JPH02665A - Phthalocyanine compound - Google Patents

Abstract

NEW MATERIAL:A phthalocyanine compound of formula I (wherein M represents two H atoms, a metal atom of a Group VIII, Ib, IIb, IIIb, IVb, Va, VIa or VIIa, its oxide or a halogen compound; and A<1>-A<4> and B<1>-B<4> are heterocyclic rings whose optical properties change when irradiated with light in such a manner that the members in each of pairs A<1> and B<1>, A<2> and B<2>, A<3> and B<3>, and A<4> and B<4> may be cyclized into a cyclohexadiene ring, provided that when M represents two H atoms, the case in which A<1>-A<4> and B<1>-B<4> are simultaneously thiophene rings is excluded. EXAMPLE:A compound of formula II. USE:Various recording, memory materials, copying materials and light intensity- regulating materials having sensitivity to a semiconductor laser and showing photochromism of good heat stability of recording. PREPARATION:A compound of formula II is produced by dissolving a diiminoindoline compound of formula II in an organic solvent and heating the solution under reflux.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel phthalocyanine compound. Specifically, the present invention relates to various recording/memory materials, copying materials, light control materials, photosensitive materials for printing photoreceptors, lasers, photosensitive materials for phototypesetting, optical filters, masking materials, and photometers.

The present invention relates to a novel phthalocyanine compound having photochromic properties useful as a display material.

[Prior Art and Prior Art] Various compounds are known that have photochromic properties that develop or discolor when irradiated with light, and photochromic materials using these compounds have been proposed.

For example, JP-A-55-149812 proposes a photochromic material in which a spiropyran compound of the following formula is dispersed in a nitrocellulose resin.

(In the formula, R″ represents a hydrogen atom or a halogen atom, and R″
represents an alkyl group, and Rc represents a hydrogen atom or an alkoxy group.) Furthermore, Japanese Patent Publication No. 45-28892 proposes a photochromic material containing a spironaphthoxazine compound as shown in the following formula.

(In the formula, R6 represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group.) In recent years, attempts have been made to use such photochromic compounds as reversible optical recording materials. In this case, the following conditions must be met:

■ Semiconductor laser sensitivity ■ Non-destructive readout ■ Thermal stability of recording ■ Fast response speed ■ Repeat durability Among the above requirements, a spirobenzopyran derivative having a benzothiopyrane ring having a benzothiopyrane ring is used as a compound that improves semiconductor laser sensitivity. A photochromic material has been proposed [Nobutoshi Asai et al., Japan Society of Applied Physics (Spring)]
Proceedings 442 (1986) Ko.

0(:)13 In addition, as a compound that particularly improves the thermal stability of recording in (2), the present inventor previously disclosed in Japanese Patent Application No. 61-122696 a dithenyldicyanoethene derivative exhibiting the following photochromism and its use. We have proposed an optical recording material with good thermal stability for recording.

(In the formula, R', Rh, R', R', R', and R' represent an alkyl group.) [Problems to be Solved by the Invention] When using a photochromic compound as an optical recording material, the above In addition to thermal stability for recording, it is also important to meet the requirements of (1) sensitivity to semiconductor lasers; however, no optical recording material that meets these requirements has hitherto been proposed. Those containing a pyran rust conductor had the disadvantage of being inferior in thermal stability ((2)), and those made of a dithenyldicyanoethene rust conductor did not have the semiconductor laser sensitivity ((3)).

An object of the present invention is to provide a novel compound suitable for use as an optical recording material, which has absorption in the semiconductor laser region (600 to 900 nm) and exhibits photochromism with good thermal stability for recording.

The phthalocyanine compound of the present invention has the general formula [] (In the formula, M is 2H or group II, group Ib, group Ilb.

III Represents metal atoms of group b, group IVa, group Va, group Via, group ■a, and their oxides and halides; A
I, A2, A3, A4, Bl
, B 2 , B 3 and B 4 represent a heterocycle. However, A1 and s I A2 and B2 A3 and B3
．． A' and B4 are heterocycles that change their optical properties by cyclizing each other with light irradiation to form a cyclohexadiene ring. however,
When M is 2H, A1-A4. B1 to B4 are not thiophene rings at the same time. ).

In particular, the phthalocyanine compound of the present invention has the general formula [H
] (In the formula, M is 2H, Group Ib, Group Ilb.

III represents metal atoms of group b, group rVa, group Va, group VTa, group ■a, and their oxides and halides, X,
Y represents S, O, Se atom, RI, R2R8,
R6, R7Ra, R eye R+2 R+3 RR+7.
RI♂, R19,R", R23,R" represent an alkyl group, R3, R4, R9, RI O, RI 5
RR21 and R22 represent a hydrogen atom or an alkyl group.

However, when M is 2H, X and Y are not S atoms at the same time. ) Preferably, it is a compound represented by
In the above [I+] formula, RI R2R3R4R5,
R6, R7, R11, R9, RI OR1l RI
RR ', R' RI 6
R17, RI 8 R”R”R21
, R22, R23, R24 represent a linear or branched alkyl group having 1 to 20 carbon atoms, and M is 2HCu, Ni, C
It is preferable that the material exhibits o, Zn, Fe, or ■0.

The present invention will be explained in detail below.

In the present invention, A I , A 2 , A 3 ,
A 4 , B 1 , B2B5. The heterocyclic group represented by B4 is, for example, represented by the following general formula [III group, halogen atom, trifluoromethyl group, or an optionally substituted alkyl group, aryl group, or cycloalkyl group. ). Specific examples of such heterocyclic groups include the following.

group, halogen atom, trifluoromethyl group, R
(2) represents a hydrogen atom or an optionally substituted resolkyl group, aryl group, or cycloalkyl group. ) Alternatively, the following -formation [IV] (wherein, ring A represents a hydrocarbon ring or a heterocyclic ring, and among these, particularly preferred heterocyclic groups are the following -formation [IV]
V] ■ ■ ■ RRR represents hydrogen or an alkyl group. ).

Note that the above [+111. In the [IV] and [V] formulas, ■ ■ ■ ■ ■ ■ ■RRRR
The alkyl groups of RR and R include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, 5e
c-butyl group, n-pentyl group, n-hebutyl group, n-
hexyl group, n-octyl group, 2-ethylhexyl group,
01-2o such as n-stearyl group, preferably 01-4
Examples include straight-chain or branched alkyl groups. R■
■ ■ ■ Examples of the halogen atoms for R, R, and R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Further, examples of substituents for the alkyl group, aryl group, or cyclohexyl group of R and R include an alkoxy group, an alkoxyalkoxy group, an alkoxyalkoxyalkoxy group, an allyloxy group, an aryl group, an aryloxy group, a cyano group, a hydroxy group, Examples include tetrahydrofuryl group.

In the present invention, in the phthalocyanine compound represented by the above-mentioned -formation [If], the alkyl group represented by formula 9 % R23, R24 is a methyl group,
Ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, 5ec-butyl group, n-pentyl group, n-heptyl group, n-hexyl group, n-octyl group, 2- C8~ such as ethylhexyl group, n-stearyl group, etc.
Most preferred are straight or branched alkyl groups with 20% preferably 01-4.

The compound of the present invention can be produced, for example, as follows. That is, first, the following -formation % formula % [ (wherein R1, R2, R3, R4, R5, R6, R7,
R8, R9R" RII RI2 R"
R14, R]5. R16R"R" R+
9 R” R”, 22. R23R2
4 is the same as the above definition. ) in the presence of metallic sodium in an organic solvent such as methanol solvent while blowing ammonia gas under heating under reflux to form the following compounds [X] and [XI], respectively.

[X[[], [X[II] (wherein, Rl, R2, R3, R4, R5, Ra,
R? , R6, R9R1o R mouth R12, R+
3. R14, R15, RR17, -R", R", R"
, R'', R22, R23 and R24 are the same as defined above.) A diiminoindoline compound is obtained.

Next, these are dissolved in an organic solvent such as 2-(N,N-dimethylamino)ethanol or butanol, and either as is (when M is 2H) or the following -formation [section] MCflx '-"[X
A phthalocyanine compound represented by -formation [II can be produced by adding a metal salt represented by IV (wherein M is the same as defined above except 2H) and cyclizing by heating and refluxing. .

R" IJ R'"l R" In addition to methanol, ethanol,
Alcohol solvents such as n-propatol, n-butanol, and 1so-propatol are preferred. Furthermore, examples of metals used include potassium in addition to sodium.

The reaction temperature is preferably from room temperature to 150°C, particularly preferably from 60 to 90°C.

In addition, the organic solvent used when producing phthalocyanine compounds from diiminoindoline compounds is N
, N-dimethylaminoethanol, N,N-diethylaminoethanol, N,N-di-n-propylaminoethanol, and other N,N-alkylamino alcohol-based or butanol-based solvents are suitable, and the reaction temperature is 80°C. -200°C, especially 100-150°C is preferred.

Such a novel phthalocyanine compound of the present invention can be used as an optical recording material by forming a recording layer containing it by a method similar to a known method as described below.

For example, ■ If necessary, the phthalocyanine compound of the present invention,
Along with binders such as polyester resin, polystyrene resin, polyvinyl butyral resin, polyvinylidene chloride, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, epoxy resin, and phenol resin, carbon tetrachloride, benzene, cyclohexane, methyl ethyl ketone, It is dispersed or dissolved in a solvent such as tetrachloroethane and applied onto a suitable substrate.

(2) The phthalocyanine compound of the present invention is vapor-deposited on a suitable substrate by a known vapor deposition method or a co-evaporation method with other compounds.

(2) The phthalocyanine compound of the present invention is dissolved in the above-mentioned solvent and sealed in a glass cell or the like.

An optical recording material can be manufactured by forming a recording layer using the method described above.

In the method (2), the substrate used may be either transparent or opaque to the light used. Examples of the substrate material include supports for general recording materials such as glass, plastic, paper, plate-like or foil-like substrates, and among these, plastic is preferable from various points of view. Examples of the plastic include acrylic resin, methacrylic resin, vinyl acetate resin, vinyl chloride resin, nitrocellulose, polyethylene resin, polypropylene resin, polycarbonate resin, polyimide resin, polysulfone resin, and the like.

Application methods include doctor blade method, casting method,
A commonly used coating film forming method such as a spinner method or a dipping method can be employed.

On the other hand, as the vapor deposition method, a vacuum vapor deposition method, a sputtering method, etc. can be adopted.

The thickness of the recording layer formed on the substrate is 100 to 100μ.
m, particularly preferably 1000 to 10 μm. The recording layer may be provided on both sides of the substrate or only on one side.

Recording on an optical recording material using the phthalocyanine compound of the present invention obtained as described above is performed on a recording layer provided on both sides or one side of a substrate or a recording layer in a cell with a thickness of 1 to 10 μm.
By applying moderately focused semiconductor laser light,
It can be done easily. As a result, the area irradiated with light undergoes a color change due to absorption of light energy. The recorded information can be reproduced by reading the difference in reflectance or absorbance between a portion where a color change due to light has occurred and a portion where no color change has occurred.

[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 (1) Preparation of diiminoindoline compound A 50 cc three-hole flask was equipped with a cooling tube with a calcium chloride tube, a thermometer, and a gas inlet. Add 50mJZ of dry methanol to this and add 0.12g of metallic sodium (5,2
xlO-'moIl) and 2.1 g (6,
5x 10''mou) were sequentially dissolved. While introducing dry ammonia gas from the gas inlet, the mixture was stirred at room temperature for 1 hour, and then reacted under rapid flow for 3 hours. After distilling off the solvent, the product was purified by silica gel column chromatography.
Diiminoindoline compound (molecular weight 343) represented by the following structural formula 1.71g (4,99X10""moλ
) was obtained. (Yield 77%).

(2) Physical property values (i)' of diiminoindoline compounds
H-NMR (CDCus) δ = 1. 76
s 3H1, 79s
3H 2,07s 3H 2,09s 3H 2,25s 6H 3,60br, s 3H (ii) 13C-NMR (CDCJZ3) δ=1
66.5,136.0 135.0134.8,131
．． 8,131.0°127.8,127.7,14.2 1 3.2. 1 3. 0 (iii) IR (KBr) 1645 cm-' (=NH) (3) Production of phthalocyanine compound-1 Phthalocyanine compound represented by the following structural formula obtained in (1) (molecular weight t306
) 16 mg was obtained. (Yield 3%).

0.5g of diiminoindoline compound (1,
46xlO-3moJ2) was dissolved in 10 ml of 2-(N,N-dimethylamino)ethanol and heated under reflux for 20 hours. This reaction solution was filtered, the product was washed several times with small amounts of methanol and acetone, and then dried. 0.15 g of a diiminoindoline compound represented by the following structural formula obtained by the following structural formula (1) was dried with calcium chloride. It was dissolved in 5 mfl of dry butanol in a flask equipped with a reflux tube and heated to reflux. After 7 hours, the formed precipitate was filtered, washed with methanol and then acetone, and dried to obtain 12.8 mH of a phthalocyanine compound similar to (2) (yield: 8.5%). Furthermore, the filtrate was returned to the reaction vessel, and after heating for 13 hours, the generated precipitate was separated by filtration, washed with methanol and then acetone, and dried to again obtain 23.8 mg of a phthalocyanine compound (yield: 16
%). The obtained materials were totaled to obtain 36.6 mg of a phthalocyanine compound (yield: 24.8%).

(5) Physical property values of phthalocyanine compounds (3) (4)
λ1llax(0
- in dichlorobenzene) is 673 as shown in Figure 1.
nm, 610 nm, semiconductor laser region (600 nm)
It was confirmed that there was absorption at 900 nm).

Example 2 A phthalocyanine compound having the following structural formula was obtained in the same manner as in Example 1 except that 2.7 g of dicyanobis(2,4,5-triethylthienyl)etheno represented by the following structural formula was used. Ta.

Instead of 2.1 g of dicyanobis(2,4,5-trimethylthienyl)etheno represented by
nm, 610 nm, and it was confirmed that there was absorption in the semiconductor laser region (600 to 900 nm), similar to that obtained in Example 1.

Examples 3 to 9 The above-mentioned -formation [1! M in C is 2H, X and Y are S atoms, R1-R24 are the first
Synthesize compounds with alkyl groups shown in the table, each with 0
- λ□8 in dichlorobenzene was measured and the results are shown in Table 1.

Example 10 The following structural formula region (600-
It was confirmed that there was absorption at 900 nm).

A dry butanol solution containing 0.17 g of a diiminoindoline compound represented by the following structural formula (% formula %) and 0.027 g of copper acetate (I+) represented by
The mixture was heated under reflux for 0 hours to react. The reaction mixture was prepared in Example 1.
80 mg of a phthalocyanine compound represented by the following structural formula was obtained (yield 46.8%).
.

λ of the obtained phthalocyanine compound. ilX (in chloronaphthalene) has a wavelength of 583 nm as shown in Figure 2.
, 639 nm, and is a semiconductor.Example 11 0.13 g of the diiminoindoline compound represented by the following structural formula obtained in Example 1 (1) and 0.13 g of nickel chloride represented by the following structural formula % formula %. 09 g was added to 5 mL of dry butanol, and the reaction was carried out by heating and passing through the mixture for 20 hours.

The reaction product was treated in the same manner as in Example 1 (4) to obtain 2.8 mg of a phthalocyanine compound represented by the following structural formula (yield: 2.2%).

λ, n! of the obtained phthalocyanine compound 8 (in 1-methylnaphthalene) is 580 nm.

639 nm, which is in the semiconductor laser region (600-90
It was confirmed that there was absorption at 0 nm).

Example 12 0.50 g of the diiminoindoline compound represented by the following structural formula obtained in (1) of Example 1 was added to 5 ml of dried 2
- (N,N-dimethylamino) dissolved in ethanol,
To this was added zinc acetate dihydrate represented by the following structural formula 2%, and the mixture was heated under reflux for 20 hours. After washing the resulting precipitate with methanol, extraction was repeated with acetone to obtain 2 mg of a phthalocyanine compound represented by the following structural formula (yield: 0.4%).

The wavelengths of the ice crystal phthalocyanine compound λ, (1-methylnaphthalene) are 590 nm and 643 nm, and it was confirmed that there is absorption in the semiconductor laser region (600 to 900 nm).

Example 1 Example 1 Examples 13 to 4 Compounds to be reacted were appropriately selected, and phthalocyanine compounds represented by the following structural formula were produced in the same manner as in the above examples.

All of these are semiconductors. It was confirmed that there is absorption in the laser region.

Example 1 Example 1 Example 1 Example 1 Example 1 Example 2 Example 2 Example 2 Example 2 Example 2 Example 2 Example 2 Example 2 Example 28 Example 3 Example 3 Example 2 Example 3 Example 3 Example 3 Example 3 Example 3 Example 39 Example 40 Example 37 Example 38 Example 41 (1) Synthesis Example 0.25 g of a diiminoindoline compound represented by the following structural formula and A dry butanol solution containing 0.027 g of copper (II) acetate represented by the following structural formula (% formula %) was heated to 2.
The mixture was heated under reflux for 0 hours to react. The reaction mixture was prepared in Example 1.
(4) to obtain 50 mg of a phthalocyanine compound represented by the following structural formula.

The weight of the obtained phthalocyanine compound is 0. X (in chloronaphthalene) was found at 630 nm and 680 nm, and it was confirmed that there was absorption in the semiconductor laser region (600 to 900 nm).

A benzene solution of the obtained compound is sealed in a glass cell,
When this glass cell was irradiated with monochromatic light of 404.5 nm for 2 minutes, it was colored from blue to bluish-purple. This colored state was thermally very stable. Next, when a mercury lamp and a filter were combined and monochromatic light of 680 nm was irradiated for 5 minutes, the color immediately disappeared. This change could be repeated reversibly.

(3) Scientific Recording Method 2 The obtained compound 200 nm and polystyrene (molecular weight 16
A recording layer was prepared by dissolving 20g of 1000g) in 400mj2 of toluene, coating the solution on a glass substrate, and drying it.

This recording layer was irradiated with monochromatic light of 404.5 nm for 3 minutes,
The entire surface was colored. This colored state was thermally stable, and no fading was observed for 12 hours or more at 80°C. Next, when writing was attempted using a He-Ne laser (633 nm) at 10 mW, the coloring immediately faded after irradiation for 10 seconds. This cycle of coloring and fading could be repeated 50 times or more.

(4) Scientific Recording Method 3 1 g of the obtained compound was heated to about 80 to 150° C. under a vacuum of 2×10 Torr, and vacuum deposited on a 12 mm thick methacrylic resin substrate.

This recording layer was irradiated with monochromatic light of 404.5 nm for 3 minutes,
The entire surface was colored. This colored state was thermally stable, and no fading was observed for 12 hours or more at 80°C. Next, when writing was attempted using a He-Ne laser (633 nm) at 10 mW, the coloring immediately faded after irradiation for 10 seconds. This cycle of coloring and fading could be repeated 50 times or more.

[Effects of the Invention] As detailed above, the phthalocyanine compound of the present invention has absorption in the semiconductor laser region (600 to 900 nm), has semiconductor laser sensitivity, and has a novel photochromism with good recording thermal stability. This is the compound shown.

In particular, in the phthalocyanine compound represented by the formula [11], especially in the formula [I+], Rl,
R2, R3, R4, RS, R8, R? , Ra
, R9, RI OR day R12R13R” RI5
R” R17R” R”, R”, R” R22,
R" and R" are straight or branched alkyl groups having 1 to 20 carbon atoms, and M is 2H, Cu, Ni, Co, or Zn.

If it is a phthalocyanine compound that is Fe or ■O,
Shows excellent semiconductor laser sensitivity and recording thermal stability.

Therefore, the compound of the present invention can be used in various recording/memory materials, copying materials, light control materials, printed photoreceptors, laser photosensitive materials,
It is extremely useful as a light-sensitive material for phototypesetting, a light filter, a masking material, a photometer, a display material, etc.

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 show Example 1, respectively. It is a diagram showing the absorption spectrum of the phthalocyanine compound according to the present invention synthesized in Example 1O, where the horizontal axis shows the wavelength (nm),
The vertical axis shows absorbance. Agent Patent Attorney Tsuyoshi Shigeno

Claims (3)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, M is 2H or group VIII, group Ib, group IIb, IIIb
Represents metal atoms of Group IVa, Group Va, Group VIa, Group VIIa, and their oxides and halides, A^1, A^2,
A^3, A^4, B^1, B^2, B^3, and B^4 represent a heterocycle. However, A^1 and B^1, A^2 and B^
2. A^3 and B^3, A^4 and B^4 are heterocycles that change their optical properties by cyclizing each other with light irradiation to form a cyclohexadiene ring. However, if M is 2H, A^1, A^
2, A^3, A^4, B^1, B^2, B^3, B^4
is not a thiophene ring at the same time. ) A phthalocyanine compound represented by (2) The phthalocyanine compound has the general formula [II]▲mathematical formula,
There are chemical formulas, tables, etc. ▼... [II] (In the formula, M is 2H or group VIII, group I b, group IIb, IIIb
Represents metal atoms of Group IVa, Group Va, Group VIa, Group VIIa, and their oxides and halides, and X and Y are S, O,
Represents Se atoms, R^1, R^2, R^5, R^6,
R^7, R^8, R^1^1, R^1^2, R^1^3
, R^1^4, R^1^7, R^1^6, R^1^9,
R^2^0, R^2^3, R^2^4 represent alkyl groups, R^3, R^4, R^9, R^1^0, R^1^
5. R^1^6, R^2^1 and R^2^2 represent a hydrogen atom or an alkyl group. However, when M is 2H, X and Y are not S atoms at the same time. ) The phthalocyanine compound according to claim 1, which is a compound represented by: (3) In the general formula [II], R^1, R^2, R
^3, R^4, R^5, R^6, R^7, R^8, R^
9, R^1^0, R^1^1, R^1^2, R^1^4
, R^1^4, R^1^5, R^1^6, R^1^7,
R^1^8, R^1^9, R^2^0, R^2^1, R
^2^2, R^2^3, R^2^4 represent a linear or branched alkyl group having 1 to 20 carbon atoms, M is 2H, Cu
, Ni, Co, Zn, Fe, or Vo.