JPH02298557A - Phthalocyanine compound and production thereof - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [M is metal (oxide), metal halide or two H atoms; X<1> to X<8> are H or imino of formula II or formula III (Y is strong organic base); X<1> and X<2>, X<3> and X<4>, X<5> and X<6>, and X<7> and X<8> are different from each other]. USE:An organic pigment for optical disk. PREPARATION:The objective compound is produced by reacting a phthalocyanine compound of formula IV (Y<1> to Y<8> are H or amino provided that Y<1> and Y<2>, Y<3> and Y<4>, Y<5> and Y<6>, and Y<7> and Y<8> are different from each other) With glyoxylic acid or terephthalaldehyde acid and reacting the resultant compound of formula V (Y<1>' to Y<8>' are H or group of formula VI or formula VII provided that Y<1>' and Y<2>', Y<3>' and Y<4>', Y<5>' and Y<6>', and Y<7>' and Y<8>' are different from each other) with a strong organic base.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a phthalocyanine compound and a method for producing the same, and more particularly to a novel phthalocyanine compound useful as an organic dye for optical discs and an efficient method for producing the same.

[Prior art and problems to be solved by the invention] Conventionally, l, 4° 5.8, 9 has been used as an organic dye for optical disks.
．． Phthalocyanine compounds having alkylamino groups at at least 5 positions (usually 8 positions) selected from the 12, 13- and 16-positions are known (Japanese Patent Application Laid-Open No. 6-11992).
0-209583).

By the way, in order for a specific substance to be effectively used as a dye for optical disks, the maximum value of the light absorption wavelength of that substance (
λmax) is required to be around 800 nm.

However, although the above-mentioned known phthalocyanine compounds almost satisfy the required performance of the dye for optical disks, they have the disadvantage that the compounds are bulky and have somewhat poor photosensitivity because they have a large number of alkylamino groups. . Furthermore, in order to introduce an alkylamino group, it is necessary to first introduce a halogen into the corresponding position and then perform alkylamino formation, which is inconvenient in terms of production.

Therefore, the present inventors solved the drawbacks of the above-mentioned conventional technology,
We have conducted extensive research in order to develop a phthalocyanine compound that has an absorption maximum near 800 nm and is highly photosensitized, as well as a method for easily producing this compound using simple operations.

[Means for solving the problem] As a result, it was discovered that a phthalocyanine compound having a specific imino group at a specific position has an appropriate maximum absorption wavelength, high photosensitivity, and can be easily produced. . The present invention was completed based on this knowledge.

That is, the present invention is based on the general formula [■] [wherein M represents a metal, a metal oxide, a metal halide, or two hydrogen atoms, and X1 to XB are hydrogen atoms or formula% (in the formula, Y is a strong organic base.) represents an imino group. However, Xl and X2°X3 and X4. χ5
and x6. x' and X8 indicate different things. ] A phthalocyanine compound represented by the following is provided.

In the phthalocyanine compound represented by the above general formula (1), the metal represented by M may be any metal that can form a complex with phthalocyanine, and specifically, Cu, C
o, Ni, Pb, Zn, V, etc. Further, as the metal oxide represented by M, for example, VO, Tie, Z
There are rO, ThO, etc., and the metal halide represented by M is Aj2CI! ,.

Aj2Br, GaCl2. Examples include GaBr. Furthermore, M may represent two hydrogen atoms.

Further, Y is a strong organic base, and specific examples thereof include 1.
5-diazabicycloC4,3,0)non-5-ene (hereinafter abbreviated as DBN); 1°8-diazabicyclo(
Examples include 5,4,0l-7-undecene (hereinafter abbreviated as DBU)il, B-bis(dimethylamino)naphthazine, tetramethylammonium hydroxide, diorthotolylguanidine, diphenylguanidine, and the like.

Furthermore, when the phthalocyanine skeleton is abbreviated as MPc, the phthalocyanine compound of the present invention is represented by the general formula or the general formula [■].

According to the method of the present invention, the phthalocyanine compound of the general formula (1) can be obtained by forming a compound of the general formula (II) [wherein M is the same as above, and Y1 to YB are hydrogen or an amino group.

However, Yl and yz, yz and Y4. Y5 and Y6. Y
7 and YB indicate different things. ] The phthalocyanine compound represented by is reacted with glyoxylic acid or terephthalaldehydic acid to obtain the general formula (III) [wherein M is the same as above, and Y1' to YB' are hydrogen or Indicates the group represented. However, Yl'' and Y2'.

Y3' and Y4', YS' and Y6" Y7° and ye' are different.] It can be produced by reacting the compound represented by these with the above-mentioned strong organic base represented by Y.

In the method of the present invention, first, 4 to 20 mol, preferably 5 to 20 mol, of glyoxylic acid or terentaldehydic acid per 1 mol of the phthalocyanine compound of the general formula [IT].
15 mol of solvent 10-100 1 preferably 20-70
I! , react inside. Here, as the solvent, dimethylbormamide, dimethyl sulfoxide, α-chloronaphculene, etc. can be used. In addition, the above reaction may optionally be performed using Tl-)luenesulfonic acid or stannic chloride.

This can be carried out in the presence of a catalyst such as zinc chloride, titanium tetrachloride, or boron trifluoride.

Other reaction conditions may be selected as appropriate depending on the situation, but
Usually 60 to 250°C1 preferably 80°C under atmospheric pressure.
2 to 20 hours at a temperature of ~200 °C, preferably 4 to 1
The reaction may be carried out for about 5 hours.

The phthalocyanine compound of the general formula ('II) used as a starting material can be prepared by a known method, for example, as disclosed in Japanese Patent Application No. 1983.
It can be produced by the method described in Japanese Patent Application No.-299818.

Next, 4 to 20 mol, preferably 5 to 15 mol of a strong organic base represented by Y is used per 1 mol of the obtained phthalocyanine derivative of the general formula (I[[), and 10 to 100 mol of the solvent is used.
The neutralization reaction is carried out in j2, preferably 20-70f. Solvents that can be used in this neutralization reaction include various alcohol solvents such as methanol, ethanol, propatool, and butanol.

For neutralization, other conditions can be selected as appropriate depending on the situation and cannot be determined uniquely, but usually at a temperature of 10 to 100°C, preferably 20 to 70°C, and 0.5 The reaction may be carried out for about 5 hours, preferably 1 to 3 hours.

1 #giE □)r 'l &Zゝ” I
J□ 'a h t knee ("307 Talocyanine compound is a substance that is solid at room temperature and soluble in water, methanol, and ethanol, and has a maximum absorption wavelength of 750 to 8
00 nm, ε (extinction coefficient) 1-2X10'.

(Example) Next, the present invention will be explained in more detail based on examples.

Example 1 Synthesis of a compound of the general formula [■], Y=DBU, M=VO, that is, a compound of the following formula 3.3°, 3”, 3” per-tetraaminovanadyl phthalocyanine (0.5 g) and α-chloronaphthalene (30 m of the mixture at 90°
After stirring for 1 hour at C, glyoxylic acid monohydrate (1 g
) and p-toluenesulfone M (30■) processed 90
Stirred for an additional 7 hours at °C. After cooling, the precipitate was collected by filtration and washed with toluene.

Add the filtered material to methanol (150mR) and further add DB
U (1 g) was added and stirred at 25°C for 1 hour. After filtering to remove insoluble matter, the filtrate was concentrated, washed with acetone, and dried. Yield 1.1 solid substance at room temperature
g' (96 mol%).

The obtained compound was confirmed to be the title compound by the following physical properties and the infrared absorption (IR) spectrum shown in FIG. 1 and the nuclear magnetic resonance (NMR) spectrum shown in FIG. 2.

λmax= 780nm (methanol) Elemental analysis CHNV Calculated value (%) 62.0 5.7 19.0 3.5
Actual value (%) 60.9 5.9 18.3 3.2
Example 2 Synthesis of a compound of general formula [v], Y=DBU, M=VO, that is, a compound of the following formula 3.3° 3 + +
, 3 + + + itetraaminovanadyl phthalocyanine (0,5 g) and α-chloronaphthalene (3
The mixture of 0d) was stirred at 90°C for 1 hour, then terephthalaldehydic acid monohydrate (1g) and P-)luenesulfonic acid (30μ) were added, and the mixture was further stirred at 150°C for 4 hours. After cooling, the precipitate was collected by filtration and washed with toluene.

Add the filtered material to methanol (150 mN) and further add DB
U (1 g) was added and stirred at 25°C for 1 hour. After filtering to remove insoluble matter, the filtrate was concentrated, washed with acetone, and dried. Yield 0.1 solid material at room temperature
5 g (11 mol %) was obtained.

The obtained compound had the following physical properties and I shown in FIG.
The title compound was confirmed by the R spectrum and the NMR spectrum shown in FIG.

λmax” 780 nm (methanol) Elemental analysis CHNV Calculated value (%) 67.6 5.7 15.8 2.9
Actual value (%) 66.0 5.5 16.4 2.8
Example 3 In the general formula [IV], synthesis of a compound where Y=DBU, M=Cu, that is, a compound of the following formula II (DBUH-0-C-CH=N)4CuPc3.3',
3”,3”'-tetraamino copper phthalocyanine (0,5
g), α-chloronaphthalene (30 ml, glyoxylic acid monohydrate (1 g) and p-toluenesulfonic acid (3
(0 mg) was stirred at 90°C for 3 hours. After cooling, the precipitate was collected by filtration and washed with toluene.

Add the filtered material to methanol (150 mF) and further add DB
U(Ig) was added and stirred at 25°C for 1 hour. After filtering to remove insoluble matter, the filtrate was concentrated. The concentrate was washed with acetone and toluene and dried. A yield of 0.6 g (52 mol %) of material that was solid at room temperature was obtained.

The obtained compound has the following physical properties and T shown in FIG.
The title compound was confirmed by the R spectrum and the NMR spectrum shown in FIG.

λmax=778nm (Quinoline) Elemental analysis CHN ICu Calculated value (%) 62.1 5.8 L9.1 4.
3 Actual value (%) 61.3 6.3 18.6 4.
0 Example 4 In general formula (IV), Y=DBL1. , M=Nt, i.e., the following formula: 3.3", 3"°
, 3”゛-tetraaminonickel phthalocyanine (0,
A mixture of α-chloronaphthalene (30g), glyoxylic acid monohydrate (1g) and p-)luenesulfonic acid (30g) was stirred at 90°C for 3 hours.

After cooling, the precipitate was collected by filtration and washed with toluene.

Add the filtered material to methanol (150 ml) and add DB
tJ (1 g) was added and stirred at 25"C for 1 hour.

After filtering to remove insoluble matter, the filtrate was concentrated. The concentrate was washed with acetone and toluene and dried. A yield of 0.3 g (26 mol %) of material that was solid at room temperature was obtained.

The obtained compound has the following physical properties and the T shown in Part 7.
The title compound was confirmed by the R spectrum and the NMR spectrum shown in FIG.

λmax = 772 nm (Quinoline) Elemental analysis CHN Ni Calculated value (%) 62.3 5.8 19.1 4.0
Actual value (%) 61.3 6.1 18.4 3.8
Example 5 Synthesis of a compound of Y-DBU, M=Cu in general formula (V), that is, a compound of the following formula 3.3", 3", 3"°
゛-Tetraamino epsilon phthalocyanine 0.5g), α
A mixture of -chloronaphthalene (30), terephthalaldehydic acid (1 g) and p-toluenesulfonic acid (30) was stirred at 150°C for 8 hours. After cooling, the precipitate was collected by filtration and washed with toluene.

Add the filtered material to methanol (150ml) and further add DB
U (1 g) was added and stirred at 25°C for 1 hour. After filtering to remove insoluble matter, the filtrate was concentrated and the concentrate was washed with acetone and toluene.

Dry. A yield of 0.3 g (22 mol %) of material that was solid at room temperature was obtained.

The obtained compound was confirmed to be the title compound based on the following physical properties and the infrared absorption TR spectrum shown in FIG. 9 and the NMR spectrum shown in FIG. 10.

λmax=781 nm (quinoline) Elemental analysis CHN Cu Calculated value (%) 67.7 5.7 18.1 3.6 Actual value (%) 66.9 6.4 17.3 3.2 Example 6 General formula [ V], synthesis of a compound where Y=DBU, M=Ni, that is, a compound of the following formula 3.3'', 3°゛, 3゛゛-tetraaminonickel phthalocyanine (0.5g)
, α-chloronaphthalene (30 mE), terephthalaldehydic acid (1 g) and p-)luenesulfonic acid (
30 mg) was stirred at 150°C for 8 hours. After cooling, the precipitate was collected by filtration and washed with toluene.

Add the filtered material to methanol (150 mN) and further add DB
U(Ig) was added and stirred at 25°C for 1 hour. After filtering to remove insoluble matter, the filtrate was concentrated and the concentrate was washed with acetone and toluene.

Dry. A yield of 0.2 g (14 mol %) of material that was solid at room temperature was obtained.

The obtained compound had the following physical properties, an infrared absorption IR spectrum shown in FIG. 11, and an NMR spectrum shown in FIG. 12.
The spectrum confirmed that it was the title compound.

1 λmax = 171 nm (Kinori elemental analysis CHN Ni calculated value (%) 67.9 5.7 1B, 1 3.3
Actual value (%) 67.0 6.1 17.5 2.9 [Effect of the invention] The phthalocyanine compound of the present invention has a substituent that is not bulky and has good photosensitivity as a pigment for optical discs. It has a suitable maximum absorption wavelength. Further, the phthalocyanine compound of the present invention is soluble in alcohol, and has the advantage that it can be dissolved in alcohol, which is a solvent that does not corrode the substrate when applied to the substrate. Such phthalocyanine compounds can be easily and efficiently produced by the method of the present invention.

Therefore, the phthalocyanine compound of the present invention is expected to be effectively utilized as a new dye for optical discs.

[Brief explanation of the drawing]

Figure 1 shows the infrared absorption spectrum of the product obtained in Example 1, Figure 2 shows the nuclear magnetic resonance spectrum of the product obtained in Example 1, and Figure 3 shows the product obtained in Example 2. 4 is the nuclear magnetic resonance spectrum of the product obtained in Example 2, FIG. 5 is the infrared absorption spectrum of the product obtained in Example 3, and FIG. 6 is the infrared absorption spectrum of the product obtained in Example 3. The obtained nuclear magnetic resonance spectrum, FIG. 7 is the infrared absorption spectrum of the product obtained in Example 4, and FIG. 8 is the infrared absorption spectrum of the product obtained in Example 4.
Figure 9 shows the nuclear magnetic resonance spectrum of the product obtained in Example 5, and the infrared absorption spectrum of the product obtained in Example 5.
Figure 0 is the nuclear magnetic resonance spectrum of the product obtained in Example 5, Figure 11 is the infrared absorption spectrum of the product obtained in Example 6, and Figure 12 is the nuclear magnetic resonance spectrum of the product obtained in Example 6. Nuclear magnetic resonance spectra of the products are shown, respectively.

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, M represents a metal, metal oxide, metal halide, or two hydrogen atoms, and X^1 to X^8 are hydrogen atoms or Indicates an imino group represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Y is a strong organic base). However, X^1 and X^2, X^3 and X^4,
^5 and X^6, X^7 and X^8 each indicate different things. ] A phthalocyanine compound represented by (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, M represents a metal, metal oxide, metal halide, or two hydrogen atoms, and Y^1 to Y^8 are hydrogen atoms or Indicates an amino group. However, Y^1, Y^2, Y^3
and Y^4, Y^5 and Y^6, and Y^7 and Y^8 each indicate different things. ] The phthalocyanine compound represented by is reacted with glyoxylic acid or terephthalaldehyde acid, and the obtained general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, M is the same as above, and Y^1'-Y ^8' indicates a hydrogen atom or a group represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. However, Y^1' and Y^2',
Y^3' and Y^4', Y^5' and Y^6', and Y^7' and Y^8' each represent different things. ] The method for producing a phthalocyanine compound according to claim 1, characterized in that the compound represented by the above is reacted with a strong organic base.