JPH0827161A - Phthalonitrile compound, diiminoisoindoline compound, near infrared absorbing material of phthalocyanine and their production - Google Patents

Abstract

PURPOSE:To obtain a new compound readily providing a new near infrared absorbing material of phthalocyanine capable of forming a coating film by a solvent coating method due to improvement in solubility without impairing excellent stability and having high near infrared absorptivity. CONSTITUTION:A compound of formula I (R<1> is a straight-chain or branched 1-8C alkylene; R<2> to R<4> are each H, a 1-12C alkyl, etc.) such as a compound of formula II. The compound is obtained by reacting 3- or 4- hydroxyphthalonitrile with a compound of formula III (Z is a halogen) such as chloromethyltrimethylsilane in an organic solvent (preferably N,N- dimethylacetamide) in the presence of an alkali such as potassium carbonate preferably at 40-180 deg.C. The amount of the compound of formula III used is preferably 1.5-3 mols based on the hydroxyphthalonitrile.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel phthalocyanine near-infrared absorbing material which can be used as an optical recording material, a photoelectric conversion material, an infrared cut filter, etc., and a novel phthalonitrile compound and diiminoiso as an intermediate thereof. The present invention relates to indoline compounds and methods for producing them.

[0002]

2. Description of the Related Art Near infrared absorbing materials are used for various purposes. Examples of such applications include the following. Infrared-sensitive safelight filter for photosensitive materials Infrared cut filter for controlling plant growth Infrared cut filter that blocks heat rays from the sun Infrared cut filter harmful to human eye tissue Infrared cut filter for semiconductor light receiving element, etc. An even greater use is as a recording material in an optical information recording medium.

Up to now, cyanine dyes, phenanthrene dyes, naphthoquinone dyes, pyrylium dyes, squarylium dyes, and the like have been known as infrared absorbing substances, and information recording media using these dyes as recording materials are also available. Known (for example, JP-A-55-9703)
3, JP-A-58-83344, JP-A-58-224.
793, JP-A-58-214162, JP-A-59-
No. 24692, etc.).

However, the above dyes have various problems when used as a recording material. For example, phenanthrene-based dyes, naphthoquinone-based dyes, and squarylium-based dyes have the advantage of easy vapor deposition, but have the problem of low reflectance. When the reflectance is low, the contrast of the reflectance between the portion recorded by laser light and the unrecorded portion is low, and it becomes difficult to reproduce the recorded information. Further, the pyrylium-based dye and the cyanine dye have the advantage that they can be coated by coating, but on the other hand, they have poor light resistance and are prone to deterioration by reproduction light (natural light). On the other hand, phthalocyanine dyes are characterized by extremely high stability (with respect to heat and light), but have poor solubility in organic solvents, and only a small portion of phthalocyanine dyes can be formed into thin films by vapor deposition. However, it was poor as a product application.

In order to solve the above problems, it has been recently practiced to introduce a substituent into phthalocyanine to form a phthalocyanine compound which can be dissolved in an organic solvent, and then apply this. JP-A-1-180865 and JP-A-2-18086
The phthalocyanine compounds disclosed in JP-A No. 265788 and JP-A-3-215466 are those obtained by introducing a long-chain alkyl group or alkoxy group into the benzene ring of phthalocyanine to obtain solubility in a hydrocarbon organic solvent. Is. In addition to these, many introduction of long-chain alkyl groups via functional groups such as ester groups, polyether groups, and thioether groups has been carried out.

[0006]

However, although these phthalocyanine compounds are soluble in nonpolar solvents, they are not yet sufficiently soluble, and their reflectance is lower than that of cyanine dyes. There was a problem that it was enough.

Therefore, an object of the present invention is to provide a novel phthalocyanine near-infrared absorbing agent which enhances solubility without sacrificing the inherent stability of phthalocyanine compounds, has high productivity, and has a high absorption in the near infrared. And an intermediate thereof and a method for producing them.

[0008]

According to the present invention, there is provided a phthalonitrile compound represented by the following general formula (I).

Embedded image (In the formula, each of R ^{1 to} R ⁴ represents the following. R ¹ : a linear or branched alkylene group having 1 to 8 carbon atoms, which contains a so-called ether bond of —C—O—C—. R ^{2 to} R ⁴ , which may be substituted or unsubstituted with a silyl group, are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a vinyl group,
Or -OSi (R ⁵⁾ ₃ group or a -CH ₂ Si (R ⁵⁾ ₃ group, R ^5: an alkyl group having 1 to 3 carbon atoms. )

According to the present invention, the following general formula (I
A diiminoisoindoline compound represented by I) is provided.

Embedded image (In the formula, each of R ^{1 to} R ⁴ represents the following. R ¹ : a linear or branched alkylene group having 1 to 8 carbon atoms, which contains a so-called ether bond of —C—O—C—. R ^{2 to} R ⁴ , which may be substituted or unsubstituted with a silyl group, are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a vinyl group,
Or -OSi (R ⁵⁾ ₃ group or a -CH ₂ Si (R ⁵⁾ ₃ group, R ^5: an alkyl group having 1 to 3 carbon atoms. )

Furthermore, according to the present invention, the following general formula (II
There is provided a phthalocyanine near-infrared absorbing material composed of one kind or a mixture of two or more kinds among four kinds represented by Ia) to (IIId).

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[Chemical 4]

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[Chemical 6] (In the formula, M and X ^{1 to} X ¹⁶ each represent the following. M: 2 hydrogen atoms, divalent metal atom, monosubstituted trivalent metal atom, disubstituted tetravalent metal atom or oxy. metal atom, X ¹ to X ^16: each independently -OR ¹ SiR ² R ³ R ⁴ group, R ^1: linear or branched alkylene group having 1 to 8 carbon atoms, in the radical -C-O-C- Which may contain a so-called ether bond or which may be substituted with a silyl group, R ^{2 to} R ⁴ : each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. Group, vinyl group,
Or —OSi (R ⁵ ) ₃ group or —CH ₂ Si (R ⁵ ) ₃ group, R ⁵ : an alkyl group having 1 to 3 carbon atoms, an atom other than X ^{1 to} X ¹⁶ attached to the benzene ring: a hydrogen atom or a halogen atom. )

According to the present invention, the following general formula (IV
Provided is a phthalocyanine near-infrared absorbing material composed of one kind or a mixture of two or more kinds among four kinds represented by a) to (IV d).

[Chemical 7]

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[Chemical 9]

[Chemical 10] (In the formula, M and X ^{1 to} X ¹⁶ each represent the following. M: 2 hydrogen atoms, divalent metal atom, monosubstituted trivalent metal atom, disubstituted tetravalent metal atom or oxy. metal atom, X ¹ to X ^16: each independently -OR ¹ SiR ² R ³ R ⁴ group, R ^1: linear or branched alkylene group having 1 to 8 carbon atoms, in the radical -C-O-C- Which may contain a so-called ether bond or which may be substituted with a silyl group, R ^{2 to} R ⁴ : each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. Group, vinyl group,
Or —OSi (R ⁵ ) ₃ group or —CH ₂ Si (R ⁵ ) ₃ group, R ⁵ : an alkyl group having 1 to 3 carbon atoms, an atom other than X ^{1 to} X ¹⁶ attached to the benzene ring: a hydrogen atom or a halogen atom. )

Further, according to the present invention, the following general formula (V
Provided is a phthalocyanine near-infrared absorbing material composed of one kind or a mixture of two or more kinds out of four kinds represented by a) to (Vd).

[Chemical 11]

[Chemical 12]

[Chemical 13]

Embedded image (In the formula, M, X ^{1 to} X ¹⁶ , Y and n ^{1 to} n 4 respectively represent the following: M: two hydrogen atoms, divalent metal atom, monosubstituted trivalent metal atom, disubstituted Tetravalent metal atom or oxymetal atom, X ^{1 to} X ¹⁶ : each independently —OR ¹ SiR ² R ³ R ⁴ group, R ¹ : a linear or branched alkylene group having 1 to 8 carbon atoms, and It may contain a so-called ether bond of C—O—C— and may be substituted with a silyl group. R ^{2 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a carbon atom. Number 1 to 3 alkoxy group, vinyl group,
Or —OSi (R ⁵ ) ₃ group or —CH ₂ Si (R ⁵ ) ₃ group, R ⁵ : an alkyl group having 1 to 3 carbon atoms, an atom other than X ^{1 to} X ¹⁶ attached to the benzene ring: a hydrogen atom or a halogen Atom, Y: halogen atom, n1 to n4: each independently represent the number of halogen substitutions,
An integer from 1 to 4. )

According to the present invention, 3- or 4-hydroxyphthalonitrile is added to an organic solvent in the presence of an alkali represented by the following general formula (VI) ZR ¹ SiR ² R ³ R ⁴ (VI) (wherein , R ^{1 to} R ⁴ and Z each represent the following: R ¹ : a linear or branched alkylene group having 1 to 8 carbon atoms, which contains a so-called —C—O—C— ether bond. it can have, may be substituted with a silyl group, R ² to R ^4: each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a vinyl group,
Or -OSi (R ⁵⁾ ₃ group or a -CH ₂ Si (R ⁵⁾ ₃ group, R ^5: an alkyl group having 1 to 3 carbon atoms, Z: halogen atoms. The present invention provides a method for producing a phthalonitrile compound represented by the general formula (I), which comprises reacting with at least one compound represented by the formula (1).

Furthermore, according to the present invention, 3- or 4-nitrophthalonitrile is reacted with sodium nitrite and potassium carbonate or sodium metal compound in an organic solvent, and then the above-mentioned general formula (VI) ZR ¹ SiR ² R ³ R ⁴ (VI) (In the formula, R ^{1 to} R ⁴ and Z each represent the following. R ¹ : a linear or branched alkylene group having 1 to 8 carbon atoms, in which -C is present. It may contain a so-called ether bond of —O—C— and may be substituted with a silyl group, R ^{2 to} R ⁴ : each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a carbon number. 1-3 alkoxy group, vinyl group,
Or -OSi (R ⁵⁾ ₃ group or a -CH ₂ Si (R ⁵⁾ ₃ group, R ^5: an alkyl group having 1 to 3 carbon atoms, Z: halogen atoms. ) At least one compound represented by the formula (1) is reacted to provide a method for producing a phthalonitrile compound represented by the general formula (I).

According to the present invention, the general formula (I)
At least one phthalonitrile compound represented by or at least one diiminoisoindoline compound represented by the general formula (II), a divalent metal, a monosubstituted trivalent metal, a disubstituted tetravalent metal, or A metal selected from oxymetals or a derivative of these metals is reacted with the above general formulas (IIIa) to (IIId) and (IVa) to (IV
A method for producing at least one phthalocyanine compound represented by d) is provided.

The present invention will be described in detail below. The novel phthalonitrile compound of the present invention is useful as an intermediate of the furocyanine near-infrared absorbing material of the present invention, and is represented by the following general formula (I).

Embedded image (In the formula, each of R ^{1 to} R ⁴ represents the following. R ¹ : a linear or branched alkylene group having 1 to 8 carbon atoms, which contains a so-called ether bond of —C—O—C—. R ^{2 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a vinyl group, or a silyl group.
Or -OSi (R ⁵⁾ ₃ group or a -CH ₂ Si (R ⁵⁾ ₃ group, R ^5: an alkyl group having 1 to 3 carbon atoms. )

In the above definition, the straight-chain or branched alkylene group having 1 to 8 carbon atoms is methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, 1,2.
Examples include -butylene group, 1,3-butylene group, 2,3-butylene group, heptamethylene group and octamethylene group. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group,
Examples thereof include an amyl group, an octyl group, a decyl group, and a dodecyl group, and examples of the alkyl group having 1 to 3 carbon atoms include those having 1 to 3 carbon atoms in the above. Moreover, a methoxy group, an ethoxy group, a propoxy group etc. are illustrated as a C1-C3 alkoxy group.

3-of the present invention represented by the general formula (I)
Or, 4-silyl group-substituted alkoxyphthalonitrile has 3
-Or 4-hydroxyphthalonitrile in the presence of an alkali in an organic solvent, the following general formula (VI) ZR ¹ SiR ² R ³ R ⁴ (VI) (wherein R ^{1 to} R ⁴ and Z are respectively the following R ^{1 is} a linear or branched alkylene group having 1 to 8 carbon atoms, which may contain a so-called ether bond of —C—O—C—, or is substituted with a silyl group. R ^{2 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a vinyl group,
Or -OSi (R ⁵⁾ ₃ group or a -CH ₂ Si (R ⁵⁾ ₃ group, R ^5: an alkyl group having 1 to 3 carbon atoms, Z: halogen atoms. ) It can manufacture by reacting with at least 1 sort (s) of compound shown by these. That is, 3- or 4-hydroxyphthalonitrile and potassium carbonate or sodium hydroxide are dissolved in an organic solvent, and ZR ¹ SiR ² R ³ R ⁴ is allowed to act on the solution to give the desired silyl group-substituted alkoxyphthalonitrile. Is obtained.

The organic solvent used here is N, N-
Examples thereof include dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, and dimethylsulfoxide, but particularly N, N-dimethylformamide, N, N-dimethylacetamide, or one of these two. And a mixed solvent of at least one of the other three. ZR ¹ SiR ² R ³
R ⁴ is usually added in an equimolar amount to the hydroxyphthalonitrile, but it is preferable to add R ⁴ in an amount of 1.5 to 3 times the molar amount, which is higher than the theoretical reaction amount, because the yield is improved. The reaction temperature at this time is 20 to 200 ° C., preferably 40 to 200 ° C.
It is 180 ° C.

Specific examples of ZR ¹ SiR ² R ³ R ⁴ include the following. ClCH ₂ SiMe ₃ , ClC ₂ H ₄
SiMe ₃ , ClC ₃ H ₆ SiMe ₃ , ClCH (Et) S
iMe ₃ , ClCH (Pr) SiMe ₃ , ClCH (iP
r) SiMe ₃ , ClCH (SiMe ₃ ) SiMe ₃ , C
lCH (Me) SiMe ₃ , ClCH ₂ OCH ₂ SiM
e ₃ , ClCH ₂ Si (Me) ₂ OEt, ClCH ₂ Si
(Me) ₂ H, ClCH ₂ Si (Me) ₂ CH = CH ₂ , C
lCH ₂ Si (Me) ₂ C ₁₂ H ₂₅ , ClCH ₂ Si (OE
t) ₃ , ClCH ₂ Si (OEt) ₂ Me, ClCH ₂ Si
(OiPr) ₂ Me, ClCH ₂ Si (Me) ₂ CH ₂ Si
Me ₃ , ClCH ₂ Si (Me) ₂ OSiMe ₃ , ClC ₃
H ₆ Si (Me) ₂ OMe, ClC ₃ H ₆ SiMe (OM
e) ₂ , ClC ₃ H ₆ Si (OEt) ₃ , ClC ₃ H ₆ Si
(OMe) ₃ , ClC ₃ H ₆ Si (OSiMe) ₃ , ClC
H ₂ Si (Me) ₂ OMe, ClCH ₂ Si (OMe) ₃ ,
ClC ₂ H ₄ OSiMe ₃ , ClCH ₂ CH (OSiM
e ₃ ) Me, ClC ₃ H ₆ OSiMe ₃ , ClCH ₂ Si
(Me) ₂ C ₄ H ₉ , ClC ₃ H ₆ Si (Me) (OSiM
e ₃ ) ₂ , ClC ₃ H ₆ Si (Me) [(CH ₂ ) ₃ C
H ₃ ] ₂ , ClCH ₂ Si (Me) ₂ H, ClCH (Bu)
SiMe ₃ etc. (Here, Me is a methyl group, Et is an ethyl group, Pr is a propyl group, iPr is an isopropyl group and B.
u is a butyl group. )

The 3- or 4-silyl group-substituted alkoxyphthalonitrile represented by the general formula (I) is 3-
Alternatively, 4-nitrophthalonitrile is reacted with sodium nitrite and a potassium carbonate or sodium metal compound in an organic solvent, and then at least represented by the general formula (VI) ZR ¹ SiR ² R ³ R ⁴ (VI). It can be produced by reacting one compound. That is, this method aims at changing the nitro group of 3- or 4-nitrophthalonitrile to a potassium oxy group or a sodium oxy group, and then adding the silicon compound represented by the general formula (VI). A silyl group-substituted alkoxyphthalonitrile is directly synthesized in one pot (one container). Specifically, 3- or 4-nitrophthalonitrile is dissolved in an organic solvent, then sodium nitrite is added and heated to 100 to 200 ° C., and further potassium carbonate or sodium metal, sodium hydride, CH ₃ is added. After adding a sodium metal compound such as ONa and heating to change the nitro group of the raw material into a potassium oxy group or a sodium oxy group, Z
The desired silyl group-substituted alkoxyphthalonitrile is obtained by adding R ¹ SiR ² R ³ R ⁴ and reacting at 20 to 200 ° C. This reaction (1 pot reaction)
The solvent used in the above can be the same as the solvent used in the above-mentioned method for producing a silyl group-substituted alkoxyphthalonitrile from hydroxyphthalonitrile.

As a method for obtaining alkoxyphthalonitrile from nitrophthalonitrile, the following reaction formula (I) is used, in which nitrophthalonitrile is reacted with alcohol in the presence of sodium hydride in an organic solvent (eg dimethylformamide). A method according to Japanese Patent Laid-Open No. 3-215466 has been proposed.

[Chemical 15] However, in order to obtain a silyl group-substituted alkoxyphthalonitrile according to the present invention, the above method is applied (ie, nitrophthalonitrile is reacted with HOR ¹ SiR ² R ³ R ^{4 in} the presence of NaH in an organic solvent). ) And C-S
i bond is cleaved, a silyl group substituted alkoxy phthalonitrile of interest without generating hardly, -OR ^2, -OR ^3, phthalonitrile is generated having a substituent such as chromatography OR ^4.

The novel diiminoisoindoline compound of the present invention is useful as an intermediate of the phthalocyanine near-infrared absorbing material of the present invention, and is represented by the following general formula (II).

Embedded image (In the formula, each of R ^{1 to} R ⁴ represents the following. R ¹ : a linear or branched alkylene group having 1 to 8 carbon atoms, which contains a so-called ether bond of —C—O—C—. R ^{2 to} R ⁴ , which may be substituted or unsubstituted with a silyl group, are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a vinyl group,
Or -OSi (R ⁵⁾ ₃ group or a -CH ₂ Si (R ⁵⁾ ₃ group, R ^5: an alkyl group having 1 to 3 carbon atoms. As specific examples of R ^{1 to} R ^{5 in} the above formula, the same ones as in the case of the general formula (I) can be mentioned.

The diiminoisoindoline compound represented by the general formula (II) of the present invention is obtained by adding at least one phthalonitrile compound represented by the general formula (I) to sodium (metal sodium or sodium alkoxide) in an alcohol solvent. In the presence of), it is obtained according to the following reaction formula (II) by reacting with ammonia gas.

Embedded image In addition, methanol is generally used as a typical rucol in this case.

The novel phthalocyanine near-infrared absorbing material of the present invention comprises one kind or a mixture of two or more kinds among the four kinds represented by the following general formulas (IIIa) to (IIId), or Among the four kinds represented by IVa) to (IVd), one kind or a mixture of two or more kinds, or the general formula (Va)
To (Vd), one kind or a mixture of two or more kinds.

[0026]

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[Chemical 4]

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[Chemical 6]

[0027]

[Chemical 7]

Embedded image

[Chemical 9]

[Chemical 10]

[0028]

[Chemical 11]

[Chemical 12]

[Chemical 13]

Embedded image

(Wherein M, X ^{1 to} X ¹⁶ , Y and n ^{1 to} n
4 represents the following, respectively. M: 2 hydrogen atoms, divalent metal atom, monosubstituted trivalent metal atom, disubstituted tetravalent metal atom or oxymetal atom, X ^{1 to} X ¹⁶ : each independently —OR ¹ SiR ² R ³ R ⁴ group, R ¹ : a linear or branched alkylene group having 1 to 8 carbon atoms, which may contain a so-called ether bond of —C—O—C— or which is substituted with a silyl group. R ^{2 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a vinyl group,
Or —OSi (R ⁵ ) ₃ group or —CH ₂ Si (R ⁵ ) ₃ group, R ⁵ : an alkyl group having 1 to 3 carbon atoms, an atom other than X ^{1 to} X ¹⁶ attached to the benzene ring: a hydrogen atom or a halogen Atom, Y: halogen atom, n1 to n4: each independently represent the number of halogen substitutions,
An integer from 1 to 4. )

The above general formulas (IIIa) to (IIId), (IV
In a) to (IV d) and (V a) to (V d), the metal atom represented by M is Al, Si, Ca, Cd,
Ti, V, Mn, Fe, Co, Ni, Cu, Zn, G
e, Mo, Ru, Rh, Pd, In, Sn, Pt, Pb
Etc. In addition, R ^{1 to} R ⁵ have the same meaning as in formula (I). It should be noted that Y is a halogen atom, and examples thereof include bromine, chlorine, fluorine, iodine, and the like, with bromine being particularly preferable in terms of the effect of increasing the wavelength of the maximum absorption wavelength.

The general formulas (IIIa) to (IIId), (IV
The phthalocyanine near-infrared absorbing materials represented by a) to (IV d) and (V a) to (V d) have high solubility in organic solvents without impairing the stability originally possessed by phthalocyanine compounds. It has, of course, a high absorption power for near infrared rays. That is, since the solubility is improved, a thin film can be formed by a solvent coating method, a film having excellent productivity, stability, and high absorptivity can be obtained, which can be applied to various electronic materials.

The above general formulas (IIIa) to (IIId) of the present invention
And the phthalocyanine near infrared absorbing material represented by (IVa) to (IVd) is at least one phthalonitrile compound represented by the general formula (I) or at least one phthalonitrile compound represented by the general formula (II). Can be produced by reacting the diiminoisoindoline compound (1) with a metal selected from divalent metals, monosubstituted trivalent metals, disubstituted tetravalent metals or oxymetals, or derivatives of these metals. .

The phthalocyanine ring synthesis in this case is preferably carried out in an organic solvent. That is, at least one kind (1 to 4 kinds) of phthalonitrile or diiminoisoindoline compound as a raw material is mixed with a metal or a metal derivative in a solvent,
Heat reaction is performed at 0 ° C to 240 ° C. Here, the reaction temperature is 9
If the temperature is lower than 0 ° C, the reaction progresses slowly or does not proceed, and if the temperature exceeds 240 ° C, a large amount of decomposition products are produced and the yield decreases. The amount of the solvent used is 1 to 100 times by weight, preferably 3 to 25 times by weight that of the phthalonitrile or diiminoisoindoline compound, and the solvent may have a boiling point of 90 ° C. or higher. The solvent used is preferably alcohol, and specific examples thereof include n-butyl alcohol, n-amyl alcohol, n-hexanol, cyclohexanol,
2-methyl-1-pentanol, 1-heptanol, 2
-Heptanol, 1-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol, ethoxy ethanol, propoxy ethanol, butkin ethanol and the like. As the metal or metal derivative used in the reaction, Al,
Si, Ca, Cd, Ti, V, Mn, Fe, Co, N
i, Cu, Zn, Ge, Mo, Ru, Rh, Pd, I
Examples thereof include n, Sn, Pt, Pb and their halides, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds, oxides and complexes.

The metal or metal derivative and the phthalonitrile or diiminoisoindoline compound are preferably used in a molar ratio of 1: 3 to 6 mol. As a catalyst for the ring formation reaction, an organic base such as diazabicycloundecene,
A strong base auxiliary agent such as diazabicyclononene may be added in an amount of 0.1 to 10 mol per 1 mol of a phthalonitrile or diiminoisoindoline compound,
It is preferably 0.5 to 2 mol.

Further, in the general formulas (IIIa) to (IIId) and (IVa) to (IVd), in the case of a so-called metal-free phthalocyanine in which M is two hydrogen atoms, It can be produced by reacting at least one phthalonitrile compound represented by the formula (I) or at least one diiminoisoindoline compound represented by the general formula (II) with lithium or sodium.

Also in the case of this reaction, it is preferable to carry out in an organic solvent (especially alcohol system). That is, phthalonitrile or diiminoisoindoline compound, Na, L
i, CH ₃ ONa, the presence of such NaH or butyllithium are reacted in 70 to 150 ° C. in an alcohol. Here, the addition amount of the metal Li or Na is preferably 0.5 to 4 times the mol of the phthalonitrile or the diiminoisoindoline compound. The specific example of the alcohol used and the amount of alcohol are exactly the same as in the production of the above-mentioned metal phthalocyanine, but the reaction temperature is 150 ° C. or lower. If it exceeds 150 ° C, the amount of decomposition products is increased.

Further, the above general formulas (V a) to (V a of the present invention are
The phthalocyanine near-infrared absorbing material represented by d) is represented by the general formula (IIIa) to (IIId) or (IVa) to (IV
It can be obtained by halogenating the phthalocyanine compound represented by d). The halogenation reaction in this case is described in JP-A-3-62878 and 3-215466.
No. 4, No. 4-348168, No. 4-226390, No. 4-15263, No. 4-15264, No. 4-152.
No. 65, No. 4-15266, No. 5-17477, No. 5-86301, No. 5-25177, No. 5-251.
No. 79, No. 5-17700, No. 5-1272, etc. can be used as they are. That is, in one or a mixture of two or more of a halogen-based solvent, hydrocarbon or water,
It is obtained by reacting a halogenating agent such as bromine.

[0038]

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

Example 1 (Synthesis of phthalonitrile) 20 g of 3-hydroxyphthalonitrile and 10.55 g of potassium carbonate were dissolved in 180 ml of N, N-dimethylformamide by heating, and 18 g of chloromethyltrimethylsilane was added dropwise at 40 ° C. under an argon atmosphere. After completion of the dropping, the reaction temperature is kept at 80 to 90 ° C. for 30
Stir for hours. After cooling the reaction tank to room temperature, 250 ml of dilute hydrochloric acid was injected, and the liquid was separated with 1.2 l of toluene.
After washing the organic layer thoroughly with water, excess water was removed with magnesium sulfate, and then toluene was distilled off to remove triene /
It was purified by a silica gel column to obtain 23.3 g (yield 73.0%) of a compound represented by the following formula (VII). This compound is a white crystal and its melting point is 112.5 ° C. The IR spectrum is shown in FIG.

[0040]

[Chemical 17]

Example 2 (Synthesis of phthalonitrile) 3-nitrophthalonitrile 3
0 g of N, N-dimethylacetamide / 1-methyl-2
-Pyrrolidone = 1/1 (volume ratio) dissolved in 180 ml of mixed solvent, 11.97 g of sodium nitrite was added, and the temperature was adjusted to 1
The mixture was stirred at 65 ° C for 40 minutes, the temperature was lowered to room temperature, 16.8 g of potassium carbonate was added, and the mixture was stirred at a temperature of 150 ° C for 40 minutes. The temperature is lowered to 40 ° C., 25 g of chloromethyltrimethylsilane is added dropwise, and the reaction temperature is 80 to 90 ° C. after completion of the addition.
And kept for 28 hours. After cooling the reaction tank to room temperature, 350 ml of dilute hydrochloric acid was injected, and toluene 1.5 was added.
After separating with l, the organic layer was thoroughly washed with water, excess water was removed with magnesium sulfate, and then toluene was distilled off, followed by purification with a triene / silica gel column, which was represented by the following formula (VII). 29.8 g (yield 74.
7%) was obtained.

Example 3 (Synthesis of diiminoisoindoline) 20 g of phthalonitrile represented by the above formula (VII) and 14 g of sodium methoxide were introduced into 180 ml of methanol and stirred at room temperature for 1 hour while blowing ammonia gas. Then, ammonia gas was blown in while heating under reflux, and the mixture was stirred for 3 hours and cooled to room temperature. The reaction product was concentrated as much as possible, dissolved in 700 ml of chloroform, thoroughly washed with water and warm water, excess water in the organic layer was removed with magnesium sulfate, chloroform was distilled off, and recrystallized with hexane. ,
19.7 g (yield 91.7%) of the compound represented by the following formula (VIII) was obtained.

[0043]

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Example 4 (Synthesis of phthalonitrile) 20 g of 4-hydroxyphthalonitrile and 10.55 g of potassium carbonate were dissolved in 200 ml of N, N-dimethylformamide by heating, and 20 g of chloromethyltrimethylsilane was added dropwise at 40 ° C. under an argon atmosphere. After the dropping, the reaction temperature is kept at 85 to 105 ° C. and 1
Stir for 8 hours. After cooling the reaction to room temperature,
250 ml of diluted hydrochloric acid was injected, 1.2 l of toluene was used for liquid separation, the organic layer was thoroughly washed with water, excess water was removed with magnesium sulfate, and then toluene was distilled off, followed by purification with a triene / silica gel column. 24.6 g (yield 77.0%) of the compound represented by the following formula (IX) was obtained.

[0045]

[Chemical 19]

Example 5 (Synthesis of phthalonitrile) 20 g of 3-hydroxyphthalonitrile and 10.55 g of potassium carbonate were dissolved in 200 ml of N, N-dimethylformamide by heating, and 20 g of 1-chloroethyltrimethylsilane was added at 30 ° C. under an argon atmosphere.
The temperature was kept at 85 to 100 ° C. at the same time when the dropping was completed, and the mixture was stirred for 36 hours. After cooling the reaction mixture to room temperature, 200 ml of dilute hydrochloric acid was injected, the mixture was separated with 1 l of toluene, the organic layer was thoroughly washed with water, and excess water was removed with magnesium sulfate, followed by purification with a toluene / silica gel column. Then, 16.9 g (yield 49.9%) of a compound represented by the following formula (X) was obtained. The compound was white crystals and had a melting point of 67.5 ° C. The IR spectrum is shown in FIG.

[0047]

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Example 6 (Synthesis of phthalonitrile) 20 g of 3-hydroxyphthalonitrile and 10.55 g of potassium carbonate were dissolved by heating in 150 ml of a mixed solvent of N, N-dimethylacetamide / dimethyl sulfoxide = 5/1 (volume ratio), Under an argon atmosphere, 31.4 g of 3-chloropropyltrimethylsilane was added to 4
Drip at 5 ° C, and at the same time the temperature is 90 to 110 ° C at the end of the dropping.
And stirred for 24 hours. After cooling the reaction product to room temperature, 180 ml of dilute hydrochloric acid was injected, and toluene 1.2 was added.
The organic layer was thoroughly washed with water, excess water was removed with magnesium sulfate, and the mixture was purified with a toluene / silica gel column to give the compound represented by the following formula (XI) to 2
5.5 g (yield 71.2%) was obtained. The compound was white crystals and had a melting point of 145 ° C. The IR spectrum is shown in FIG.

[0049]

[Chemical 21]

Comparative Example 20 g of trimethylsilylmethanol was dissolved in 60 ml of N, N-dimethylformamide, the temperature was adjusted to 5 ° C. in a water bath, 4.6 g of sodium hydride was added under an argon atmosphere, and the mixture was stirred at 5 ° C. for 1 hour. Then, 33.3 g of 3-nitrophthalonitrile dissolved in 160 ml of N, N-dimethylformamide was gradually added dropwise. After completion of the addition, the ice bath was removed and the mixture was stirred at room temperature for 24 hours. 200 ml of dilute hydrochloric acid was fed to the reaction product, liquid separation was carried out with 1 l of toluene, the organic layer was thoroughly washed with water, and then excess water was removed with magnesium sulfate, and then purification was carried out with a toluene / silica gel column. The target compound of the formula (VII) is hardly obtained, the yield is about 1%, and 3-methoxyphthalonitrile is a by-product of the formula (VII).
It was produced in several times as much weight as the compound represented by.

Example 7 (Synthesis of phthalocyanine) 10 g of phthalonitrile represented by the above formula (VII) was dissolved in 32 g of hexanol by heating, 4 g of diazabicyclononene was added, and further 1.8 g of nickel chloride was added. 120 to 1 under Ar atmosphere
The mixture was stirred at 30 ° C for 24 hours. The reaction product was cooled to room temperature, the insoluble matter was filtered off, the hexanol of the filtrate was dried as much as possible, and the following formulas (1A) (1B) (1C) and (1D) were applied to a toluene / silica gel column. Indicated by (1
A) / (1B) / (1C) / (1D) = 30/48/2
5.6 g of a 2/0 mixture (yield 52.6%) was obtained. The λmax of this mixture in chloroform was 700.
was nm.

[0052]

[Chemical formula 22]

[Chemical formula 23]

[Chemical formula 24]

[Chemical 25]

Example 8 (Synthesis of phthalocyanine) 10 g of phthalonitrile represented by the above formula (IX) was dissolved in 30 g of butanol by heating, and then 4.1 g of diazabicycloundecene was added,
Furthermore, 1.7 g of copper chloride was added, and the mixture was heated under reflux for 36 hours in an Ar atmosphere. The reaction product is cooled to room temperature, the insoluble matter is filtered off, the butanol in the filtrate is distilled off, and the product is represented by the following formulas (2A) (2B) (2C) and (2D) on a toluene / silica gel column. (2A) / (2B) / (2C) /
6.8 g (yield 63.6%) of a mixture of (2D) = 38/42/15/5 was obtained. The λmax in chloroform of this mixture was 682 nm.

[0054]

[Chemical formula 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

Example 9 (Synthesis of phthalocyanine) 10 g of the diiminoisoindoline represented by the formula (VIII) was dissolved in 30 g of n-amyl alcohol by heating, 2 g of palladium chloride was added, and the mixture was refluxed under heating in an Ar atmosphere. It was stirred for 28 hours. The reaction product is cooled to room temperature, the insoluble matter is filtered off, the amyl alcohol in the filtrate is dried, and the product is represented by the following formulas (3A) (3B) (3C) and (3D) on a toluene / silica gel column. (3A) / (3B) / (3C) / (3D) = 4
6.2 g of a mixture of 0/40/20/0 (yield 59.7)
%) Was obtained. Λm of this mixture in chloroform
The ax was 693 nm.

[0056]

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[Chemical 31]

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[Chemical 33]

Example 10 (Synthesis of phthalocyanine) 10 g of the phthalonitrile represented by the formula (X) was dissolved in 25 g of n-amyl alcohol by heating, 4.5 g of diazabicycloundecene was added, and then palladium chloride 2 was added. 0.3 g was added, and the mixture was stirred under Ar atmosphere at 120 to 125 ° C. for 32 hours, cooled to room temperature, the insoluble matter was filtered off, the amyl alcohol in the filtrate was dried, and the mixture was dried with a toluene / silica gel column. (4A) / (4B) / (4C) / (4D) = 10/80 represented by the following formulas (4A), (4B), (4C) and (4D)
4.8 g of a mixture of / 10/10 was obtained (yield 43.3%). The λmax in chloroform of this mixture is
It was 699 nm.

[0058]

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Example 11 (Synthesis of phthalocyanine) 10 g of the phthalonitrile represented by the formula (XI) was dissolved in 40 g of n-amyl alcohol under heating, and 4 g of diazabicycloundecene was added,
Then, 2 g of palladium chloride was added and 115
Stir at ~ 130 ° C for 27 hours, cool the reaction mixture to room temperature, collect the insolubles by filtration, dry the amyl alcohol in the filtrate, and dry with toluene / chloroform = 1/1 (volume ratio) / silica gel column. , The following formulas (5A) (5B) (5C)
And (5A) / (5B) / (5C) indicated by (5D)
5.8 g of a mixture of / (5D) = 20/80/0/0
(Yield 52.6%) was obtained. The λmax of this mixture in chloroform was 691 nm.

[0060]

[Chemical 38]

[Chemical Formula 39]

[Chemical 40]

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Example 12 (Halogenation of phthalocyanine) The phthalocyanine mixture obtained in Example 9 was dissolved in a mixed solvent of dichloromethane and water, bromine was added, the mixture was heated to 40 to 60 ° C., and the organic layer was cooled. By concentrating, the following formulas (6A) (6B)
(6A) / (6B) / shown by (6C) and (6D)
A mixture of (6C) / (6D) = 40/40/20/0 was obtained. The λmax in chloroform was 707 nm, which was a long wavelength. The phthalocyanine mixture obtained in Examples 7, 8, 10 and 11 can also be halogenated.

[0062]

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[Chemical 43]

[Chemical 44]

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Table 1 shows examples of phthalonitrile and diiminoisoindoline other than the compounds obtained in Examples 1 to 6.

[0064]

[Table 1]

Table 2 shows examples of phthalocyanines other than the compounds obtained in Examples 7 to 11. The isomers as described above are not listed separately (of course, isomers exist).

[0067]

[Table 2- (1)]

[0068]

[Table 2- (2)]

(Evaluation) The phthalocyanine compounds obtained in Examples 7 to 11 are soluble in various solvents, a coating film obtained by a solvent coating method can be easily obtained, and excellent absorption ability in the near infrared region is obtained. Have.

Application Example 1 On a polymethylmethacrylate plate having a thickness of 1.2 mm, using a photopolymer, a depth of 1000Å and a half value width of 0.4 μ
m, track pitch of 1.4 μm, a 1,2-dichloroethane solution of the mixture of the formulas (6A) to (6D) was spinner coated on a substrate having a guide groove formed thereon, and a recording layer having a thickness of 1000 Å was provided for additional writing. Type recording medium.

Application Examples 2 to 5 In Example 1, instead of the mixture of the formulas (6A) to (6D), the compound Nos. 22, No.
25, no. 26, No. Recording media of Application Examples 2 to 5 were obtained in the same manner except that 33 was used.

Application Comparative Example 1 Recording of the application comparative example was performed in the same manner as in Application Example 1 except that the phthalocyanine compound represented by the following formula (XII) was used in place of the mixture of the formulas (6A) to (6D). The medium was obtained.

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Using the recording media of Application Examples 1 to 5 and Application Comparative Example 1 described above, recording was performed through the substrate under the following recording conditions,
Then, the recording position was reproduced with a continuous laser beam, and the C / N was measured under the following conditions. The reflectance was also measured. Table 3 shows the results. Recording conditions: linear velocity 2.1 m / sec recording frequency 1.25 MHz laser oscillation wavelength 680 nm pickup lens N.P. A. 0.5 Playback condition: Scanning filter 30KHz Bandwidth Playback power 0.25-0.3mW

[0074]

[Table 3] ┛

Application Example 6 Thickness 1.2 mm, groove depth 1000 Å, half width 0.45 μ
m and a 1.2 mm thick injection-molded polycarbonate substrate having guide grooves with a track pitch of 1.6 μm, the mixture of the above formulas (6A) to (6D) was mixed with ethyl cellosolve / T.
Dissolve it in a mixed solution of HF, apply it with a spinner, provide a recording layer with a thickness of 1800 Å, and further add 110 Au on it.
A reflective layer was vacuum-deposited to a thickness of 0Å, and an acrylate-based photopolymer was applied onto the reflective layer by spinner to form a protective layer having a thickness of about 6 μm.

Application Examples 7 to 10 In Application Example 6, instead of the mixture of formulas (6A) to (6D), compound Nos. 22, No. Two
3, No. 33, No. Recording media of Application Examples 7 to 10 were obtained in the same manner except that No. 35 was used.

Application Comparative Example 2 In Application Example 6, a mixture of brominated alkoxyphthalocyanine isomers 2/8 represented by the following formulas (XIIIa) and (XIIIb) is used instead of the mixture of formulas (6A) to (6D). A recording medium of Application Comparative Example 2 was obtained in the same manner except that it was omitted.

[Chemical 47]

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Application Comparative Example 3 In Application Example 6, a mixture of brominated alkoxyphthalocyanine isomers 2/8 represented by the following formulas (XIIIc) and (XIIId) is used instead of the mixture of formulas (6A) to (6D). A recording medium of Application Comparative Example 3 was obtained in the same manner except that it was omitted.

[Chemical 49]

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Using the recording media of Application Examples 6 to 10 and Application Comparative Examples 2 to 3, a laser oscillation wavelength of 790 nm and a linear velocity of 1.
The EFM signal was recorded under the recording condition of 4 m / sec, the C ₁ error at the optimum recording power Po and the optimum recording power × 0.82 was measured, and further 75,000 Lux light at Po and the C after 700 hours were measured. _The number of errors was measured. The results are shown in Table 4.

[0080]

[Table 4]

(Evaluation) Since the phthalocyanine compound of the present invention is highly stable and has a high refractive index in the range of 770 to 830 nm, it is possible to give excellent properties to an optical recording material.

[0082]

The phthalocyanine near-infrared absorbing materials according to claims 3 to 5 have the general formulas (IIIa) to (IIId) and (IVa).
To (IV d) and (V a) to (V d) have a structure represented by
It is soluble in various organic solvents while maintaining stability to light and has a high near-infrared absorption ability. As a result, it becomes possible to form a coating film by a solvent coating method, the application form is greatly expanded, and it is useful as an optical recording medium.

The phthalonitrile compound of claim 1 and the diiminoisoindoline compound of claim 2 have the structures represented by the general formula (I) and the general formula (II), respectively. It becomes useful as an intermediate for phthalocyanine near-infrared absorbing materials.

A method for producing the phthalonitrile compound represented by the general formula (I) in claims 6 to 7 and the general formulas (IIIa) to (IIId) and (IVa) to (IVd in claim 8 )
In any of the methods for producing a metal phthalocyanine compound represented by, it is possible to easily obtain the target product under mild conditions, and thus all are industrially extremely advantageous production methods.

[Brief description of drawings]

1 is the I of the phthalonitrile compound obtained in Example 1. FIG.
It is an R spectrum figure.

FIG. 2 I of the phthalonitrile compound obtained in Example 5
It is an R spectrum figure.

FIG. 3 I of the phthalonitrile compound obtained in Example 6
It is an R spectrum figure.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C09B 47/073 47/18 C09K 3/00 105

Claims (8)

[Claims] 1. A phthalonitrile compound represented by the following general formula (I): Embedded image (In the formula, each of R ^{1 to} R ⁴ represents the following. R ¹ : a linear or branched alkylene group having 1 to 8 carbon atoms, which contains a so-called ether bond of —C—O—C—. R ^{2 to} R ⁴ , which may be substituted or unsubstituted with a silyl group, are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a vinyl group,
Or -OSi (R ⁵⁾ ₃ group or a -CH ₂ Si (R ⁵⁾ ₃ group, R ^5: an alkyl group having 1 to 3 carbon atoms. ) 2. A diiminoisoindoline compound represented by the following general formula (II). Embedded image (In the formula, each of R ^{1 to} R ⁴ represents the following. R ¹ : a linear or branched alkylene group having 1 to 8 carbon atoms, which contains a so-called ether bond of —C—O—C—. R ^{2 to} R ⁴ , which may be substituted or unsubstituted with a silyl group, are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a vinyl group,
Or -OSi (R ⁵⁾ ₃ group or a -CH ₂ Si (R ⁵⁾ ₃ group, R ^5: an alkyl group having 1 to 3 carbon atoms. ) 3. A phthalocyanine near-infrared absorbing material composed of one or a mixture of two or more of four kinds represented by the following general formulas (IIIa) to (IIId). Embedded image [Chemical 4] Embedded image [Chemical 6] (In the formula, M and X ^{1 to} X ¹⁶ each represent the following. M: 2 hydrogen atoms, divalent metal atom, monosubstituted trivalent metal atom, disubstituted tetravalent metal atom or oxy. metal atom, X ¹ to X ^16: each independently -OR ¹ SiR ² R ³ R ⁴ group, R ^1: linear or branched alkylene group having 1 to 8 carbon atoms, in the radical -C-O-C- Which may contain a so-called ether bond or which may be substituted with a silyl group, R ^{2 to} R ⁴ : each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. Group, vinyl group,
Or —OSi (R ⁵ ) ₃ group or —CH ₂ Si (R ⁵ ) ₃ group, R ⁵ : an alkyl group having 1 to 3 carbon atoms, an atom other than X ^{1 to} X ¹⁶ attached to the benzene ring: a hydrogen atom or a halogen atom. ) 4. A phthalocyanine near-infrared absorbing material comprising one kind or a mixture of two or more kinds out of four kinds represented by the following general formulas (IVa) to (IVd). [Chemical 7] Embedded image [Chemical 9] [Chemical 10] (In the formula, M and X ^{1 to} X ¹⁶ each represent the following. M: 2 hydrogen atoms, divalent metal atom, monosubstituted trivalent metal atom, disubstituted tetravalent metal atom or oxy. metal atom, X ¹ to X ^16: each independently -OR ¹ SiR ² R ³ R ⁴ group, R ^1: linear or branched alkylene group having 1 to 8 carbon atoms, in the radical -C-O-C- Which may contain a so-called ether bond or which may be substituted with a silyl group, R ^{2 to} R ⁴ : each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. Group, vinyl group,
Or —OSi (R ⁵ ) ₃ group or —CH ₂ Si (R ⁵ ) ₃ group, R ⁵ : an alkyl group having 1 to 3 carbon atoms, an atom other than X ^{1 to} X ¹⁶ attached to the benzene ring: a hydrogen atom or a halogen atom. ) 5. A phthalocyanine near-infrared absorbing material composed of one or a mixture of two or more of four kinds represented by the following general formulas (Va) to (Vd). [Chemical 11] [Chemical 12] [Chemical 13] Embedded image (In the formula, M, X ^{1 to} X ¹⁶ , Y and n ^{1 to} n 4 respectively represent the following: M: two hydrogen atoms, divalent metal atom, monosubstituted trivalent metal atom, disubstituted Tetravalent metal atom or oxymetal atom, X ^{1 to} X ¹⁶ : each independently —OR ¹ SiR ² R ³ R ⁴ group, R ¹ : a linear or branched alkylene group having 1 to 8 carbon atoms, and It may contain a so-called ether bond of C—O—C— and may be substituted with a silyl group. R ^{2 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a carbon atom. Number 1 to 3 alkoxy group, vinyl group,
Or —OSi (R ⁵ ) ₃ group or —CH ₂ Si (R ⁵ ) ₃ group, R ⁵ : an alkyl group having 1 to 3 carbon atoms, an atom other than X ^{1 to} X ¹⁶ attached to the benzene ring: a hydrogen atom or a halogen Atom, Y: halogen atom, n1 to n4: each independently represent the number of halogen substitutions,
An integer from 1 to 4. ) 6. A compound of the following general formula (VI) ZR ¹ SiR ² R ³ R ⁴ (VI) (wherein R ^{1 to} R ^{4 is} prepared by reacting 3- or 4-hydroxyphthalonitrile in the presence of an alkali in an organic solvent. And Z each represent the following: R ¹ : a linear or branched alkylene group having 1 to 8 carbon atoms, which may contain a so-called ether bond of —C—O—C— or silyl. R ^{2 to} R ⁴ , which may be substituted with groups, each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a vinyl group,
Or -OSi (R ⁵⁾ ₃ group or a -CH ₂ Si (R ⁵⁾ ₃ group, R ^5: an alkyl group having 1 to 3 carbon atoms, Z: halogen atoms. ) A compound for producing a phthalonitrile compound represented by the above general formula (I), which comprises reacting with at least one compound represented by the formula (1). 7. 3- or 4-nitrophthalonitrile,
After reacting with sodium nitrite and potassium carbonate or a sodium metal compound in an organic solvent, the above general formula (VI) ZR ¹ SiR ² R ³ R ⁴ (VI) (wherein R ^{1 to} R ⁴ and Z are Respectively represent the following: R ¹ : a linear or branched alkylene group having 1 to 8 carbon atoms, which may contain a so-called ether bond of —C—O—C— or which is substituted with a silyl group. R ^{2 to} R ⁴ , which may be each, independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a vinyl group,
Or -OSi (R ⁵⁾ ₃ group or a -CH ₂ Si (R ⁵⁾ ₃ group, R ^5: an alkyl group having 1 to 3 carbon atoms, Z: halogen atoms. ) A method for producing a phthalonitrile compound represented by the general formula (I), which comprises reacting at least one compound represented by the formula (1). 8. At least one phthalonitrile compound represented by the general formula (I) or at least one diiminoisoindoline compound represented by the general formula (II), a divalent metal and a mono-substituted compound. Reacting with a metal selected from a trivalent metal, a disubstituted tetravalent metal or an oxymetal, or a derivative of these metals.
A method for producing at least one phthalocyanine compound represented by IIa) to (IIId) and (IVa) to (IVd).