JPS62138459A - Squarylium compound and optical recording material containing said compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [A is azulenyl; R<1> and R<2> are H, alkyl, allyl, aralkyl, aryl or together with N form a heterocyclic group; R<3> is group of formula II or -SO2R<6>, (R<5> and R<6> are alkyl, alkoxy, vinyl, etc.); R<4> is H or alkoxy]. USE:An optical recording material. The compound has high solubility in organic solvent, is applicable by coating and has high reflectance, contrast and resistance to light and reproduced light. PREPARATION:The compound of formula I can be produced by reacting the benzene derivative to formula III with 3,4-dihydroxy-3-cyclobutene-1,2-dione of formoula IV in a solvent such as methanol, benzene, etc., at 70-150 deg.C, preferably 90-120 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel squarylium compound and an optical recording medium using the compound.

BACKGROUND OF THE INVENTION Optical recording using lasers has been particularly desired in recent years because it enables high-density information 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 (1-) provided on a circular base with a focused laser beam of about 0.5 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.
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.

As Shikatsu-C1 recording media, it is safe to efficiently absorb the energy of laser light, so it has a high absorption of laser light of a specific wavelength used for recording. It is essential that the reflectance for the laser beam of the specific wavelength used is high.

Various configurations of optical recording media for hats are known.

For example, Tokukai Akira! ! Japanese Patent No. 97033 discloses a device in which a single layer of a phthalocyanine dye is provided on a substrate. 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. .

-! ! Hi, Tokukai Akira! No. 1♂Gugu No. 33 discloses a phenalene color chart, and Japanese Patent Application Laid-Open No. 1996-Lμ793 discloses that a naphthoquinone base material is provided in the recording layer.

However, although such dyes have the advantage of being easy to vapor deposit, they also have the problem of low reflectance. If the reflectance is low, the contrast related to the reflectance between the portion recorded by the laser beam and the unrecorded portion will be low, making it difficult to reproduce the recorded information.

Also, JP-A No. 5'-2'16F2, JP-A No. 3-
9-6709λ official uniform, Tokukai Sho! Turf/? No. 5 discloses a recording layer in which a cyanine dye is provided. However, although such dyes have the advantage of being usable for coating by coating, they also have the problem of light resistance and deterioration with respect to reproduction light.

Problems to be Solved by the Present Invention The present invention has 8 problems to be solved by the present invention. To provide a dye compound that has high solubility in a solvent, can be coated by coating, has high reflectance, good contrast, and has excellent light resistance and resistance to reproduction light, and an optical recording medium using the compound. The purpose is to

Sixth way to solve problem skin The gist of the invention is as follows.

General formula C1) [In the formula, A represents azulenyl which may have a substituent, R1 and R2 are an alkyl group, an allyl group, an aralkyl group or It represents an aryl group, and R1 and R2 may be linked to each other to form a ring with a nitrogen atom. R8 is -δ-R5 or -8O2R' (R5 and R6 are an alkyl group which may have a substituent, an alkoxy group, a vinyl group, a cycloalkyl group, a cycloalkyloxy group, an allyl group, an aralkyl group, an aryl group) The following groups represent aryloxy groups.

) and R4 is a hydrogen atom '-! or an alkoxy group which may have a substituent. ] The present invention relates to an optical recording medium characterized by comprising a Guqua IJ compound represented by the following formula and a recording layer containing the compound.

The substituent group of the azulenyl group A of the general formula [1) or an alkyl group having a carbon number of 1 to 1) or an alkoxy group that may have a substituent (for example, an alkoxy group having a carbon number of 7 to 2!, preferably is an alkoxy group having a carbon number of /~?, which may have a substituent such as an alkoxy group or an alkoxyalkoxy group), or an aralkyl group which may have a substituent (for example, a carbon number of /~ The alkyl group, an alkoxy group, or a benzyl group, a phenenal group, or a phenyl group, which may be substituted with an atom, is an aryl group which may have a substituent (for example, the above-mentioned, Examples thereof include a phenyl group (which is similar to an aralkyl group and may be substituted with one substituent) or a halogen atom such as a chlorine atom or a bromine atom.

The azulenium ring of the azulenyl group is a benzene ring, a cyclohexene ring, and a cyclopentene ring.

Fu may be fused with a dihydrothiophene ring, a tetrahydro-pyridine term, a furan term, a dihydrofuran ring, a pyrrole ring, a dihydropyrrole ring, a thiazole ring, etc.

R1 and R2 in the general formula [1] are a water I atom or the number of carbon atoms which may have a substituent/~co! , preferably alkyl having carbon number /~/θ? Mr Allyl group which may have a substituent; benzyl group, phenethyl group which may have a substituent.

Examples include aralkyl groups such as phenylpropyl groups; aryl groups such as phenyl groups and naphthyl groups which may have substituents. As the substituent for the above alkyl group,
For example, human axyl group, cyano group, number of carbon atoms /~/! alkoxy group, alkoxyalkoxy group, fluorine atom,
Halogen atoms such as chlorine atoms and bromine atoms, arylcarbonyloxy groups, allyloxy groups, aryloxy groups, tetrahydrofuryl groups, and amino groups.

Alkylamino group, dialkylamino group, trialkylamino group, alkoxycarbonyl group.

Examples include a cyclohexyloxycarbonyl group, an alkylcarbonyloxy group, an aryloxycarbonyl group, an alkoxycarbonyloxy group, a cyclohexylcarbonyloxy group, and an aryloxycarbonyloxy group.

As substituents for allyl groups, alkyl groups such as methyl groups,
Examples include halogen atoms such as chlorine atoms, aryl groups such as phenyl groups, and examples of substituents for aralkyl groups and aryl groups include alkyl groups having 7 to 9 carbon atoms,
Examples include alkoxy groups, halogen atoms such as chlorine atoms, bromine atoms, fluorine atoms, and iodine atoms, and nitro groups.

Also, %R1 and R2 are connected to each other and together with the nitrogen atom! For example, the member ring is a compound ring of the member term.

It may form a biarydin ring, a piperidine ring, a morpholine ring, etc.

Substituents R5 and H6 are an alkyl group, an alkoxy group, a vinyl group, a cycloalkyl group, a cycloalkyloxy group, and an allyl group, which may have a substituent.

The substituents for these alkyl groups, allyl groups, aralkyl groups, and aryl groups include aralkyl groups, aralkyl groups, and aryl groups such as aralkyl groups, aralkyl groups, and aryloxy groups. Q
As a +6, the same as mentioned above can be mentioned, and as a substituent for a vinyl group, alkylno such as methyl pigeon, (, 7-reel type such as phenyl group, etc.) can be used.

I! One substituent R4 is a hydrogen atom or an alkoxy group which may have a substituent (for example, an alkoxy group having carbon number/♂♂).
The Squa IJ IJ compound represented by 1) is an azulene compound which may have a substituent (the general formula [
1], represented by "A", ) and the benzene derivative represented by the general formula ["[T1] (wherein, Hl, R2, R8 and R4 have the same meanings as those in the general formula [■]) ) and the formula [1
3,4t-dihydroxy-3-cyclobutene-
/ can be easily produced by reacting with cordion.

In addition, the solvent used in the manufacturing reaction is:
For example, methanol, ethanol%/-pohanol,
Imp apanol/-) pnol% λ-butanol, amyl alcohol.

/-Heki? Alcohols such as /-ru, cyclohexanol, /-heptatool, /-nonanol, or mixtures of these alcohols with benzene, toluene, xylene, chlorobenzene, aromatic 1M hydrocarbon solvents What can you learn?

In addition, the reaction size in the production reaction is usually 7
0~/! A warm temperature of θ°C, preferably 90 to 720°C is used.

The squarylium compound represented by the general formula [■] of the present invention is soluble in a wide range of solvents.

For example, halogen-containing hydrocarbon purple solvents such as lyoform, dichloromethane, dichloroethane, dibromoethane, and tetracumylethane, diethyl ether, dioxane, and tetrahydrofuran.

Ether solvents such as dimethoxyethane, ester solvents such as ethyl acetate and ethyl cellosolve acetate, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, acetamide, N,N-dimethyl 7-cetamide, N-methyl biaridone, etc. amide solvents, methanol, ethanol, methylcellosolve, etc. benzene, toluene, xylene.

It is soluble in aromatic hydrocarbon solvents such as chlorobenzene and solvents such as dimethyl sulfoxide.

Examples of substrate materials for the optical recording medium of the present invention include glass and plastics. Plastics are preferred due to their safety and multi-layer properties.

Plastics include acrylic resin, methacrylic resin, polycarbonate resin, vinyl chloride resin, vinyl acetate resin, and polyester resin.

Examples include polyethylene II gamma resin, polypropylene resin, polyamide it II&, polystyrene resin, epoxy resin, and the like.

The recording layer can be formed on the substrate by vacuum evaporation, or by mixing it with a resin solution and coating it.

Known methods such as dissolving it in a solvent and applying or dipping it can be used. In particular, the compound of the present invention has good solubility in solvents and is therefore suitable for coating methods.

Film formation by coating can be obtained by, for example, dissolving the compound represented by the above general formula [■] in a solvent, mixing it with a binder as the case may be, and spin-coding the mixture. As a binder, polyimide, polyamide resin, polystyrene resin, acrylic! T4 fat, polyester resin.

Examples include polycarbonate resin and cellulose resin.

In this case, the ratio of the squarylium compound as a light-absorbing substance to the resin is preferably /Owt% or more.

In the case of film formation using the spinner method, the number of rotations per rotation is! 00~j 0
00 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, in order to improve the stability and light resistance of the recording medium, transition metal chelate compounds (including acetylacetonate chelate, bisphenyldithiol, salicylaldehyde oxime, bisditheo-α- It may contain diketone #) or a tertiary amine compound. Furthermore, other dyes can be used in combination as necessary. Other dyes have different fI
It may be an IrM squarylium dye, or it may be a phthalocyanine-based, naphthoquinone-based, anthraquinone-based, triarylmethane-based, azo dye, cyanine-based, indophenol-based, lyconium-based, or naphtholactam-based dye, or other dyes.

Coating solvents for forming a recording layer by a coating method such as a doctor blade method, a casting method, a spinner method, a dipping method, and especially a spinner method include bumoform, dibuamoethane, ethyl cellosolf, xylene, and lya. Those having a boiling point of 7.20 to 760°C, such as lobenzene and cyclohexanone, are preferably used.

The thickness of the recording layer of the optical recording medium of the present invention is 1/x
/ 00 X-jpl Liket L <&txaoni
-32.

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.

The recording on the recording medium obtained as described above is as follows.

By emitting laser light, preferably semiconductor laser light, focused to about 7 gm on the recording layer provided on both sides or one side of the substrate? Te now. In the portion irradiated with the laser beam, thermal deformation of the P-tS such as decomposition, evaporation, and melting occurs due to absorption of laser energy.

The recorded information is reproduced by using a laser beam to read the difference in reflectance between areas where thermal deformation has occurred and areas where no thermal deformation has occurred.

As a light source, Hθ-Ne laser, Ar laser,
Although various lasers such as semiconductor lasers can be used, semiconductor lasers are particularly preferred due to concerns about cost and size.

As the semiconductor laser, lasers having a center wavelength of /3θ nm, a center wavelength of 710 nm, and shorter wavelengths can be used.

Examples Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these Examples.

Example/3,a-dihydroxy-3-cyclobutene-7,λ-
Zeon l! 30 ml of 4Cn-butyl alcohol was added and dissolved by heating to about 100°C.

To this solution, 240q of 4t-dimethyl-7-1ao-propylazulene (guaiazulene), 310q of m-benzoylamino-N,N-diethylaniline, and toluene/! - is sword 0, lθ! While water produced at ~/10°C was azeotropically distilled off, the mixture was stirred for about 2θ minutes to complete the reaction. After cooling, the reaction solution was subjected to column quadrography.
Make one.

The following structural formula: Id yc, this compound is /♂6~/
It showed a melting temperature of 7°C. Furthermore, the major absorption wavelength of the autumn yield spectrum of this compound in aaa form is 724'nm.

In this example, the squarylium compound was dissolved in /, /,, 2° cortitrachloride, and the meta-afri roof was wide by spin code (rotation speed/r00rptn).

Center wavelength in this thin film! When irradiated with a semiconductor laser beam of jOnm at an output of gmW and a beam diameter of about /μm, clear holes (bits) with a width of about /μm and a bit length of about λμm were formed. Carrier level/noise level (
c/N) ratio was j2dB.

The light resistance and resistance to reproduction light were also good.

Example m-benzoylamino-N in Example/.

m-7 ceteramino-N instead of N-dimethylaniline
, N-diethylaniline and the method of Example/1
* Obtain the compound represented by the following structural formula.

Oe The absorption spectrum of this compound in chloroform (j) had a large absorption wavelength of ?2!nrn.

This compound was cold-blooded in the same manner as in Example 1 to obtain a thin film of J''!0λ. The maximum absorption wavelength of thin H1 was 77 nm. The O/N ratio was determined in the same manner as in Example. Measure and compare
It was 2 dE. The light resistance and resistance to reproduction light were also good.

Example 3 Example 7 Kl! A 1M film of the SQUA IJium compound synthesized in Table 4 and listed in Table 7 of FC Aoi was formed on a methacrylic resin plate under the same conditions as in Example.

The maximum absorption wavelength 1 of the squarylium thread compound in chloroform and the maximum absorption wavelength of the red membrane are shown in Figure 1.

When the obtained coating was irradiated with a half-heavy laser beam of middle wavelength ♂3θ run, 5 holes (bits) with very clear outlines were formed. The reflectance is also low.

The 0/N ratio was also excellent. In addition, it has good monochromaticity and resistance to reproduction light.

,/'' Effects of the Invention The squarylium compound of the present invention has high solubility in a single organic solvent, so it can be coated by coating when preparing an optical He recording medium.In addition, the compound has a high reflectance. Since the compound has good contrast and excellent light resistance and resistance to reproduction light, an excellent optical recording medium can be obtained by incorporating the compound as a light-absorbing substance in the recording layer.

Founder: Mitsubishi Chemical Industries, Ltd. (7 others)

Claims (2)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
... [I] [In the formula, A represents an azulenyl group which may have a substituent, R^1 and R^2 are a hydrogen atom, an alkyl group which may have a substituent, allyl group, an aralkyl group, or an aryl group, and R^1 and R^2 may be linked to each other to form a heterocycle with a nitrogen atom. R^3 is ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ or -SO_2R^
6 (R^5 and R^6 are an alkyl group, an alkoxy group, a vinyl group, a cycloalkyl group, a cycloalkyloxy group, an allyl group, an aralkyl group, which may have a substituent,
Indicates an aryl group or an aryloxy group. ), and R^4 represents a hydrogen atom or an alkoxy group which may have a substituent. ] A squarylium compound represented by (2) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
[I] [In the formula, A represents an azulenyl group which may have a substituent, and R^1 and R^2 are a hydrogen atom, an alkyl group, an allyl group, an aralkyl group which may have a substituent. represents a group or an aryl group, and R^1 and R^2 may be linked to each other to form a heterocycle with a nitrogen atom. R^3 is ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ or -SO_2R^
6 (R^5 and R^6 are an alkyl group, an alkoxy group, a vinyl group, a cycloalkyl group, a cycloalkyloxy group, an allyl group, an aralkyl group, which may have a substituent,
Indicates an aryl group or an aryloxy group. ), and R^4 represents a hydrogen atom or an alkoxy group which may have a substituent. ] An optical recording medium comprising a recording layer containing a squarylium compound represented by the following.