxy) dodecafluoro (dichlorosilicon) phthalocyanine,

[0104]

Embedded image

General formula (5)

[0106]

Embedded image

In the formula, two of Y _{1 to} Y ₄ are fluorine atoms, and the remaining two are compounds represented by the following formula (M: V
O); Compound 30: bis (2- (2-tetrahydrofurfuryloxy) carbonylphenoxy) tetradecafluorovanadyl phthalocyanine,

[0108]

[Chemical 38]

Similarly, two of Y ₁ to Y ₄ are fluorine atoms and the other two are represented by the following formula (M:
Compound 31: bis (2- (2-tetrahydrofurfuryloxy) carbonyl-6-methylphenoxy) tetradecafluorovanadyl phthalocyanine,

[0110]

[Chemical Formula 39]

General formula (6)

[0112]

[Chemical 40]

In the formula, Z is a compound (M: VO) represented by the following formula: Compound 32: octakis (2- (2-tetrahydrofurfuryloxy) carbonylphenoxy) octafluorovanadyl phthalocyanine,

[0114]

Embedded image

Similarly, Z is a compound (M: VO) represented by the following formula: Compound 33: Octakis (2- (2-tetrahydrofurfuryloxy) carbonyl-6-methylphenoxy) octafluorovanadyl phthalocyanine ,

[0116]

Embedded image

The method for producing the novel phthalocyanine compound of the present invention will be described in detail below.

First, the novel phthalocyanine compound of the present invention is a phthalonitrile compound substituted with a phenoxy group substituted with one or more carboxylic acid ester groups having a heterocycle represented by COOR, or substituted with the phenoxy group. It can be produced by reacting a metal compound with a mixture of phthalonitrile which is not present.

In the phthalonitrile compound substituted with the phenoxy group, a part or all of the residue may be further substituted with a substituent other than the phenoxy group. That is, when referring to the phthalonitrile compound substituted with the phenoxy group alone, it is not limited to one kind of the phthalonitrile compound substituted with only the phenoxy group, and in addition to this, further substituted with the above-mentioned phenoxy group, A phthalonitrile compound in which a part or all of the residue is substituted with a substituent other than a phenoxy group, and a phthalonitrile compound in which these two are combined may be used. Also,
Also in the phthalonitrile which is not substituted with the phenoxy group, a part or all of the substitutable positions of the benzene nucleus may be further substituted with a substituent other than the phenoxy group. That is, in the case of phthalonitrile not substituted with the phenoxy group, it is not limited to only phthalonitrile not substituted with a phenoxy group, in addition to this, is not substituted with the above-mentioned phenoxy group, further phenoxy It may be a phthalonitrile compound in which some or all of the substitutable positions of the benzene nucleus are substituted with a substituent other than a group, and a phthalonitrile compound in which these two are combined is further substituted. Therefore, when referring to a mixture of a phthalonitrile compound substituted with a phenoxy group and a phthalonitrile not substituted with the phenoxy group, one or more of the above-mentioned phthalonitrile compounds substituted with a phenoxy group are used. And a mixture of one or more phthalonitriles not substituted with the phenoxy group.

Examples of the substituent other than the phenoxy group in the phthalonitrile compound substituted with the phenoxy group alone or in the phthalonitrile not substituted with the phenoxy group include a halogen atom, an alkyl group, an aryl group and a hetero group. Cyclic group, cyano group, hydroxy group, nitro group, amino group (including substituted amino group), alkoxy group, acylamino group, aminocarbonylamino group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, Sulfonylamino group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group,
Azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, imide group,
Examples thereof include a heterocyclic thio group, a sulfinyl group, a phosphoryl group and an acyl group. The type of the substituent may be one type or two or more types. A preferable substituent is a halogen atom, particularly a chlorine atom or a fluorine atom, and particularly a fluorine atom.

The phthalonitrile used in the production of the phthalocyanine compound of the present invention may be the above-mentioned phthalonitrile compound substituted with a phenoxy group alone or a mixture with a phthalonitrile not substituted with the phenoxy group. However, it is preferable that the phthalonitrile compound substituted with a phenoxy group is used alone.

A method for producing a preferable one represented by the general formula (1) among the novel phthalocyanine compounds of the present invention will be described in detail below.

Suitable novel phthalocyanine compounds represented by the general formula (1) include, for example, the following general formula (3)

[0124]

[Chemical 43]

[Wherein, COOR represents a carboxylic acid ester group having a heterocycle, X represents a halogen atom,
It represents at least one selected from the group consisting of an alkyl group which may be substituted with a halogen atom, an alkoxy group and a carboxylic acid ester group, m represents an integer of 0 to 3, and n represents an integer of 0 to 4. Represent ] It can manufacture by making a phthalonitrile compound and metal compound shown by these react.

In the method for producing a novel phthalocyanine compound of the present invention, the reaction of the phthalonitrile compound alone or a mixture of the phthalonitrile not substituted with the phenoxy group and the metal compound can be carried out in the absence of a solvent. It is preferable to use it. The organic solvent may be any inert solvent that is not reactive with the starting materials, such as benzene, toluene, xylene, nitrobenzene, monochlorobenzene, dichlorobenzene,
Inert solvent such as trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, benzonitrile, or pyridine, N, N-dimethylformamide, N-methyl-2-pyrrolidinone, N, N-
Dimethylacetophenone, triethylamine, tri-n
-Aprotic polar solvent such as -butylamine, dimethyl sulfoxide, sulfolane, etc. can be used, and preferably 1-chloronaphthalene, 1-methylnaphthalene,
Benzonitrile.

In the present invention, 2 to 40 parts, preferably 20 to 35 parts, of a phthalonitrile compound (or a mixture with a phthalonitrile which is not substituted with the phenoxy group) is added to 100 parts of the organic solvent (hereinafter, referred to as "parts by weight"). Range of parts,
1-2 mol, preferably 1.1-, of a metal compound with respect to 4 mol of the phthalonitrile compound (or a mixture of the phthalonitrile not substituted with the phenoxy group).
The reaction temperature is 30 to 250 ° C. in the range of 1.5 mol.
The reaction is preferably carried out in the range of 80 to 200 ° C.

Examples of the metal compound include halides such as chlorides, bromides and iodides, metal oxides such as metal oxides and acetates, complex compounds such as acetylacetonate, metal carbonyl compounds and metal powders. .

In the present invention, the phthalonitrile compound as a starting material is, for example, the phthalonitrile compound represented by the general formula (3).
Can be synthesized according to. Then, in the synthesis of the novel phthalocyanine compound represented by the general formula (1) of the present invention, the target product can be obtained according to step B using the raw materials of these phthalonitrile compounds alone.

[0130]

[Chemical 44]

The novel phthalocyanine compounds represented by the general formulas (5) and (6) can be synthesized, for example, by the same method as the synthetic method of the novel phthalocyanine compound represented by the general formula (1). That is, the novel phthalocyanine compound represented by the general formula (5) can be used as a starting material in step B of the above synthetic scheme with 3,4,5,6-
It can be synthesized by using a 1: 1 (molar ratio) mixture of tetrafluorophthalonitrile and the above phthalonitrile compound (preferably the phthalonitrile compound represented by the general formula (3)). In addition, the novel phthalocyanine compound represented by the general formula (6) can be obtained by the step A in the above synthetic scheme.
By using twice the amount of phenol as the raw material of

[0132]

Embedded image

It can be synthesized by producing the phthalonitrile compound represented by the formula (1) and then using the phthalonitrile compound represented by the general formula (7) as a raw material in step B.

Since the novel phthalocyanine compound of the present invention has high solubility and excellent reflectance, sensitivity and light resistance,
In particular, as a write-once type optical recording medium for a compact disc, which is required to have these characteristics, is composed of a transparent resin substrate, a recording layer provided on the substrate, and a metal reflection layer,
For example, a CD for playing music such as audio, a PHOTO-CD for storing photos, or a CD-RO for a computer.
The effect can be exhibited as a write-once type optical recording medium having compatibility and commonality with M players.

As an optical recording medium containing a phthalocyanine compound in a recording layer provided on a substrate, a phthalocyanine compound having a carboxylic acid ester group having a heterocycle in the 2-position of a phenoxy group in the general formula (1) is used. It is preferable in terms of recording sensitivity in the optical recording medium.

A phthalocyanine compound in which a heterocycle is substituted with a phenoxy group having a carboxylic acid ester group bonded to a carboxylic acid via an alkylene group is preferable from the viewpoint of recording sensitivity.

The novel phthalocyanine compound of the present invention has excellent controllability of absorption wavelength while maintaining light resistance, optical properties in a thin film, and excellent solubility in an organic solvent, and further has a heterocyclic carboxylic acid ester group. The phthalocyanine compound at the 2-position of the phenoxy group can lower the thermal decomposition temperature, and can exert an excellent effect on an optical recording medium compatible with a compact disc.

The disk substrate used in this case is preferably one through which light for recording or reading signals is transmitted. It is desirable that the light transmittance is 85% or more and the optical anisotropy is small. Examples include substrates made of glass, acrylic resin, polycarbonate resin, polyester resin, polyamide resin, vinyl chloride resin, polystyrene resin, epoxy resin, and the like. Of these, a polycarbonate resin is preferable because of its optical properties, ease of molding, mechanical strength, and the like.

The above-mentioned dye is first formed on this substrate, and a metal reflection film layer is formed thereon. Examples of the metal used as the reflective film layer include aluminum, silver, gold, copper, platinum, and the like, and the reflective film layer is usually formed by a method such as vacuum deposition or sputtering.

In order to form the recording layer containing the dye on the substrate in the optical recording medium of the present invention, it is preferable to use a usual coating method. The method can be a spin coating method, a dipping method, or a roll coating method, and the spin coating method is particularly preferable. The organic solvent used at this time is one that does not attack the substrate. For example, hexane,
Aliphatic and alicyclic hydrocarbon solvents such as octane and cyclohexane, or methyl alcohol, ethyl alcohol, isopropyl alcohol, allyl alcohol, 2-
Alcoholic solvents such as methoxyethanol, 2-ethoxyethanol and diacetone alcohol are preferred.
Since the dye of the present invention is particularly well dissolved in an alcohol solvent, it is preferable to use these solvents.

The CD which is one kind of the optical recording medium of the present invention is
From the viewpoint of compatibility with the player, it is required that the reflectance of the read laser beam through the substrate is 60% or more.

These are possible by optimizing the film thickness according to each dye, and usually 50 nm to 3
00 nm, especially 80 nm to 200 nm is preferable.

[0143]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 Production of Compound 4 In a 100 ml four-necked flask, 4.02 g (0.01 mol) of a phthalonitrile compound represented by the following structural formula (8) and 0.57 g (3 mmol of stannous chloride) were added. ) And 15 ml of benzonitrile were charged and reacted at 175 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to give the desired green cake (tetrakis (4- (2-tetrahydrofurfuryloxy) carbonylphenoxy) dodecafluoro (dichlorotin). Phthalocyanine (Compound 4)) 3.85
g was obtained. (Yield, 92.2 based on phthalonitrile
%).

Visible absorption spectrum Maximum absorption wavelength 729.0 nm in 2-ethoxyethanol (ε = 5.68 × 10 ⁴ ) Thin film 730.5 nm Solubility 12 wt% with respect to 2-ethoxyethanol Elemental analysis H C N F Theoretical value 2.89% 53.40% 6.23% 12.68% Analytical value 2.95% 53.52% 6.53% 12.51%

[0146]

Embedded image

Example 2 Preparation of Compound 2 In a 100 ml four-necked flask, 4.16 g (0.01 mol) of a phthalonitrile compound represented by the following structural formula (9) and 0.47 g (3 mmol) of vanadium trichloride. Then, 15 ml of benzonitrile was charged and reacted at 175 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to obtain 3.60 g of a target green cake. (Yield, 83.2% based on phthalonitrile). The obtained tetrakis (2-
(2-Tetrahydrofurfuryloxy) carbonyl-6
The infrared absorption spectrum of -methylphenoxy) dodecafluorovanadyl phthalocyanine (Compound 2) is shown in Fig. 1.

Visible absorption spectrum Maximum absorption wavelength 711.5 nm in 2-ethoxyethanol (ε = 8.22 × 10 ⁴ ) Thin film 672.5 nm Solubility 12 wt% with respect to 2-ethoxyethanol Elemental analysis H C N F Theoretical value 3.49% 58.24% 6.47% 18.16% Analytical value 3.67% 58.39% 6.55% 13.02%

[0149]

[Chemical 47]

Example 3 Preparation of Compound 5 In a 100 ml four-necked flask, 4.46 g (0.01 mol) of a phthalonitrile compound represented by the following structural formula (10) and 0.47 g (3 mmol) of vanadium trichloride. Then, 15 ml of benzonitrile was charged and reacted at 175 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to give the target green cake (tetrakis (2- (2-tetrahydrofurfuryloxy) carbonyl-6-ethoxyphenoxy) dodecafluoro). 3.89 g of vanadyl phthalocyanine (Compound 5) was obtained. (Yield, 84.1% based on phthalonitrile).

Visible absorption spectrum Maximum absorption wavelength 711.5 nm in 2-ethoxyethanol (ε = 1.37 × 10 ⁵ ) Thin film 729.0 nm Solubility 13 wt% with respect to 2-ethoxyethanol Elemental analysis H C N F Theoretical value 3.70% 57.06% 6.05% 12.31% Analytical value 3.55% 56.84% 6.00% 12.41%

[0152]

Embedded image

Example 4 Preparation of Compound 16 In a 100 ml four-necked flask, 5.30 g (0.01 mol) of a phthalonitrile compound represented by the following structural formula (11) and 0.47 g (3 mmol) of vanadium trichloride. Then, 15 ml of benzonitrile was charged and reacted at 175 ° C. for 4 hours. After the completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to obtain 3.90 g of a target green cake. (Yield, 71.3% based on phthalonitrile). The obtained tetrakis (2,
The infrared absorption spectrum of 6-di (2-tetrahydrofurfuryloxy) carbonylphenoxy) dodecafluorovanadyl phthalocyanine (Compound 16) is shown in FIG.

Visible absorption spectrum Maximum absorption wavelength 713.0 nm in 2-ethoxyethanol (ε = 1.57 × 10 ⁵ ) Thin film 733.5 nm Solubility 7% by weight with respect to 2-ethoxyethanol Elemental analysis H C N F Theoretical value 3.87% 57.07% 5.12% 10.42% Analytical value 3.90% 56.99% 5.09% 10.51%

[0155]

[Chemical 49]

Example 5 Preparation of Compound 23 In a 100 ml four-necked flask, 4.30 g (0.01 mol) of a phthalonitrile compound represented by the following structural formula (12) and 0.47 g (3 mmol) of vanadium trichloride. Then, 15 ml of benzonitrile was charged and reacted at 175 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to obtain 3.32 g of a target green cake. (Yield, 74.3% based on phthalonitrile). The obtained tetrakis (2-
(2-Tetrahydropyranylmethoxy) carbonyl-6
The infrared absorption spectrum of -methylphenoxy) dodecafluorovanadyl phthalocyanine (Compound 23) is shown in FIG.

Visible absorption spectrum Maximum absorption wavelength 712.0 nm in 2-ethoxyethanol (ε = 8.99 × 10 ⁴ ) Thin film 676.0 nm Solubility 10 wt% with respect to 2-ethoxyethanol Elemental analysis H C N F Theoretical value 3.87% 59.10% 6.27% 12.75% Analytical value 3.95% 58.93% 6.25% 12.88%

[0158]

Embedded image

Example 6 Production of Compound 19 4.02 g (0.01 mol) of a phthalonitrile compound represented by the following structural formula (13) and 0.47 g (3 mmol) of vanadium trichloride were placed in a 100 ml four-necked flask. Then, 15 ml of benzonitrile was charged and reacted at 175 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off, and the obtained solid content was washed with 200 ml of methyl alcohol to obtain 3.88 g of a target green cake. (Yield, 92.7% based on phthalonitrile). The obtained tetrakis (2-
The infrared absorption spectrum of (3-tetrahydrofuranoxy) carbonyl-6-methylphenoxy) dodecafluorovanadyl phthalocyanine (Compound 19) is shown in FIG.

Visible absorption spectrum Maximum absorption wavelength 710.0 nm in 2-ethoxyethanol (ε = 8.31 × 10 ⁴ ) Thin film 674.5 nm Solubility 11 wt% with respect to 2-ethoxyethanol Elemental analysis H C N F Theoretical value 3.13% 57.32% 6.68% 13.50% Analytical value 3.20% 57.49% 6.70% 13.49%

[0161]

[Chemical 51]

Examples 7 to 15 Phthalocyanine compounds were produced in the same manner as in Examples 1 to 6 by using the phthalonitrile compounds and metal compounds shown in Tables 1 to 3. The yield with respect to the phthalonitrile compound and the maximum absorption wavelength in 2-ethoxyethanol at this time were as shown in Tables 1 to 3.

[0163]

[Table 1]

[0164]

[Table 2]

[0165]

[Table 3]

Example 16 The phthalocyanine compound of Example 1 was treated with 2-methoxy on a polycarbonate resin substrate having a depth of 80 nm and a spiral guide groove having a pitch of 1.6 μm, a thickness of 1.2 nm, an outer diameter of 120 mm and an inner diameter of 15 mm. A coating liquid dissolved in ethanol at a concentration of 5% by weight was formed into a film having a thickness of 120 nm using a spin coater. Next, gold was formed into a film having a thickness of 75 nm by vacuum vapor deposition on the coating film thus obtained. Further, a protective coating film made of an ultraviolet curable resin was provided on the above to prepare an optical recording medium. The reflectance of the optical recording medium thus obtained was measured and found to be 770 nm to 80 nm.
It was 78% in the wavelength range of 0 nm, and stable optical characteristics were obtained.

Using this optical recording medium, a semiconductor laser having a wavelength of 780 nm was used, and an output of 6.5 mW and a linear velocity of 1.
When the EMF signal was recorded at 4 m / s, recording was possible. As a result of analyzing the obtained signal, the signal was at a level that could be reproduced by a commercially available CD player.

Examples 17 to 30 Optical recording media were prepared in the same manner as in Example 16 except that the compounds shown in Examples 2 to 15 were used. This optical recording medium was used and evaluated in the same manner as in Example 16. As a result, the reflectance was 75% or more, and stable optical characteristics were obtained.

Using these optical recording media, a semiconductor laser having a wavelength of 780 nm was used, and an EMF signal was recorded at an output of 6.5 mW at a linear velocity of 1.3 m / s. It was As a result of analyzing the obtained signal, the signal was at a level that could be reproduced by a commercially available CD player.

Further, the phthalocyanine compounds obtained in Examples 1 to 15 were measured for light resistance, solubility and association, and the results shown in Table 4 were obtained.

[0171]

[Table 4]

The light resistance was evaluated by the following method.

1 g of the dye was dissolved in 20 g of methyl ethyl ketone, and a dye thin film was formed on a glass substrate by spin coating to prepare a sample. This sample was set in a xenon light resistance tester (irradiation light amount 100,000 Lux), and the decrease in absorbance with time was measured. Then, the following three-stage evaluation was performed based on the residual ratio of the absorbance after 100 hours.

Residual rate of absorbance after 100 hours is 80% or more. Δ Residual rate of absorbance after 100 hours is 30% to 80% × Residual rate of absorbance after 100 hours is less than 30%. Solubility in
The following three-stage evaluation was performed.

○ Solubility of 5% or more Δ Solubility of 2% to 5% × less than 2% The absorption wavelength was measured in 2-methoxyethanol.

The association peak was evaluated in the following two stages.

○ 20% or less association peak × 20% or more association peak

[0178]

According to the production method of the present invention, it is possible to regioselectively introduce a substituent into the phthalocyanine skeleton. That is, according to the production method of the present invention, it is possible to design a molecule of a compound having a near infrared absorption wavelength region or solubility changed according to the use, and at that time, industrially without the need for complicated production steps. It is advantageous. The fluorine atom in the novel phthalocyanine compound of the present invention rather has the effect of increasing the solubility.

As described above, the novel compound of the present invention has excellent absorption characteristics, solubility, light resistance and economical efficiency as compared with the conventionally known phthalocyanine compound, and also has absorption in the near infrared region of 650 to 900 nm. Therefore, it can be practically used as a near infrared absorbing dye. Especially CD, P
When used in a write-once type optical recording medium having compatibility and sharing with a HOTO-CD or CD-ROM player, an excellent effect can be exhibited.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of the phthalocyanine compound 2 according to the present invention.

FIG. 2 is an infrared absorption spectrum of the phthalocyanine compound 16 according to the present invention.

FIG. 3 is an infrared absorption spectrum of the phthalocyanine compound 23 according to the present invention.

FIG. 4 is an infrared absorption spectrum of the phthalocyanine compound 19 according to the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Koji Yoshito, 12-chome, Kannondai, Tsukuba, Ibaraki Prefecture 12 Stock Company, Nippon Shokubai

Claims (10)

[Claims] 1. 16 of benzene nucleus of phthalocyanine skeleton
1-8 of these substitutable positions are substituted with a phenoxy group, and the phenoxy group is one or more CO
A novel phthalocyanine compound, which is substituted with a carboxylic acid ester group having a heterocycle represented by OR. 2. The following general formula (1): [Wherein, COOR represents a carboxylic acid ester group having a heterocycle, X is selected from the group consisting of a halogen atom, an alkyl group which may be substituted with a halogen atom, an alkoxy group and a carboxylic acid ester group. Represents at least one kind, m represents an integer of 0 to 3, and n represents 0 to 4
Represents an integer, and M represents a metal, a metal oxide, or a metal halide. ] The novel phthalocyanine compound of Claim 1 shown by these. 3. The following general formula (2): [Wherein, COOR represents a carboxylic acid ester group having a heterocycle, X is selected from the group consisting of a halogen atom, an alkyl group which may be substituted with a halogen atom, an alkoxy group and a carboxylic acid ester group. Represents at least one kind, n represents an integer of 0 to 4, M represents a metal,
Represents a metal oxide or a metal halide. ] The novel phthalocyanine compound of Claim 2 shown by these. 4. The phthalocyanine compound according to claim 1, wherein the carboxylic acid ester group having a heterocycle is at the 2-position of the phenoxy group. 5. The phthalocyanine compound according to claim 1, wherein the hetero ring is a carboxylic acid ester group having an oxygen atom. 6. The phthalocyanine compound according to claim 2, wherein in the general formula (1), one X is at the 6-position of the phenoxy group. 7. A phthalonitrile compound substituted with a phenoxy group, which is substituted with one or more carboxylic acid ester groups having a heterocycle represented by COOR, or a mixture with a phthalonitrile which is not substituted with the phenoxy group. 2. A reaction with a metal compound.
7. A method for producing the novel phthalocyanine compound according to any one of items 1 to 6. 8. The following general formula (3): [Wherein, COOR represents a carboxylic acid ester group having a heterocycle, X is selected from the group consisting of a halogen atom, an alkyl group which may be substituted with a halogen atom, an alkoxy group and a carboxylic acid ester group. Represents at least one kind, m represents an integer of 0 to 3, and n represents 0 to 4
Represents the integer. ] The phthalonitrile compound shown by these and a metal compound are made to react, The manufacturing method of the novel phthalocyanine compound of Claim 7 characterized by the above-mentioned. 9. An optical recording medium containing the novel phthalocyanine compound according to claim 1 in a recording layer provided on a substrate. 10. A write-once type optical recording medium for a compact disc, comprising a recording layer and a metal reflection layer provided on a transparent resin substrate, wherein the recording layer is the recording layer according to claim 9. recoding media.