JPH01254772A - Metal-containing indoaniline compound and optically recording medium using said compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [M is metal of group VIII, group Ib, group IIb, group IIIb, group IVa, group Va, group VIa or group VIIa, halide or oxide thereof; rings A, B, C, D, E, F, G, H and I may contain substituent group: R<1>-R<6> are nonsubstituted alkyl; Q is anion (except PF)]. USE:An optically recording medium having high solubility in organic solvents, capable of being coated by application and yet having high reflectance, good contrast and excellent shelf stability. PREPARATION:A compound shown by formula II (R<7> and R<8> are, halogen, alkyl, alkoxy, acylamino, etc.) is oxidatively condensed with a hydrochloride of a compound shown by formula III (X<1> and Y<1> are as shown for R<1> and R<2>) to give a compound shown by formula IV. The compound is reacted with compounds shown by formulas V and VI (R<9>4-R<2>, X<3> and Y<3> are as shown for R<1> and R<2>) and a compound shown by the formula MQ.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a metal-containing indoaniline compound and an optical recording medium using the compound.

[Conventional technology]

Optical recording using a laser has been particularly developed in recent years because it enables high-density information recording storage and reproduction.

An example of an optical recording medium is an optical disc.

In general, optical discs record high-density information by irradiating a thin recording layer provided on a circular base with laser light focused on the order of /μm. The recording is performed by causing thermal deformation such as decomposition, evaporation, and melting in the recording layer at that location by absorption of the irradiated laser light energy. Furthermore, the recorded information is reproduced by reading the difference in reflectance between a portion where deformation has occurred and a portion where no deformation has occurred using a laser beam.

Therefore, as an optical recording medium, it is necessary to efficiently absorb the energy of laser light, so the absorption of laser light of a specific wavelength used for recording is large, and in order to accurately reproduce information, it is necessary to efficiently absorb the energy of laser light. It is necessary that the reflectance for laser light of a specific wavelength is high.

Various configurations of this type of optical recording medium are known.

For example, JP-A Showa Tatar 970. : Publication No. 13 discloses a single layer of a phthalocyanine dye provided on a substrate. However, phthalocyanine dyes have problems such as low sensitivity and high decomposition point (difficult to vapor deposit), and extremely low solubility in organic solvents (and cannot be used for coating by coating). have.

Furthermore, JP-A Shojg-g3J'l'1 discloses a phenalene dye, and JP-A Shoj! ;g-, 22da 79g discloses a recording layer in which a naphthoquinone dye is provided. However, although such dyes have the advantage of being easy to deposit, they have the problem of low reflectance.

If the reflectance is low, the contrast related to the reflectance between the area recorded by the laser beam and the unrecorded area will be low.
It becomes difficult to reproduce recorded information. Furthermore, organic dyes generally have a problem of poor storage stability.

[Problem to be solved by the invention]

The present invention relates to a metal-containing indoaniline compound that has high solubility in organic solvents (can be coated by coating, has high reflectance, good contrast, and has excellent storage stability), and an optical system using the compound. Its purpose is to provide recording media.

[Means to solve the problem]

The present invention provides a recording layer consisting of a novel metal-containing indoaniline compound and a dye supported on a substrate. This optical recording medium is an optical recording medium in which recording is performed by recording the changed portion, and then reproduction is performed by reading the changed portion, the optical recording medium having a substrate supporting a metal-containing indoaniline compound generally represented by the following 2m as a dye. That is.

(In the formula, M represents a metal atom of the ■ group, ■b group, lb group, ■b group, IVa group, Va group, Via group, and ■a group, its halide, and its oxide; ring A, B %C,D,E,
FlG, H, and King may have a substituent. R1, R
2, R3, R4, R5 and R6 represent unsubstituted alkyl groups. Q is an anion (excluding PF6-).More preferable metal-containing indoaniline compounds include those represented by the following general formula crt.

(In the formula, M is X] Group ■, Group Ib, Group nb, Group ■b, ■a
Represents a metal atom of Group Va, Group Via, Group ■a, its halide and its oxide, R7, R8, R9,
RIOlRll, RI2, xl, mo, N3, Yl,
, T2 and T3 are hydrogen atoms, halogen atoms, alkyl groups,
represents an alkoxy group, an acylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, and R1
, R2, R3, R4, R5, R6 are c, -20 alkyl groups, and Q represents an anion (excluding PF6-). Examples of metal atoms include N1, Zn, Cu, Co1Fe(1
,I),Fe(rII),Pd,A,1,T1,pt,
V, Cr, Mn, etc. are added, and examples of their oxides and halides include VQ, AlCl, etc.

Examples include substituted alkoxy groups, acylamino groups, alkoxycarbonylamino groups, alkylsulfonylamine groups, and phenylaminocarbonyl groups for rings A, B%C%D, E, F, G, H, and I. Examples of the group include an acyl group having 7 to 7 carbon atoms (including a benzoyl group), an alkoxy group of an alkoxycarbonylamino group, and an alkylsulfonylamino group.

Furthermore, particularly preferred compounds of the present invention in which R1, R2, R3, R4, R5, and R6 are unsubstituted include those represented by the following general formula (IID).

U-) represents a metal atom, and N4, N5, a hydrogen atom, -~
4 represents an alkyl group, R13, R14, R151,
R16, R17, and R18 represent an alkyl group of 01 to 8, and R19, R20° and R21 represent a hydrogen atom, an alkyl group of 01 to 4, and a halogen atom. Q is an anion (PF
Represents 6- minus (). ) In one form CI] to (III), examples of the anion represented by Q include Ni, Br-1C1-1F-1CI
O4-1BF4-1SCN-1C'H3[yS O3-
1a3C,3-10H s 03N H;, 5bF6-1Z r F7, C(g
R35! ')2-1TiF, etc., preferably l-1Br-1C1-1C104-
It is an anion selected from 1BF4-.

The metal-containing indoaniline compound represented by the general formula [I] has absorption in the wavelength band of 600 to 50 nm, and has a molecular absorption coefficient as high as 705Cfn= or more, and is suitable for optical recording. It has excellent suitability for use as a medium.

The general synthesis of the metal-containing indoaniline compound represented by the general formula QI) used in the present invention is described by, for example, Yuji Kubo, Masako Sasaki, Kappei Yoshida; Proceedings of the 53rd Autumn Annual Meeting of the Chemical Society of Japan/q :A.

It can be done according to the description in A39. That is,
The following general formula (wherein, XI, Yl, Hl, and R2 are the same as defined above) is added to the compound represented by the general formula (wherein, R7 and R8 are the same as defined above).

) was subjected to oxidative condensation to obtain a compound of the following general formula (wherein R7, R8, R1, R2, Xi, and Yl are the same as defined above).

Next, the above compound and the following general formula (in the formula, R3, R4, R5, R6, R9, RIOlRl
l, R12, X2, and χ3 and Y3 are the same as defined above.

) and the following general formula (In the formula, M and Q are the same as defined above.) It can be produced by reacting with.

The optical recording medium of the present invention is basically composed of a substrate and a recording layer containing a metal-containing indoaniline compound, but if necessary, an undercoat layer may be provided on the substrate and an undercoat layer may be added on the recording layer. You can put a protective layer on it.

The substrate in the present invention may be either transparent or opaque to the laser beam used. Examples of the substrate material include supports for general recording materials such as glass, plastic, paper, plate-shaped or foil-shaped metal, etc.
Plastic is preferred for various reasons. Examples of the plastic include acrylic resin, methacrylic resin, vinyl acetate resin, vinyl chloride resin, nitrocellulose, polyethylene resin, polypropylene resin, polycarbonate resin, polyimide resin, epoxy resin, polysulfone resin, and the like.

Among these, injection molded polycarbonate resin substrates are particularly preferred in terms of high productivity, cost, and moisture absorption resistance.

When a metal-containing indoaniline compound is used as the information recording layer in the optical recording medium of the present invention, the film thickness is 10oA.
~ S μm, preferably 1 oooλ ~ 3 μm. The film can be formed by a commonly used thin film forming method such as a vacuum evaporation method, a sputtering method, a doctor blade method, a casting method, a spinner method, or a dipping method. Moreover, a binder can also be used if necessary.

Known binders such as PVA, PVP, nitrocellulose, [1 cellulose, polyvinyl butyral, and Ho'J carbonate are used, and the amount of the metal-containing indoaniline compound based on the resin is 7% or more by weight. desirable. In the case of film formation using the spinner method, the rotation speed is! ; 00 to j 000 rpm is preferable, and after the spin code, treatment such as heating or exposure to solvent vapor may be performed depending on the case. In addition, to improve the stability and light resistance of the recording medium, transition metal chelate compounds (e.g., acetylacetonate chelate, bisphenyldithiol, salicylaldehyde oxime, bisdithio-α-diketone, etc.) are used as heavyt oxygen quenchers.
It may contain (・.

Furthermore, other dyes can be used in combination if necessary.

The other dyes may be other types of compounds of the same type, or dyes of other types such as triarylmethane dyes, azo dyes, cyanine dyes, squarylium dyes, etc.

When forming a recording layer by a coating method such as a doctor blade method, a casting method, a spinner method, or a dipping method, especially a spinner method, coating solvents such as tetrachloroethane, bromoform, cyfuromoethane, ethyl cellosol, xylene, chlorobenzene, cyclohexanone, etc. boiling point 720
~/60°C is preferably used.

Among them, diacetone alcohol, 3-hydroxy-3-
An injection molded polycarbonate resin substrate in which a ketone alcohol solvent such as methyl-λ-butanone is preferably used as the substrate can be suitably used without any side dish, and is particularly preferred.

The recording layer of the optical recording medium of the present invention may be provided on both sides of the substrate or only on one side.

Recording on the recording medium obtained as described above is carried out by irradiating the recording layer provided on both sides or one side of the substrate with laser light, preferably semiconductor laser light, focused to about 7 μm. In the portion irradiated with the laser beam, thermal deformation of the recording layer such as decomposition, evaporation, and melting occurs due to absorption of laser energy.

The recorded information is reproduced by using laser light to read the difference in reflectance between areas where thermal deformation has occurred and areas where thermal deformation has not occurred.

Laser beams used for the optical recording medium of the present invention include N2, He-Cd, Ar, He-Ne, ruby, semiconductor, and dye lasers, but are especially lightweight, easy to handle, and compact. Semiconductor lasers are suitable for these reasons.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples, but these Examples are not intended to limit the present invention.

Examples/(a) Production Example 0.9 g of the compound represented by the following structural formula was added to 99% ethanol! ; Zn(C1○4
) 2・1, N20 o, 3 r,! 9 to 500 water
ml under a nitrogen atmosphere, and stirred at room temperature for about 3 ml.
Stir for hours. The obtained precipitate was suction filtered, washed with water, and dried to obtain a metal-containing indoaniline compound having the following structural formula.

The visible absorption spectrum (in chloroform) of this metal-containing indoaniline compound is λmax 7gOnm (
εmaxt, gooo).

(b) Recording medium example The metal-containing indoaniline compound obtained in the above production example (a). /59 was dissolved in 70 g of 3-hydroxy-3-methyl-cobutanone and filtered through a 0.22μ filter to obtain a solution. This melt Iys me to a depth of 700^,
Dropped onto a polycarbonate injection molded resin substrate (5 inches) with grooves (groups) with a width of 0.7 μ, using the spinner method. Coating was carried out at a rotation speed of 0.00 rpm. After application, 6
It was dried at 0°C for 70 minutes.

CC) Optical recording method While rotating the S-inch polycarbonate resin substrate on which the above-mentioned recording layer was formed at lIm/s, the center wavelength was 7 g.
Onm semiconductor laser light with a pulse width of 500 n5ec
When it was irradiated with 100 MHz, a C/N ratio of 53 dB was obtained with an output of AmW. Storage stability (60°C, go%RH) was also good.

Example Co(a) Production Example In place of 95g of compound Q used in Example/,
Example/ except that 0.999 of the compound represented by the following structural formula was used.
In the same manner as above, a metal-containing indoaniline compound represented by the following structural formula was obtained.

The measured values of elemental analysis of this compound agreed well with the calculated values as shown below.

The visible absorption spectrum (in chloroform) of this metal-containing indoaniline compound is λm at 5 as shown in Figure -/.
Ax 7? Onm ('maxqoooo).

(b) Recording medium example The metal-containing indoaniline compound obtained in the above production example (a) was used. /! ; Dissolve 0.g in 10g of diacetone alcohol. - Filtered through a 1μ filter to obtain a solution. Spread 3ml of this solution into a groove with a depth of 700mm and a width of 0.7μ.
Polycarbonate injection molded resin substrate (S
700 rpm using a spinner method.
It was applied at a rotation speed of After coating, it was dried at AO° C. for 10 minutes. Figure-,! shows the absorption and reflection spectra of the coating film. The maximum absorption wavelength of the coating film was 7q0 nm, and the reflectance was 3% (g30 nm).

(C) Optical recording method While rotating a polycarbonate resin substrate of 1/2 inch diameter, which simulates the formation of the above-mentioned recording layer, at a speed of m/s, the central wavelength g 3
Pulse width so on with 0 nm semiconductor laser light
When irradiated at 5ec, the C/N ratio was 5 at the output ArnVJ.
I got udB. Storage stability (60°C, go%RH) was also good.

Example 3 Instead of the metal-containing indoaniline compound used in Example 1, a metal-containing indoaniline compound having the structure shown in Table 1 was applied in the same manner, resulting in the results shown in Table 7. A thin film substrate with maximum absorption wavelength was obtained. When writing was performed on the thin film thus obtained using a semiconductor laser as a light source, bits with a uniform and clear shape were obtained. The C/N ratio was also good, and the storage stability was also good.

M, X, R1%R2 and Z in the table are based on the following general formula.

General formula In addition to the compounds used in the above examples, specific examples of metal-containing indoaniline compounds suitably used in the optical recording medium of the present invention include those shown in Tables 2 and 3.

Lake, third coat M, R13, R14, R15, R16, R
]7, RI8 and Q are based on the above-mentioned formula [■], in which the other x4, x5 and x6 represent a methyl group, and RI9, R20 and R21 represent a hydrogen atom.

〔Effect of the invention〕

The metal-containing indoaniline compound used in the present invention has high solubility in organic solvents (can be coated by coating), high reflectance (good contrast, and excellent storage stability). Therefore, optical recording media using this compound are extremely useful.

[Brief explanation of the drawing]

Figure -/ represents the visible region absorption spectrum of the metal-containing indoaniline compound of the present invention (Example 2), where the vertical axis represents absorbance and the horizontal axis represents wavelength (nm). Figure-Y represents the absorption spectrum and reflection spectrum of a coated thin film of the metal-containing indoaniline compound of the present invention (Example-Y), where the vertical axis represents the absorbance on the left, the reflectance on the right, and the horizontal axis represents the absorbance. The axis represents wavelength (nm).

Claims (2)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I
] (In the formula, M is group VIII, group Ib, group IIb, group IIIb, IVa
Represents metal atoms of group Va, group VIa, group VIIa, their halides and their oxides, and rings A, B, C, D, E
, F, G, H, and I may have a substituent. R^1
, R^2, R^3, R^4, R^5, and R^6 represent unsubstituted alkyl groups. Q represents an anion (excluding PF_6^-). ) is a metal-containing indoaniline compound. (2) Recording is performed by irradiating a recording layer containing a dye supported on a substrate with a focused laser beam that causes a thermal change in the dye to cause a partial change in the recording layer, and then performing the recording. An optical recording medium in which reproduction is performed by selecting a portion, characterized in that a metal-containing indoaniline compound represented by the general formula [I] according to claim 1 is used as a dye.