JPH01216966A - Metal-containing compound and optically recording medium using said compound - Google Patents

Abstract

NEW MATERIAL:A metal-containing compound of formula I (M is the group VIII, Ib, IIb, IIIb, IVa, Va, VIa or VIIa metal atom, a halide thereof or an oxide thereof; K is the residue of a substituted or unsubstituted aromatic amine; the rings A and B may each have one or more substituents; n is 2 or 3). EXAMPLE:A compound of formula II. USE:A colorant for optically recording media whose states are changed by the irradiation of laser rays to regenerate records. The compound has high solubility in organic solvents, coating ability by coating methods, high reflectance, good contrast and excellent preservability. PREPARATION:For example, the compound of formula I is obtained by reacting a compound of formula III with a compound of formula IV and subsequently oxidatively condensing the reaction product with the hydrochloride salt of a compound of formula V.

Description

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

[Conventional technology]

Optical recording using lasers has been particularly encouraged in recent years for its development because it enables high-density information storage, storage, and reproduction.

An example of optical recording is an optical disc.

In general, optical discs record high-density information by irradiating a thin recording layer provided on a circular substrate with a laser beam focused to about 1 μm.

Recording is done by absorbing the irradiated laser energy.
The reproduction of recorded information is generated by thermal deformation such as decomposition, evaporation, and melting of the recording layer at that location.
This is done by using a laser beam to read the difference in reflectance between areas where deformation has occurred and areas where deformation has not occurred.

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, Tokukai Akira! ! ;-9'1033 discloses a method in which a single layer of a phthalocyanine dye is provided on a substrate. However, phthalocyanine dyes have problems such as low sensitivity, high decomposition point, and difficulty in vapor deposition.Furthermore, they have extremely low solubility in organic solvents, making them unsuitable for use in coatings. ing.

Also, JP-A-5TR-v3. YQlI discloses a recording layer in which a phenalene dye is provided, and JP-A-5G-Ikkoguku-9G discloses a naphthoquinone dye in a recording layer. 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 portion recorded by laser light and the unrecorded portion will be low, making it difficult to reproduce the 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 novel metal-containing 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 recording medium using the compound. The purpose is to provide the following.

[Means to solve the problem]

The present invention provides a metal-containing compound represented by the following formula [l] suitable as a dye for an optical recording medium for recording and reproducing by 2 causing a state change with a laser beam, and a recording layer containing the compound on a substrate. The gist of the invention is an optical recording medium supported by a.

In the formula, M is the ■ group, the lb group, the Ilb group, the lb group, the ■a group,
Represents a metal atom of Group Va, Group ■a, Group ■a, its halide, and its oxide, K represents a substituted or unsubstituted aromatic amine residue, and ring AXB has a substituent. You can. n represents ko or 3. ) In the general formula (1), the substituted or unsubstituted aromatic amine residue represented by Kte includes, for example, a heterocyclic amine residue containing a crab atom, an oxygen atom, or a sulfur atom;
Tetrahydroquinolines, julolidine ring or the following -
Formula (wherein, Xa and Yb represent a hydrogen atom, an alkyl group, an acylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an alkoxy group, or a halogen atom, and Ba and Rb represent a hydrogen atom or C□ to C2
represents a substituted or unsubstituted alkyl group, aryl group, alkenyl group or cycloalkyl group. ) and the like. Substituents for the alkyl group, aryl group, allyl group or cyclohexyl group represented by Ra and Rb include, for example, 1-alkoxy group, alkoxyalkoxy group, alkoxyalkoxyalkoxy group, allyloxy group, aryl group, aryloxy group, cyano group, hydroxy group, tetrahydrofuryl group, alkylsulfonylamino group, etc.

Preferably, - formula [II] (wherein M is N
i, CuSCo, Zn, pd, pt, V or Fe metal atom, R3, R4, X, Y are hydrogen atom, halogen atom, alkyl group, alkoxy group, acylamino group, alkoxycarbonylamino group, alkylsulfonylamino represents a group, R", R" is a hydrogen atom, C
It represents an alkyl group, aryl group, alkenyl group, or cycloalkyl group of 1 to 2°, and these groups may be substituted, and n represents co or the number of 3. ) are listed.

Among them, the alkyl group represented by R", R',
The alkoxy group of the alkoxycarbonylamino group includes an alkoxy group having 1 to 6 carbon atoms, the acyl group of the acylamino group includes an acyl group having 1 to 2 carbon atoms, and the halogen atom includes a chlorine atom, a bromine atom, a fluorine atom, etc. is,
Examples of the aryl group represented by R1 and R2 include a phenyl group and a naphthyl group, examples of the alkenyl group include an allyl group, and examples of the cycloalkyl group include a cyclohexyl group.

The remaining metal-containing compound in formula [1] is 400-
It has an absorption in the wavelength band of 100 nm and a high molecular absorption coefficient of 105 cm-' or more, making it highly suitable as an optical recording medium.

The general synthesis of the metal-containing compound represented by the general formula [1] used in the present invention is, for example, a compound represented by the following formula [seal] (wherein R" and R' are the same as defined above) is reacted with a compound represented by the following formula [■] MC10...[■] (wherein M is the same as defined above), and then, the compound represented by the following formula [v] (formula Medium, X, Y,
It can be produced by oxidative condensation of the hydrochloride of the compound represented by (R' and R2 are the same as defined above).

The optical recording medium of the present invention basically consists of a substrate and a recording layer containing a metal-containing compound, but if necessary, it may further include an undercoat layer on the substrate and a protective layer on the recording layer. can be provided.

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. Plastics include acrylic resin, methacrylic resin, vinyl acetate resin, vinyl chloride resin, nitrocellulose, polyethylene resin, polypropylene resin, polycarbonate resin,
Examples include polyimide resin, epoxy resin, polysulfone resin, and the like.

When the metal-containing compound of the present invention is used as the information recording layer in the optical recording medium of the present invention, the film thickness is / 00 A -
! ; am, preferably 1OOOA to 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. The binder is P V AX PVP.

Known materials such as nitrocellulose, cellulose acetate, polyvinyl butyral, and polycarbonate are used, and the amount of resin (binder) added to the pigment is 30 wt%.
The following is desirable. In the case of film formation by the spinner method, the rotational speed is preferably soo to k 000 rpm, and after the spin code, treatment such as heating or exposure to solvent vapor may be performed as the case requires.

In order 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) are added as singlet oxygen quenchers to the recording layer. etc.) may be included. Furthermore, other dyes can be used in combination as 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, in particular, a spinner method, the coating solvents include tetrachloroethane, bromoform, dibromoethane, diacetone alcohol, ethyl cellosolve, and xylene. , 3-hydroxy-3-methyl-J-7'tanone, chlorobenzene, cyclohexanone and the like having a boiling point of 10° C. to 16° C. are preferably used.

Among these, cellosolve-based solvents such as methyl cellosolve and ethyl cellosolve are particularly suitable for injection-molded polycarbonate resin substrates, which have excellent productivity, cost, and moisture absorption resistance, and can be used without destroying the substrate. ; Examples include ketone alcohol solvents such as diacetone alcohol and 3-hydroxy-3-methyl-coptano 7.

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 a laser beam, preferably a semiconductor laser beam, focused to a diameter of about 1 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 a laser beam and by reading the difference in reflectance between a portion where thermal deformation has occurred and a portion where no thermal deformation has occurred.

The laser beams used for the optical recording medium of the present invention include N2, He-Cd, Ar, He-Ne, Ruby,
Semiconductor lasers, dye lasers, etc. may be mentioned, and semiconductor lasers are particularly suitable from the viewpoint of light weight, ease of handling, and compactness.

〔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.

Example 1 (a) Production example/-Hydroxy-naphthoic acid'1.7fi (0,0
25 mol) in water/DO-, sodium carbonate u,
01 was added and dissolved. This thing nickel dichloride 6
, Rizay (o, o s mol) was added, and a pale colored precipitate was formed. The mixture was cooled to 0-5° C. with stirring and diluted with dimethylaniline hydrochloride s, t 7 J9 (o, 0 coS mol) 1-water!
dissolved in Omt and ammonium persulfate s0
A solution of g 2i (o, o coS mol) dissolved in water SOd was simultaneously added dropwise over about 30 minutes. θ℃〜s℃
After stirring for another 2 hours, filter the green crystals.
3! ; Got I. The crystals were dispersed in methanol (about SOd), stirred for a period of time at room temperature, and filtered to obtain a green substance having the structure shown in the following formula [A]. λmaX Huff F9nm of this in chloroform solution,
ε=su,koX/0'.

(a) Example of a recording medium The metal-containing compound obtained in Production Example (a) was dissolved in 0.19f tetrachlorothane log and filtered through a 0.2.2μ filter to obtain a solution. This solution/agl was dropped onto a polymethyl methacrylate (PMMA) resin substrate (j coφ) and coated by a spinner method at a rotation speed of E 00 rprn. After coating, it was dried at 60° C. for io minutes.

What is the maximum absorption wavelength of the coating film? It was 70 nm.

The shape of the spectrum was wide.

(C) Optical recording method The coating film on the above PMMA resin substrate was coated with a center wavelength of 7 g.
When irradiated with Onm semiconductor laser light, pits with clear outlines were formed.

The storage stability (bo°C, go%RH) of this coating film was good.

Example) Production example Salicylic acid 3. Disperse q s I (0, o 2.t mol) in 100 - of water and carbonate it) IJum! , 2 f
, 9 were added and dissolved. Nickel chloride 3.
4Ig (0,025 mol) was added. This mixture f
Cool to 0°C to S°C and add 5.37 g of gudiethylamino-λ-methylaniline hydrochloride while stirring.
Mol) dissolved in water 50-, and ammonium persulfate! r0g 2 # (0,023 mol) in water SO
d was added dropwise at the same time over about 30 minutes. After stirring for an additional hour at θ°C to s°C, filter it.
By washing with a small amount of methyl alcohol, the following formula [
A greenish-brown substance O0za311f having the structure shown in [Image Omitted] was obtained. The λmax of this substance in a chloroform solution is 73! ;n
m.

ε=λ, /X/0'.

(b) Recording Medium Example The metal-containing compound obtained in Production Example (a) was applied onto a PMMA resin substrate with grooves (groups) using a spinner method according to the method described in Example 1. The maximum absorption wavelength of the coating film was 760 nm, and the shape of the spectrum was wide.

(c) Optical recording method The coating film on the above PMMA resin substrate was coated with a center wavelength of 7 g.
When irradiated with Onm semiconductor laser light at an output of bmW, pits with clear outlines were formed.

The storage stability (AO"C, 10% RH) of this coating film was good.

Example 3 In Example 1, nickel chloride t, IIg g(O6O
Vanadium chloride 6 gas I (θ,
A metal-containing compound represented by the following structural formula was obtained in the same manner as in Example 1, except that OS mol) was used. What is the λmax of this substance in chloroform solution? j Onm.

EXAMPLES When the compounds shown in Table 1 were used in place of the compounds used in Example 1 and applied, thin film substrates having the maximum absorption wavelengths shown in Table 1 were obtained. When writing was performed on the thin film thus obtained using a semiconductor laser as a light source, pits with a uniform and clear shape were obtained.

In addition to the compounds used in the above examples, specific examples of metal-containing compounds preferably used in the optical recording medium of the present invention are shown in Table 1.

〔Effect of the invention〕

The metal-containing compound of the present invention has high solubility in organic solvents, can be coated by coating, has high reflectance, good contrast, and has excellent storage stability. Optical recording media using compounds are extremely useful.

Claims (4)

[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 a metal atom of Group Va, Group VIa, or Group VIIa, its halide, or its oxide, K represents a substituted or unsubstituted aromatic amine residue, and rings A and B have a substituent. You may do so. n represents 2 or 3. ) metal-containing compounds. (2) The metal-containing compound described in claim 1 has the general formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[II] (In the formula, M is Ni, Cu, Co, Zn, Pd, Pt, V
or represents a metal atom of Fe, R^3, R^4, X, Y
represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group; group, cycloalkyl group, these groups may be substituted, n represents the number of 2 or 3. ). (3) 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 recording. An optical recording medium in which reproduction is performed by selecting a portion, characterized in that a metal-containing compound represented by the general formula [I] according to claim (1) is used as a dye. (4) The metal-containing compound used in the optical recording medium according to claim 3 is
Those represented by the general formula [II] described in Section 1.