EP1377970A1

EP1377970A1 - Optical data carrier containing a cyclizable compound in the information layer

Info

Publication number: EP1377970A1
Application number: EP02706771A
Authority: EP
Inventors: Horst Berneth; Friedrich-Karl Bruder; Wilfried Haese; Rainer Hagen; Karin HASSENRÜCK; Serguei Kostromine; Peter Landenberger; Rafael Oser; Thomas Sommermann; Josef-Walter Stawitz; Thomas Bieringer
Original assignee: Bayer Chemicals AG
Current assignee: Lanxess Deutschland GmbH
Priority date: 2001-03-28
Filing date: 2002-03-20
Publication date: 2004-01-07
Also published as: US20020197561A1; CN1513173A; WO2002080163A1; JP2004525801A; TWI246686B

Abstract

The invention relates to an optical data carrier containing a preferably transparent substrate that is optionally already coated with a protective layer already. An information layer that can be written using light, an optional protective layer, an optional adhesive layer and, finally, a covering layer are applied to the surface of the substrate. The optical data carrier can be written and read using blue light, preferably laser light, whereby the information layer contains a light-absorbing compound. The data carrier is characterized in that at least one colorant, which is thermally cyclized, is used as the light-absorbing compound.

Description

Optical data carrier containing a cyclizable compound in the information layer

The invention relates to a write-once optical data carrier, which in the

Information layer contains a cyclizable, light-absorbing compound, as well as a process for the production of the optical data carriers, their use and still new cyclizable light-absorbing compounds.

The write-once optical data carriers using special light-absorbing substances or mixtures thereof are particularly suitable for use with high-density writable optical data storage devices that work with blue laser diodes, in particular GaN or SHG laser diodes (360 - 460 nm) and / or for use with DVD-R or CD-R discs that work with red (635 - 660 nm) or infrared (780 - 830 nm) laser diodes, as well as the application of the above-mentioned dyes to a polymer substrate, in particular polycarbonate, by spin coating or vapor deposition.

The compact disk (CD-R, 780 nm), which can be written on once, has experienced enormous volume growth recently and represents the technically established system.

The next generation of optical data storage media - the DVD - is currently being launched on the market. The storage density can be increased by using shorter-wave laser radiation (635 to 660 nm) and a higher numerical aperture NA. The recordable format in this case is the DVD-R.

Today optical data storage formats using blue laser diodes (based on GaN, JP 08191171 or Second Harmonie Generation SHG JP 09050629) (360 nm to 460 nm) with high laser power are being developed. Writable optical data storage devices will therefore also be used in this generation. The achievable storage density depends on the focus of the laser spot in the Information level. The spot size scales with the laser wavelength λ / NA is the numerical aperture of the objective lens used. In order to obtain the highest possible storage density, the aim should be to use the smallest possible wavelength λ. 390 nm are currently possible on the basis of semiconductor laser diodes.

The patent literature describes dye-based writable optical data memories which are equally suitable for CD-R and DVD-R systems (JP-A 11 043 481 and JP-A 10 181 206). For a high reflectivity and a high modulation level of the readout signal, as well as for a sufficient sensitivity when writing, use is made of the fact that the IR wavelength 780 nm of the CD-R lies at the foot of the long-wave flank of the absorption peak of the dye, the red one Wavelength 635 nm or 650 nm of the DVD-R lies at the foot of the short-wave flank of the absorption peak of the dye. This concept is described in JP-A 02 557 335, JP-A 10 058 828, JP-A 06 336 086, JP-A

02 865 955, WO-A 09 917 284 and US-A 5 266 699 extended to the 450 nm working wavelength range on the short-wave flank and the red and IR range on the long-wave flank of the absorption peak.

In addition to the optical properties mentioned above, the writable information layer made of light-absorbing organic substances must have a morphology which is as amorphous as possible in order to keep the noise signal as small as possible when writing or reading. For this purpose, it is particularly preferred that when the substances are applied by spin coating from a solution, by vapor deposition and / or sublimation, subsequent crystallization of the light-absorbing substances with metallic or dielectric layers in vacuum is prevented.

The amorphous layer of light-absorbing substances should preferably have a high heat resistance, since otherwise further layers of organic or inorganic material, which are applied to the by sputtering or vapor deposition light-absorbing information layer are applied, form diffuse interfaces by diffusion and thus adversely affect the reflectivity. In addition, a light-absorbing substance with too low heat resistance at the interface to a polymeric carrier can diffuse in the latter and in turn adversely affect the reflectivity.

An excessively high vapor pressure of a light-absorbing substance can sublimate the above-mentioned sputtering or vapor deposition of further layers in a high vacuum and thus reduce the desired layer thickness. This in turn leads to a negative influence on the reflectivity.

/

The object of the invention is therefore to provide suitable compounds which meet the high requirements (such as light stability, favorable signal-to-noise ratio, damage-free application to the substrate material, etc.) for use in the information layer in a write-once optical data carrier, in particular for high-density recordable optical media Meet data storage formats in a laser wavelength range from 360 to 460 nm.

Surprisingly, it was found that cyclisicherbar, light-absorbing compounds can meet the above-mentioned requirement profile particularly well.

The invention therefore relates to an optical data carrier, comprising a preferably transparent substrate, possibly already coated with a protective layer, on the surface of which an information layer which can be written on with light, optionally a protective layer, optionally an adhesive layer and finally a cover layer which is coated with blue light are applied , preferably laser light, particularly preferably light with 360-460 nm, in particular 380-440 nm, very particularly preferably at 395-415 nm can be written and read, the information layer containing a light-absorbing compound and optionally a binder, characterized in that the light absorbing compound has a chemical arrangement that cyclizes thermally to 5, 6 or 7 rings when written.

The light-absorbing compound should preferably be caused to shift the local absorption maximum in the range of 350-470 nm by the thermal cyclization of the chemical arrangement. In particular, the shift is more than 25 nm (Δλ max), particularly preferably more than 35 nm, very particularly preferably more than 45 nm. The shift is preferably hypsochromic.

The thermal change is preferably carried out at a temperature <600 ° C., particularly preferably at a temperature <400 ° C., very particularly preferably at a temperature <300 ° C., in particular <200 ° C.

The thermal cyclization is likewise preferably carried out only at a temperature of> 100 ° C., in particular> 140 ° C., preferably at> 180 ° C.

The cyclization _temperature T _C y _C is determined, for example, by means of differential thermal analysis DTA. In the preferred exothermic cyclization, it corresponds to the maximum of the rearrangement signal. The heating rate for DTA measurements is, for example, 10 ° C per minute. The full width at half maximum of the rearrangement signal under these conditions is preferably less than 10 ° C., particularly preferably less than 7 ° C., very particularly preferably less than 5 ° C. Half-width in the sense of the invention is the width of the signal that the signal has halfway up from the base point to the maximum.

A compound which has a chemical arrangement which can thermally cyclize to 5-, 6- or 7-rings is preferably used as the light-absorbing compound. A compound which corresponds to the formula (I) or (II) is particularly preferably used as the light-absorbing compound.

X ')

\ stands for X ^* -x ⁷ i (II l

stands in what

X ^{1 represents} NR ¹ , O or S,

X ^{2 represents} CR ² or N,

X ^{3 represents} CR ³ or N,

X ^{4 represents} CR ⁴ or N,

X ³ is CR ^D or N, where in the row X ^■ 2 - no two nitrogen atoms are adjacent X5 _v ^D - _v X3 ^J - _v X

X ° for CR, 6 ^Ö rR) 7'rR) 8 ^B , C

X ^{7 stands} for CR ¹³ R ¹⁴ or for C = R ¹⁵ ,

X ⁸ for O, NO .1 ¹ 6 ⁰ , CrR. l ¹ 7 'rR, 1 ^ι 8 ^s or C = R ^ιy X ^{9 represents} O, NR ²⁰ , CR ²¹ R ²² or C = R ²³ , where X ⁹ does not represent O if X ^{8 represents} O,

n, m independently of one another represent 0 or 1,

R ^{1 is} hydrogen, Ci to C ₆ alkyl, Ci to C ₆ alkenyl, Ci to C ₆ alkynyl, C ₄ to C ₇ cycloalkyl, C ₇ to Cis aralkyl, Ci to C ₆ -alkoxycarbonyl, aryl or

Hetaryl, where the hetaryl radical can contain up to 3 heteroatoms and the aryl or hetaryl radical can be substituted by up to 3 nonionic radicals,

R ^{2 represents} hydrogen, bromine, Ci to C ₆ alkyl, Ci to C ₆ alkenyl, Ci to C ₆ alkynyl, C ₆ to C ₁₀ aryl, C ₇ to s-araryl, hetaryl, Ci to C ₆ alkoxy, mono- or di-Cr to C ₆ alkylamino, N-Ci to C ₆ alkyl-NC ₆ to C ₁₀ arylamino or with R ¹ together part of a five- or sixth is a membered aromatic or partially hydrogenated ring which may contain 1 to 4 heteroatoms or carbonyl groups and / or benzene or naphthane fused and / or may be substituted by nonionic, preferably electron donor,

R ³ for hydrogen, Cj to C ₆ alkyl, Ci to C ₆ alkenyl, C ₆ to C ₁₀ aryl, C ₇ to C ₁₅ araryl, hetaryl, Ci to C ₆ alkoxycarbonyl, formyl , Cyano, nitro, halogen or together with R ^{2 is} part of a five- or six-membered aromatic or partially hydrogenated ring which may contain 1 to 4 heteroatoms or carbonyl groups and / or benzylated or naphthanellated and / or their rings by nonionic radicals can be substituted

R ⁴ for hydrogen, amino, bromine, Ci to C ₆ alkyl, Cr to C ₆ alkenyl, Ci to

C ₆ -alkynyl, C ₆ - to C ₁₀ -aryl, C ₇ - to C ₁₅ -aryl, hetaryl, - to C ₆ -alkoxy, Cj- to C ₆ -thioalkoxy, mono- or di-C to C ₆ - Alkylamino, NC to C ₆ -

Alkyl-NC ₆ - to Qo-arylamino or together with R ^{3 is} part of a five- or is a 6-membered aromatic or partially hydrogenated ring which may contain 1 to 4 heteroatoms or carbonyl groups and / or benzylated or naphthanellated and / or substituted by nonionic, preferably electron donor,

R ^{5 represents} hydrogen or an electron acceptor, in particular cyano, nitro, - (C = R ²⁴ ) R ²³ , cationic radicals such as ammonium or pyridinium or together with R ⁴ forms part of a five- or six-membered aromatic or partially hydrogenated ring is, which can contain up to 4 heteroatoms or carbonyl groups and / or fused to benzene or naphthane and / or by nonionic

Residues can be substituted,

R ^{6 represents} hydrogen, bromine, chlorine, methoxy or ethoxy,

R ^{7 represents} hydrogen, bromine, chlorine or methoxy if R ^{6 represents} methoxy or represents ethoxy if R ^{6 represents} ethoxy,

R ^{8 represents} bromine, chlorine, iodine, cyano, tosylate, trifiate, Ci to C ₆ alkanoyloxy, C to C ₆ alkylthio or represents methoxy if R ^{7 represents} methoxy or represents ethoxy if R ^{7 represents} ethoxy,

R ⁹ , R ¹⁰ and R ⁿ independently of one another for Ci to C ₆ alkoxy, chlorine, bromine, iodine, Ci to C ₆ alkanoyloxy, Ci to C ₆ alkylthio, C ₆ to o-aryloxy, C ₆ - are to Cio-arylcarbonylamino or one of these radicals together with R ^{5 is} part of a five- or six-membered aromatic or partially hydrogenated ring which

May contain carbonyl groups or 1 to 4 heteroatoms and / or benzyl or naphthanellated and / or may be substituted by nonionic radicals,

R ^{12 is} hydrogen, Ci to C ₆ alkyl, d to C ₆ alkenyl, Q to C ₆ alkynyl, C ₄ to C ₇ cycloalkyl, C ₇ to C ₁₅ aralkyl, Ci to C ₆ alkoxycarbonyl, aryl or Hetaryl, where the hetaryl radical can contain up to 3 heteroatoms and the aryl or hetaryl radical can be substituted by up to 3 nonionic radicals,

R ¹³ ₅ R ¹⁴ , R ¹⁷ , R ¹⁸ , R ²¹ and R ²² independently of one another represent hydrogen, CC ₃ alkyl, fluorine, chlorine or bromine,

R is O, S, = NR ²⁶ or CR ²⁷ R ²⁸ ,

R ¹⁶ and R ²⁰ independently of one another for hydrogen, d- to C ₆ - alkyl, Ci to C ₆ -

Alkenyl, Cj to C ₆ alkynyl, C ₄ to C ₇ cycloalkyl, C ₇ to C ₅ aralkyl, Ci to C ₆ alkoxycarbonyl, aryl or hetaryl, where the hetaryl radical can contain up to 3 heteroatoms and the aryl or hetaryl radical can be substituted by up to 3 nonionic radicals,

R, 1 ^ι 9 ^{y stands} for O, S, = NR ²⁹ or CR ³⁰ R ³¹ ,

R ^{23 stands} for O, S, = NR ³² , CR ³³ R ³⁴ ,

R ^{24 stands} for O, S or NR ³⁵ ,

R ²⁵ for bromine, amino, N-Ci to C ₆ alkylamino, di-N-Ci to C ₆ alkylamino, N- Ci to C ₆ alkyl-NC ₆ to d _ö arylamino, Ci to C ₆ -alkanoyloxy, C ₆ - to Cio-aryloxy, Ci- to C ₆ -alkyl, Ci- to C ₆ -alkoxy, Ci- to C ₆ -alkylthio or X ^{6 is} part of a 5- or 6-membered ring is

R ²⁶ , R ²⁹ , R ³² and R ³⁵ independently of one another are hydrogen, Ci to C ₆ alkyl, Ci to C ₆ alkenyl, C to C ₆ alkynyl, C ₄ to C ₇ cycloalkyl, C ₇ - to cis

Aralkyl, Ci- to C ₆ alkoxycarbonyl are, aryl or hetaryl, wherein the hetaryl radical can contain up to 3 hetero atoms, and the aryl or

Hetarylrest can be substituted by up to 3 nonionic residues and R ²⁷ , R ²⁸ , R ³⁰ , R ³¹ , R ³³ and R ³⁴ independently of one another for hydrogen, C _r to C ₆ alkyl, Ci to C ₆ alkenyl, C ₄ to C ₇ cycloalkyl, C ₇ to Cis-aralkyl, aryl or hetaryl, where the hetaryl radical can contain up to 3 heteroatoms and the aryl or hetaryl radical can be substituted by up to 3 nonionic radicals.

The thermal cyclization product of the formula (I) corresponds to the formula (Ia), that of the formula II corresponds to the formula (Ila)

wherein

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁷ , X ⁸ , X ⁹ , n and m have the meaning given above.

X ^{6a represents} CR ⁶ R ⁷ , CO, CS, C = NR ¹² or C-NH,

in which

R ⁶ , R ⁷ and R ^{12 have} the meaning given above.

Both compounds of the formula (Ia) and those of the formula (Ila) are also the subject of the invention.

Examples of nonionic radicals are Ci to C alkyl, Ci to C ₆ alkoxy, halogen, cyano, nitro, d to C alkoxycarbonyl, Ci to C alkylthio, Ci to C ₄ Alkanoylamino, benzoylamino, mono- or di-d to C -alkylamino, Ci- to C ₆ -alkanoyloxy, l- (l, 2,3) triazole and 2- (l, 2,3) triazole in question.

Electron donor residues are, for example, Ci to C ₄ alkoxy, C ₆ to Cio aryloxy, mono- or di-d to C ₆ alkylamino, Nd to C ₆ alkyl-NC ₆ to do-arylamino.

Examples of hetaryl are pyrrole, thiophene, furan, oxazole, isoxazole, imidazole, pyrazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, 1,2,3-triazole, 1, 2,4-triazole and their benzene-fused representatives Question.

Hetaryl in the sense of the invention are also piperidine, pyrrolidine, morpholine, piperazine and chroman.

Alkyl, alkoxy, aryl and heterocyclic radicals can optionally further radicals such as alkyl, halogen, nitro, cyano, CO-NH ₂ , alkoxy, trialkylsilyl,

Wear trialkylsiloxy or phenyl, the alkyl and alkoxy radicals can be straight-chain or branched, the alkyl radicals can be partially or perhalogenated, the alkyl and alkoxy radicals can be methoxylated, ethoxylated or propoxylated or silylated, adjacent alkyl and or alkoxy radicals on aryl or heterocyclic radicals can together form a three- or four-membered bridge and the heterocyclic radicals can be benzannellated and / or quaternized.

In a particularly preferred form, the light-absorbing compounds of the formula I used are those which correspond to the formula (III) (the group capable of cyclization is highlighted in bold).

wherein

R _> 45 represents hydrogen, bromine, chlorine, Ci to C alkyl, Cj to C ₄ alkoxy, cyano, Ci to C alkoxycarbonyl, mono- or di Cj to C ₄ alkylamino,

R ⁴⁶ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ independently of one another for hydrogen, methyl, ethyl, Ci to C ₆ - alkoxy, fluorine, chlorine, bromine, cyano, nitro, Ci to C -alkoxycarbonyl, mono- or di- d to C alkylamino,

R 50 represents hydrogen, methyl, cyano, C ₁ -C ₆ -alkoxycarbonyl, formyl, bromine, chlorine,

R _> 51 for hydrogen, methyl, bromine, amino, N-methylamino, dimethylamino,

Methoxy, ethoxy, -S-CH ₃ ,

R, 52 stands for cyano, C] - to d-alkoxycarbonyl, C ₆ - to do-aryloxycarbonyl, Cj- to C ₆ -alkanoyloxycarbonyl and

X ^{6 represents} cyano, Ci to C ₆ alkoxycarbonyl, C ₆ to C ₁₀ aryloxycarbonyl, Ci to C ₆ alkanoyloxycarbonyl or -CH ₂ -O-SO ₂ - ^ - C ₆ H -CH ₃ .

The dyes of the formula (III) are very particularly preferred Wonn

R ^{45 represents} hydrogen, methyl, ethyl, isopropyl,

R ⁴⁶ , R ^{49 represents} hydrogen,

R ⁴⁷ , R ⁴⁸ independently of one another represent hydrogen, Ci to C ₆ alkoxy, mono- or di-Ci to C ₄ alkylamino,

R ⁵⁰ is hydrogen, methyl, cyano, Ci to C _ö alkoxycarbonyl,

R ^{51 represents} hydrogen, methyl, amino, N-methylamino, dimethylamino, methoxy, ethoxy,

R ⁵² for cyano, Cj to C ₆ alkoxycarbonyl, C ₆ to C ₁₀ aryloxycarbonyl, Ci to

C ₆ -alkanoyloxycarbonyl and

X ⁶ for cyano, Ci to C ₆ alkoxycarbonyl, C ₆ to Cio aryloxycarbonyl, Ci to C ₆ alkanoyloxycarbonyl, -CH ₂ -O-SO ₂ - _. pC ₆ H -CH ₃ .

The light-absorbing compounds of the formula (III) are particularly preferred,

wherein

R ⁴⁵ , R ⁴⁶ , R ^{49 represents} hydrogen,

R ⁴⁷ , R ⁴⁸ independently of one another represent hydrogen, C ₁ -C ₃ -alkoxy, mono- or di-C ₁ to d-alkylamino,

R> 50, _Ώ R51 stands for hydrogen, R 52 is cyano, Ci to Coe-alkoxycarbonyl, Ci to C stands ₆ and alkanoyloxycarbonyl

X ^{6 represents} cyano, Ci to C ₆ alkoxycarbonyl, C ₆ to do aryloxycarbonyl.

The thermal cyclization product of the formula (III) corresponds to the formula (purple)

wherein the radicals R ⁵ -R ^{52 have} the above meanings and

χ6a _represents c-NH, CO or CH ₂ .

In a likewise particularly preferred form, the light-absorbing compounds of the formula I used are those which correspond to the formula (IV)

worm

R ^{66 represents} hydrogen, bromine, chlorine, d to C alkyl, Ci to C ₆ alkoxy, cyano, d to C alkoxycarbonyl, mono- or di-d to C ₄ alkylamino,

R ⁶⁷ for hydrogen, d- to C ₆ -alkyl, d- to C ₆ -alkenyl, C ₆ - to C ₁₀ -aryl, C ₇ - to Cι- ₅ araryl, hetaryl, Ci- to C ₆ -alkoxycarbonyl, formyl , Cyano, nitro, halogen or together with R ^{66 is} part of a five- or six-membered aromatic or partially hydrogenated ring which can contain 1 to 4 heteroatoms and / or benzylated or naphthanellated and / or whose rings are substituted by nonionic radicals can,

R, R, R and R independently of one another are hydrogen, methyl, ethyl, isopropyl, d- to C ₆ -alkoxy, fluorine, chlorine, bromine, cyano, nitro, d- to C ₄ -alkoxycarbonyl, mono- or di Ci bis C ₄ alkylamino, d- to C ₄ -

Are alkanoyloxy or 2 adjacent residues form a butadiene bridge,

70

R can additionally stand for l, 2,3-triazol-2-yl, which can also be benzene-fused or naphthane-fused at the 4,5-position,

R ^{72 represents} O, NH, N-Ci to NC ₃ alkyl,

R ^{73 represents} O, Nd to NC ₆ alkyl, NC ₆ to C ₁₀ aryl,

X ⁶ for cyano, -CH ₂ -O-SO ₂ -i? -C ₆ H ₄ -CH ₃ , -CH ₂ -O-SO ₂ -CF ₃ , Ci to C ₆ alkoxycarbonyl, C ₆ - to Cio-aryloxycarbonyl, Ci- to C ₆ -alkanoyloxycarbonyl and

R ⁷⁵ for hydrogen d to C ₆ alkyl, d to C ₆ alkenyl, d to C ₆ alkynyl, C ₄ to C ₇ cycloalkyl, C ₇ to C ₅ aralkyl, Ci to C ₆ - alkoxycarbonyl, aryl or

Hetaryl stands, where the hetaryl residue can contain up to 3 heteroatoms and the aryl or hetaryl radical can be substituted by up to 3 nonionic radicals.

The compounds of the formula (IV) are very particularly preferred

wherein

R ^{66 represents} hydrogen, Ci to C ₄ alkyl, Ci to C ₆ alkoxy, cyano, mono- or di- Ci to C alkylamino,

R ⁶⁷ represents hydrogen, d- to C ₆ alkyl, C ₆ - to C ₁₀ -aryl, hetaryl, Ci to C ₆ - alkoxycarbonyl, formyl, cyano, nitro, halogen,

R ⁶⁸ , R ⁷¹ stand for hydrogen,

R ⁶⁸ , R ^{69 can} additionally form a butadiene bridge,

R ⁶⁹ and R ⁷⁰ independently of one another represent hydrogen, methyl, Ci to C ₂ alkoxy, chlorine, Ci to C ₂ alkoxycarbonyl, mono- or di Ci to C ₄ alkylamino, d- to C -alkanoyloxy,

R ^{70 can} additionally represent l ₅ 2,3-triazol-2-yl, which can also be benzene-fused or naphthane-fused at the 4,5-position,

R ^{72 represents} O or NH,

R ⁷³ stands for O,

X ⁶ for cyano, -CH ₂ -O-SO ₂ - -C ₆ H ₄ -CH3, -CH ₂ -O-SO ₂ -CF ₃ , Ci to C ₆ alkoxycarbonyl, C ₆ to -Cι ₀ Aryloxycarbonyl, Ci to d-alkanoyloxycarbonyl and R> 7 "5 is hydrogen, d- to C ₆ -alkyl, C ₅ - to C ₆ -cycloalkyl, C ₇ - to -CC ₅ aralkyl, Ci- to Cδ-alkoxycarbonyl, aryl.

The compounds of the formula (IV) are particularly preferred,

wherein

R ⁶⁶ , R ⁶⁷ , R ⁶⁸ and R ^{71 represent} hydrogen,

R ⁶⁹ and R ⁷⁰ independently of one another are hydrogen, methyl, Ci to C ₂ alkoxy,

Chlorine, C ₁ -C ₂ -alkoxycarbonyl, mono- or di C 1 -C 4 -alkylamino, d- to C -alkanoyloxy,

R 72 represents O or NH,

R, 7 "3 stands for O,

X> -6 ^D is cyano, Ci to C ₆ alkoxycarbonyl, C ₆ - to Cio-aryloxycarbonyl and is

R> 7 "5 represents hydrogen, d- to C ₆ -alkyl, C ₅ - to C ₆ -cycloalkyl, C ₇ - to -CC ₅ aralkyl, Ci to C ₆ - alkoxycarbonyl, aryl.

The thermal cyclization product of the formula (IV) corresponds to the formula (IVa)

wherein

R ⁶⁸ - R ⁷³ and R ^{75 have} the meaning given above and

X ^{6a represents} C = NH, CO or CH ₂ .

In a particularly preferred form, the thermally cyclizable dye used is one of the formula (V)

wherein

X ^{1 represents} NR ¹ , O or S,

R is hydrogen, Ci to C ₆ alkyl, Ci to C ₆ alkenyl, Ci to C ₆ alkynyl, C to C ₇ cycloalkyl, C ₇ to C ₅ aralkyl, Ci to C ₆ Alkoxycarbonyl, aryl or hetaryl, where the hetaryl radical can contain up to 3 heteroatoms and the aryl or hetaryl radical can be substituted by up to 3 nonionic radicals,

R ⁸⁵ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ independently of one another are hydrogen, methyl, ethyl, isopropyl, Ci to C ₆ alkoxy, fluorine, chlorine, bromine, cyano, nitro, Ci to C ₄ alkoxycarbonyl, Mono- or Di Ci to C ₄ alkylamino, Ci to C alkanoyloxy or 2 adjacent radicals form a butadiene bridge, R ^{87 can} additionally stand for l, 2,3-triazol-2-yl, which can also be benzene-fused or naphthane-fused at the 4,5-position,

R _> 8 ^a 9 ^{y represents} O, NH, N-Ci to NC ₃ alkyl,

R _> 9 ^y 0 ^{υ is} O, N-Ci to C ₆ alkyl or NC ₆ to C ₁₀ aryl,

R> 9 ^y 1 'for hydrogen, cyano or .d _Λ e „_r, stands,

X6 stands for CR ⁹⁸ R "R ¹⁰⁰ , CR ^m = 0, CR ¹⁰² = S, CR ¹⁰³ = NR ¹⁰⁴ or C ^ N,

R ^{93 represents} O, S or = NR ⁹⁵ ,

R ⁹⁴ for Ci- to C ₆ alkoxy, Ci to C ₆ - alkyl, Ci to C ₆ alkanoyloxy, C _\ - to C ₆ -

Alkylthio, C ₆ - to Cι ₀ aryloxy, C ₆ - to Cio-arylcarbonylamino, amino, N-Ci to C ₆ alkylamino, di-N-Ci to C ₆ alkylamino, N-Ci to C ₆ -Alkyl-N- C ₆ - to -CC ₀ arylamino,

R ^{95 represents} hydrogen, Ci to C ₆ alkyl, Ci to C ₆ alkenyl, C ₄ to C ₇ cycloalkyl,

C - to Ci ₅ aralkyl, Ci to C _ö alkoxycarbonyl, aryl,

R ^{98 represents} hydrogen, bromine, chlorine, methoxy or ethoxy,

R ^{99 stands} for hydrogen, bromine, chlorine or for methoxy if R ⁹⁸ stands for methoxy or stands for ethoxy if R ⁹⁸ stands for ethoxy,

R ^{100 represents} leaving groups such as bromine, chlorine, iodine, cyano, tosylate, triflate, Ci to C ₆ alkanoyloxy, Ci to C ₆ alkylthio or represents methoxy if R ^{99 represents} methoxy or represents ethoxy if R ^{99 represents} ethoxy, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ for d- to C ₆ -alkoxy, chlorine, bromine, iodine, d- to C ₆ -alkanoyloxy ₅ Cj- to C ₆ -alkylthio, C ₆ - to Cio-aryloxy, C ₆ - to Cio-arylcarbonylamino and

R ¹⁰⁴ for hydrogen, Ci to C ₆ alkyl, d to C ₆ alkenyl, d to C ₆ alkynyl, C ₄ to C ₇ cycloalkyl, C to C ₅ aralkyl, Ci to C ₆ -alkoxycarbonyl, aryl or hetaryl, where the hetaryl radical can contain up to 3 heteroatoms and the aryl or hetaryl radical can be substituted by up to 3 nonionic radicals.

10

The compounds of the formula (V) are very particularly preferred

wherein

15 X ^{1 represents} NR ¹ , O or S,

R ^{1 represents} hydrogen, Ci to C ₆ alkyl, C ₅ to C ₆ cycloalkyl, C _r to C ₆ alkoxycarbonyl, aryl,

20 R ⁸⁵ and R ⁸⁸ independently represent hydrogen or

R ⁸⁵ and R ^{86 can} additionally form a butadiene bridge or

R ⁸⁶ and R ⁸⁷ independently of one another are hydrogen, methyl, ethyl, isopropyl, d- 25 to C ₆ -alkoxy, chlorine, bromine, cyano, nitro, d- to C ₄ -alkoxycarbonyl,

Mono- or Di Ci to C ₄ alkylamino, Ci to C alkanoyloxy, or

R ^{87 can} additionally stand for l, 2,3-triazol-2-yl, which can also be benzene-fused or naphthane-fused at the 4,5-position,

^'30

R, 8 ^δ 9 ^{y represents} O or NH, R ⁹⁰ stands for O,.

R ^{91 represents} hydrogen, cyano or (C = R ⁹³ ) R ⁹⁴

X6 stands for CR ⁹⁸ R "R ¹⁰⁰ , CR ¹⁰¹ = O, CR ^{, 02} = S or C _≡ N,

R ⁹³ stands for O,

R ⁹⁴ for Ci to C ₆ alkoxy, Ci to C ₆ alkanoyloxy, C ₆ to C ₀ aryloxy, C ₆ to

Cio-arylcarbonylamino stands,

R ⁹⁸ and R ^{99 represent} hydrogen,

R ¹⁰⁰ for leaving groups such as bromine, chlorine, iodine, cyano, tosylate, triflate, Ci bis

C ₆ alkanoyloxy, Ci to C ₆ alkylthio and

R ¹⁰¹ and R ¹⁰² independently of one another for Cj to C ₆ alkoxy, chlorine, bromine, iodine, Ci to C ₆ alkanoyloxy, Ci to C ₆ alkylthio, C ₆ to Cio aryloxy, C ₆ to do- Arylcarbonylamino stand.

The compounds of the formula (V) are particularly preferred,

wherein

R ^{1 represents} hydrogen, Ci to C ₆ alkyl, C ₅ to C ₆ cycloalkyl, Ci to C ₆ alkoxycarbonyl, aryl,

X ^{1 represents} NR ¹ ,

R ^8S , R ^{88 represent} hydrogen, R ⁸⁶ , R ⁸⁷ independently of one another represent hydrogen, methyl, Ci to C ₄ alkoxy, chlorine, Ci to C ₄ alkoxycarbonyl, Ci to C dialkylamino, Ci to C alkanoyloxy,

R & 9 stands for O or NH,

R) 9 ^y 0 ^υ stands for O,

R ^{91 represents} hydrogen or Ci to C ₄ alkoxycarbonyl

X6 stands for CR ¹⁰¹ = O or C≡N,

R ^{101 represents} Ci to C ₆ alkoxy, Ci to C ₆ alkanoyloxy, Ci to C ₆ alkylthio, C ₆ to Cio aryloxy.

The thermal cyclization product of the formula (V) corresponds to the formula (Va)

wherein

R ¹ , R ⁸⁵ - R ⁹¹ and X ^{1 have} the meanings given above and

X ^{6a stands} for CR9SR9, CO, CS, C = NR ¹⁰⁴ or C = NH. In a likewise preferred form, the light-absorbing compounds of the formula (I) used are those with the formula (VI)

wherein

X ^{1 represents} NR ¹ ,

R ¹ for hydrogen, Ci to C ₆ alkyl, Ci to C ₆ alkenyl, Ci to C ₆ alkynyl, C to C cycloalkyl, C ₇ to ds-aralkyl, Ci to C ₆ Alkoxycarbonyl, aryl or

R ¹¹¹ for hydrogen, methyl, bromine, amino, N-methylamino, dimethylamino,

Methoxy, ethoxy, -S-CH ₃ ,

R ¹¹² for cyano, Ci- to C ₆ -alkoxycarbonyl, C ₆ - to Cio-aryloxycarbonyl, Cι ~ to C ₆ -alkanoyloxycarbonyl, mono- or di-Ci- to C ₆ -, alkylaminocarboxylic acid amide, mono- or diarylaminocarboxylic acid amide, Monoaryl-mono- Ci to C ₆ -alkylaminocarboxamide, carboxamide,

Ring A stands for a 5-9 membered partially unsaturated, aromatic or quasi-aromatic ring which can contain 1-4 heteroatoms or carbonyl groups and / or benzene or naphthane fused and / or substituted by nonionic radicals and X ^{6 represents} cyano, d- to C ₆ -alkoxycarbonyl, C ₆ - to C ₁₀ -aryloxycarbonyl or Cr to Cö-alkanoyloxycarbonyl.

Compounds of the formula (VI) in which

X ^{1 represents} NR ¹ ,

R ^{1 is} Ci to C ₆ alkyl, d to C ₆ alkenyl, d to C ₆ alkynyl, C ₄ to C ₇ cycloalkyl, C ₇ to C 1 aralkyl, aryl or hetaryl, the hetaryl radical can contain up to 3 heteroatoms and the aryl or hetaryl radical can contain up to

3 nonionic radicals can be substituted,

R ^{111 represents} hydrogen, methyl, bromine, methoxy, ethoxy,

R ¹¹² for cyano, Cj- to C ₆ -alkoxycarbonyl, C ₆ - to Cio-aryloxycarbonyl, Cj- bis

C ₆ -alkanoyloxycarbonyl,

Ring A represents a 5-7-membered, partially unsaturated, aromatic or quasi-aromatic ring which can contain 1-4 heteroatoms or carbonyl groups and / or benzene- or naphthannellated and / or can be substituted by nonionic radicals and

X ^{6 represents} cyano, C _\ - to C ₆ -alkoxycarbonyl, C ₆ - to Cio-aryloxycarbonyl.

The compounds of the formula (VI) are very particularly preferred

X ^{1 represents} NR ¹ ,

R ^{1 is} C to C ₆ alkyl, C _r to C ₆ alkenyl, C ₅ to C ₇ cycloalkyl, C ₇ to C ₅ aralkyl, aryl or hetaryl, the hetaryl radical having up to 3 heteroatoms may contain and the aryl or hetaryl radical may be substituted by up to 3 nonionic radicals,

R ^u 'represents hydrogen,

R ^{112 represents} cyano, Ci to C ₆ alkoxycarbonyl or C ₆ to Cio aryloxycarbonyl,

Ring A stands for a 5-6-membered, partially unsaturated, aromatic or quasi-aromatic ring which may contain 1-4 heteroatoms or carbonyl groups and / or benzene or naphthane fused and / or substituted by nonionic radicals and

X ^{6 represents} cyano, Ci to C _ö alkoxycarbonyl, C ₆ to Cio-aryloxycarbonyl.

The thermal cyclization product of the formula (VI) corresponds to the formula (Via)

wherein

the radicals X - ^• 1, R Tj H 1, u, n “d RTJ 112 have the above meanings and

X ^{6a stands} for C = NH or C = O.

For example, mixtures of the compounds of the formula (I) can also be used to optimize the physical properties of the information layer. For a write-once optical data carrier _according to the invention which is written and read with the light of a blue laser, preference is given to those light-absorbing compounds whose absorption maximum λ _{max is} in the range from 350 to 470 nm and which are above the cyclization _temperature T _{cyc in} a ring-closed form have converted.

_Light- absorbing compounds with a cyclization _temperature T _cyc of at least 100 ° C. are preferred, particularly preferably greater than _or equal to 140 ° C., in particular greater than _or equal to 180 ° C.

Preferred dyes are those in which the shift in the absorption maximum Δλ _max induced by the thermal cyclization is 25 nm or more, preferably> 35 nm, in particular> 45 nm. If there is a preferably hypsochromic shift, Δλ _{max is} negative. Absorption maximum in the sense of the invention is the local one

Maximum in the range of 350 to 470 nm; it is not necessarily the absolute maximum of the UV / NIS spectrum in the range from 190 to 800 nm.

At the absorption maximum λ _ma χ, the light-absorbing compounds preferably have a molar extinction coefficient ε> 20,000 1 / mol cm, preferably

> 30,000 l / mol cm, particularly preferably> 40,000 l / mol cm, very particularly preferably> 50,000 l / mol cm.

The absorption spectra are measured, for example, in solution.

Compounds of the formula (I) which cyclize thermally to form 6 rings are known in some cases, for example from Arch. Pharm. 1987, 320, 577-581.

The light-absorbing compounds described, in particular of the formula (I), guarantee a sufficiently high reflectivity (> 10%) of the optical data carrier in the blank state and a sufficiently high absorption for the thermal Degradation of the information layer in the case of selective lighting with focused light if the light wavelength is in the range from 360 to 460 nm. The contrast between written and unwritten points on the data carrier is realized by the change in reflectivity of the amplitude as well as the phase of the incident light by the optical properties of the information layer which have changed after thermal degradation.

The light-absorbing compounds are preferably applied to the optical data carrier by spin coating. They can be mixed with one another or with other dyes with similar spectral properties. The

In addition to the light-absorbing compounds, the information layer can contain additives such as binders, wetting agents, stabilizers, thinners and sensitizers and other constituents.

In addition to the information layer, the optical data storage device can carry further layers such as metal layers, dielectric layers and protective layers. Metal and dielectric layers and / or the protective layer (s) serve among other things. to adjust the reflectivity and the heat balance. Depending on the laser wavelength, metals can be gold, silver, aluminum, etc. his. Dielectric layers are, for example, silicon dioxide and silicon nitride. Protective layers are, for example, photocurable lacquers, (pressure-sensitive) adhesive layers and protective films.

Pressure-sensitive adhesive layers mainly consist of acrylic adhesives. Nitto Denko DA-8320 or DA-8310, disclosed in patent JP-A 11-273147, can be used for this purpose, for example.

The optical data carrier has, for example, the following layer structure (cf. FIG. 4): a transparent substrate (1), optionally a protective layer (2), an information layer (3), optionally a protective layer (4), optionally an adhesive layer (5), a cover layer (6). The structure of the optical data carrier can:

contain a preferably transparent substrate (1), on the surface of which at least one information layer (3) which can be written on with light and which can be written on with light, preferably laser light, optionally one

Protective layer (4), optionally an adhesive layer (5), and a transparent cover layer (6) are applied.

contain a preferably transparent substrate (1), on the surface of which a protective layer (2), at least one information layer (3) which can be written on with light, preferably laser light, optionally an adhesive layer (5), and a transparent cover layer (6) are applied.

contain a preferably transparent substrate (1), on the surface of which there is optionally a protective layer (2), at least one information layer (3) which can be written on with light, preferably laser light, optionally a protective layer (4), optionally an adhesive layer (5), and a transparent cover layer (6) are applied.

- Contain a preferably transparent substrate (1), on the surface of which at least one information layer (3) which can be written on with light, preferably laser light, optionally an adhesive layer (5), and a transparent cover layer (6) are applied.

The invention further relates to optical data carriers according to the invention described with blue light, in particular laser light.

The following examples illustrate the subject matter of the invention. Examples

example 1

3.3 g of ethyl ethoxymethylene-cyanoacetate were added to a solution of 4.0 g of 6,7-dimethoxy-3,4-dihydro-l-methylisoquinoline in dry methanol within 30 minutes. The mixture was stirred for 3 hours at 25 ° C. and 3 hours at 40 ° C. The precipitate was filtered off and washed with cold methanol. 3.0 g (52% of theory) of orange powder of the formula (1) were obtained:

Cyclization _temperature T _cyc : 123 ° C (determined with DTA, see description. This also applies to the other examples). λ _max (methanol) = 447 nm ε = 47560 1 / mol cm

Solubility:> 2% in TFP (2,2,3, 3-tetrafluoropropanol) absorption shift after cyclization: Δλ _max - - 49 nm glassy film

A 2% by weight solution of the dye in 2,2,3,3-tetrafluoropropanol was prepared at room temperature. This solution was applied to quartz glass substrate using spin coating. The resulting film thickness of the dye was approximately 150 nm. This sample was heated in a helium stream with an average heating rate of 3 K / min from 50 ° C to 133 ° C and then with an average cooling rate of 1.4 K / min to 81 ° C cooled. During the heating and cooling phase, transmission spectra in the wavelength range from 200 nm to 1700 nm were recorded from the sample. Using the transmission spectra as a function of the Temperature changes in the optical properties can be observed through the ring closure reaction. Figure 1 shows the transmission spectra at the beginning and end of the temperature cycle described above.

Obviously, the absorption band disappears almost completely in the 450 nm range and leads to a change in the absorption properties, which can be used in the wavelength range from 400 to 500 nm for optical storage and reproduction of data, e.g. a laser beam with a suitable pulse duration and pulse energy heats the dye layer above 133 ° C. In addition, each absorption also produces a dispersion of the refractive index above that

Wavelength. This leads to low (short-wave flank) or higher (long-wave flank) refractive indices than 1.4-1.6, which is the usual range for colorless organic materials, especially on the flanks of the absorption bands. At 405 nm, for example, the refractive index of the dye at the beginning of the temperature cycle is 1.17 and at 515 nm it is 2.17 nm. After the temperature cycle, when the absorption band has practically completely disappeared, the decolorized dye has a refractive index in the range from 1.4 to 1.6 in the visible spectrum , This change in the refractive index can also be used for optical storage and reproduction of data, e.g. if a laser beam with a suitable pulse duration and pulse energy heats the dye layer above 133 ° C. Changes in the refractive index and / or the absorption change the reflection and / or transmission properties of thin films on a transparent substrate (glass or polymer) and can therefore be changed by a laser beam which is scanned over markings written with a pulsed and focused laser beam the reflected and / or transmitted amount of light are transformed. The relevant film thicknesses are preferably in the range from 10 nm to 2000 nm.

Figure 2 and Figure 3 show an example of the change in transmission of the sample described above at 405 nm during the temperature cycle. Figure 2 shows the Transmission curve shown over the temperature and Figure 3 over time. It is clear that the ring closure reaction takes place in a very narrow temperature window and time window and is therefore suitable to write data with high speed and small edge blur with a focused and pulsed laser beam that scans over the sample. For the reasons mentioned above, the laser wavelength is preferably in the range from 360 nm to 600 nm, particularly preferably in the range from 380 nm to 550 nm.

Example 2

4 gj> t-butylaniline and 3 g (E -4- (2-dimethylaminoetnenyl) -2-oxo-l, 2-dihydro-quinolin-3-carbonitrile in 15 ml glacial acetic acid were added and the mixture was stirred at 60 ° C. for 6 hours The solid was filtered off with suction and recrystallized from glacial acetic acid, giving 3.90 g (95%) of an orange powder (2):

(2)

Cyclization _temperature T _cyc :. 141 ° C λ _max (DMF) = 464 nm ε = 30620 1 / mol cm

Solubility: 1% in TFP (2,2,3,3-tetrafluoropropanol)

Absorption shift after cyclization: Δλ _max => 1 1001 nm (browning leads to decomposition of the rearranged product; therefore no local maximum in the range of 360-560 nm can be detected. Glass-like film Example 3

To a suspension of 10.0 g of 4-chloro-7-ethyl-3- (2'-methoxycarbonyl) vinyl-coumarin in ethanol was added 6.8 g of isopropylamine and heated under reflux for 6 hours. A solid separated from the solution on cooling and was purified by chromatography with toluene / methanol. 7.3 g (67% of theory) of a pale yellow powder of the formula (3) were obtained:

(3)

Cyclization _temperature T _cyc : 206 ° C λmax (methanol) = 359 nm ε = 20700 1 / mol cm

Solubility: 1% in TFP (2,2,3,3-tetrafluoropropanol)

Absorption shift after cyclization: Δλ _max = -20 nm glass-like film

Example 4

A solution of 3.7 g of ethyl ethoxymethylene cyanoacetate in 10 ml of methanol is added dropwise to a solution of 3 g of cyclopentyl-N-butylimine in 10 ml of methanol at 25 ° C. in the course of 30 minutes. After about 1 hour, an orange-yellow precipitate precipitates, which is filtered off and washed with petroleum ether. Yield: 4.2 g (77%) of dye (4):

(4)

Cyclization _temperature T _cyc : 198 ° C λ _max (methanol) = 441 nm ε = 36910 1 / mol cm

Solubility:> 2% in TFP (2,2,3, 3-tetrafluoropropanol)

Absorption shift after cyclization: Δλ _max = -72 nm glassy film

Suitable dyes that thermally cyclize to 5-7 rings are listed in the following tables:

Examples of compounds of the formula (III)

Examples of compounds of the formula (IV)

* Browning causes decomposition of the rearranged product; no local maximum in the range of 360-560 nm can be detected

Example of compounds of the formula (V)

Examples of compounds of the formula (VI)

Claims

claims

Optical data carrier containing a preferably transparent substrate, possibly already coated with a protective layer, on the surface of which an information layer which can be written on with light, optionally a protective layer, optionally an adhesive layer and finally a cover layer, which are written and read with blue light, preferably laser light, are applied can, wherein the information layer contains a light-absorbing compound, characterized in that the light-absorbing compound has a chemical arrangement which thermally cyclizes to 5-, 6- or 7-rings when written.

2. Optical data carrier according to claim 1, characterized in that the light-absorbing compound of the formula (I) or (II) corresponds

H \ m

(II) stands, ^x \ X ³ X ⁷ μL

wherein

X ¹ for ΝRl. Is O or S,

X ^{2 represents} CR ² or Ν,

X ^{3 represents} CR ³ or Ν, X ^{4 represents} CR ⁴ or N,

X ^{5 stands} for CR ⁵ or N, where in the row X ² -X ³ -X ⁴ -X ⁵ there are no two N atoms adjacent,

X ^{6 stands} for CR ⁶ R ⁷ R ⁸ , CR ⁹ = O, CR ¹⁰ = S, CR ¹ '= NR ¹² or C≡N,

X ^{7 stands} for CR ¹³ R ¹⁴ or for C = R ¹⁵ ,

X ^{8 represents} O, NR ¹⁶ , CR ¹⁷ R ¹⁸ or C = R ¹⁹ ,

X ^{9 represents} O, NR ²⁰ , CR ²¹ R ²² or C = R ²³ , where X ⁹ does not represent O if X ^{8 represents} O,

n, m independently of one another represent 0 or 1,

R ¹ for hydrogen, Cj- to C ₆ -alkyl, C to C ₆ -alkenyl, C _\ - to C ₆ -

Alkynyl, C ₄ - to C ₇ -cycloalkyl, C ₇ - to C ₁₅ -aralkyl, C to C ₆ -alkoxycarbonyl, aryl or hetaryl, the hetaryl radical being up to

Can contain 3 heteroatoms and the aryl or hetaryl radical can be substituted by up to 3 nonionic radicals,

R ² is hydrogen, bromine, C _r to C ₆ alkyl, C to C ₆ alkenyl, C _r to C ₆ alkynyl, C ₆ - to Cι ₀ aryl, C ₇ - to C Araryl, hetaryl, C - up to C ₆ -

Alkoxy, mono- or di-Cr to C ₆ -alkylamino, N- - to C ₆ -alkyl-NC ₆ - to C ^ -arylamino or is together with R ¹ part of a five- or 6-membered aromatic or partially hydrogenated ring that 1 to

May contain 4 heteroatoms or carbonyl groups and / or benzylated or naphthanellated and / or by nonionic, preferably

Electron donor residues can be substituted, R ^{3 is} hydrogen, C to C ₆ alkyl, C to C ₆ alkenyl, C ₆ to C ₁₀ aryl, C ₇ to Cis araryl, hetaryl, Cr to C ₆ alkoxycarbonyl, formyl, cyano, nitro Is halogen or together with R ^{2 is} part of a five- or six-membered aromatic or partially hydrogenated ring which is 1 to

4 may contain heteroatoms or carbonyl groups and / or benzyl or naphthane fused and / or their rings may be substituted by nonionic radicals,

R ^{4 represents} hydrogen, amino, bromine, Cr to C ₆ alkyl, Cr to C ₆ alkenyl,

Cr to C _ö alkynyl, C ₆ to C ₁₀ aryl, C ₇ to C ₁₅ araryl, hetaryl, to Ce alkoxy, Cr to C ₆ thioalkoxy, mono- or di-Cr to C ₆ Alkylamino, N-Cr to C ₆ -alkyl-NC ₆ - to C ₁₀ -arylamino or together with R ^{3 is} part of a five- or six-membered aromatic or partially hydrogenated ring which may contain 1 to 4 heteroatoms or carbonyl groups and / or benzylated or naphthanellated and / or substituted by nonionic, preferably electron donor,

R ^{5 represents} hydrogen or an electron acceptor, in particular for

Cyano, nitro, - (C = R ²⁴ ) R ²⁵ , cationic radicals such as ammonium or pyridinium or together with R is part of a five- or six-membered aromatic or partially hydrogenated ring which can contain up to 4 heteroatoms or carbonyl groups and / or benzylated or naphthane fused and / or substituted by nonionic radicals,

R ^{6 represents} hydrogen, bromine, chlorine, methoxy or ethoxy,

R ^{7 represents} hydrogen, bromine, chlorine or methoxy when R ^{6 is}

Is methoxy or is ethoxy when R ^{6 is} ethoxy, R ^{8 represents} bromine, chlorine, iodine, cyano, tosylate, triflate, Cr to C ₆ alkanoyloxy, Cr to C ₆ alkylthio or stands for methoxy if R ⁷ stands for methoxy or stands for ethoxy if R stands for ethoxy .

R ⁹ , R ¹⁰ and R ¹¹ independently of one another for Cr to C ₆ alkoxy, chlorine, bromine, iodine, Cr to C ₆ alkanoyloxy, Cr to C ₆ alkylthio, C ₆ to Cio-aryloxy, C ₆ to Cio-arylcarbonylamino or one of these radicals together with R ^{5 is} part of a five- or six-membered aromatic or partially hydrogenated ring which may contain carbonyl groups or 1 to 4 heteroatoms and / or benzylated or naphthanellated and / or substituted by nonionic radicals can

R ¹² for hydrogen, Cr to C ₆ alkyl, Cr to C ₆ alkenyl, Cr to C ₆ alkynyl, C to C cycloalkyl, C ₇ to C ₁₅ aralkyl, Cr to C ₆

Alkoxycarbonyl, aryl or hetaryl, where the hetaryl radical can contain up to 3 heteroatoms and the aryl or hetaryl radical can be substituted by up to 3 nonionic radicals,

R ¹³ , R ¹⁴ , R ¹⁷ , R ¹⁸ , R ²¹ and R ²² independently of one another for hydrogen, C

C _{3 are} alkyl, fluorine, chlorine or bromine,

R ^{15 stands} for O, S, = NR ²⁶ or CR ²⁷ R ²⁸ ,

R ¹⁶ and R ²⁰ independently of one another for hydrogen, Cr to C ₆ alkyl, Cr to C ₆ alkenyl, Cr to C ₆ alkynyl, C ₄ to C ₇ cycloalkyl, C ₇ to C ₁₅ aralkyl, Cr to C ₆ - alkoxycarbonyl, aryl or hetaryl, where the hetaryl radical can contain up to 3 heteroatoms and the aryl or hetaryl radical can be substituted by up to 3 nonionic radicals, R ^{19 stands} for O, S, = NR ²⁹ or CR ³⁰ R ³¹ ,

R ^{23 stands} for O, S, = NR ³² , CR ³³ R ³⁴ ,

R ^{24 stands} for O, S or NR ³⁵ ,

R ²⁵ for bromine, amino, N-Cr to C ₆ -alkylamino, di-N-Cr to C ₆ -alkylamino, N-Cr to C ₆ -alkyl-NC ₆ - to C ₁₀ -arylamino, Cr to C ₆ -

Alkanoyloxy, C ₆ - to Cio-aryloxy, Cr to C ₆ - alkyl, Cr to C ₆ - alkoxy, CJ -C ₆ -alkylthio, or X ⁶ is part of a 5- or 6-membered ring is' -

R ²⁶ , R ²⁹ , R ³² and R ³⁵ independently of one another for hydrogen, Cr to C ₆ -

Alkyl, Cr to C ₆ alkenyl, Cr to C ₆ alkynyl, C ₄ to C ₇ cycloalkyl, C to Cis aralkyl, Cr to C ₆ alkoxycarbonyl, aryl or hetaryl, the hetaryl radical being up to 3 May contain heteroatoms and the aryl or hetaryl radical may be substituted by up to 3 nonionic radicals and

R ²⁷ , R ²⁸ , R ³⁰ , R ³¹ , R ³³ and R ³⁴ independently of one another for hydrogen, C, - to C ₆ - alkyl, Cr to C ₆ -alkenyl, C ₄ - to C ₇ -cycloalkyl, C ₇ - to Cι ₅ - aralkyl, aryl or hetaryl, where the hetaryl radical can contain up to 3 heteroatoms and the aryl or hetaryl radical can be substituted by up to 3 nonionic radicals.

Optical data carrier according to Claim 1 or 2, characterized in that a compound of the formula (III), is used,

worm

R ⁴⁵ for hydrogen, bromine, chlorine, to C alkyl, G _\ to C ₄ alkoxy,

Cyano, Cj to C ₄ - alkoxycarbonyl, mono- or di C _\ to C ₄ -

Alkylamino stands,

R ⁴⁶ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ independently of one another are hydrogen, methyl, ethyl,

Cr to C ₆ alkoxy, fluorine, chlorine, bromine, cyano, nitro, Cr to C ₄ alkoxycarbonyl, mono- or di-Ci to C ₄ alkylamino,

R ^{50 represents} hydrogen, methyl, cyano, Cr to C ₆ -alkoxycarbonyl, formyl, bromine, chlorine,

R ^{51 represents} hydrogen, methyl, bromine, amino, N-methylamino, dimethylamino, methoxy, ethoxy, -S-CH ₃ ,

R ⁵² for cyano, Cr to Cβ-alkoxycarbonyl, C ₆ to Cio-aryloxycarbonyl,

Ci to C _ö alkanoyloxycarbonyl and

X ^{6 represents} cyano, Cr to C ₆ alkoxycarbonyl, C ₆ to Cio-aryloxycarbonyl, Cr to C ₆ alkanoyloxycarbonyl or -CH ₂ -O-SO ₂ -pC ₆ H -CH ₃ . Optical data carrier according to Claim 1 or 2, characterized in that a compound of the formula (IV) as the light-absorbing compound

is used,

wherein

R '66 represents hydrogen, bromine, chlorine, C 1 to C ₄ -alkyl, Cr to C ₆ -alkoxy, cyano, C 1 to C -alkoxycarbonyl, mono- or di-C 1 to C ₄ -alkylamino,

R '67 is hydrogen, CJ to C ₆ alkyl, Cr to C ₆ alkenyl, C ₆ - to Cι ₀ - aryl, C ₇ - to Cι ₅ -Araryl, hetaryl, Cr to C ₆ alkoxycarbonyl, formyl, Cyano, nitro, halogen or together with R ^{66 is} part of a five- or six-membered aromatic or partially hydrogenated ring which can contain 1 to 4 heteroatoms and / or benzylated or naphthanellated and / or whose rings can be substituted by nonionic radicals .

R ⁶⁸ , R ⁶⁹ , R ⁷⁰ and R ⁷¹ independently of one another for hydrogen, methyl, ethyl, isopropyl, Cr to C ₆ alkoxy, fluorine, chlorine, bromine, cyano, nitro, Ci to C - alkoxycarbonyl, mono- or di Cj to C ₄ alkylamino, Cr to C alkanoyloxy or 2 adjacent residues form a butadiene bridge, R ^{70 can} additionally stand for l, 2,3-triazol-2-yl, which can also be benzene-fused or naphthane-fused at the 4,5-position,

R> ^7/2 ^z for O, NH, N-Cr to NC ₃ alkyl;

R 7 "3 represents O, Nd to NC ₆ alkyl, NC ₆ to C ₁₀ aryl,

X6 for cyano, -CH ₂ -O-SO ₂ - / C ₆ H ₄ -CH ₃ , -CH ₂ -O-SO ₂ -CF ₃ , Cr to C ₆ - alkoxy-carbonyl, C ₆ - to Cio-aryloxycarbonyl , Cr to C ₆ alkanoyl oxycarbonyl and

R 75 for hydrogen, Cr to C ₆ alkyl, Cr to C ₆ alkenyl, Cr to C ₆ alkynyl, C ₄ to C cycloalkyl, C ₇ to C ₅ aralkyl, Cr to C ₆ alkoxycarbonyl, Aryl or hetaryl, where the hetaryl radical can contain up to 3 heteroatoms and the aryl or hetaryl radical can be substituted by up to 3 nonionic radicals.

5. Optical data carrier according to claim 1 or 2, characterized in that the light-absorbing compound is one of the formula (V)

is used,

wherein

Xl represents NR ¹ , O or S, R ¹ for hydrogen, d- to C ₆ -alkyl, d- to C ₆ -alkenyl, Cr to C ₆ -

Alkynyl, C ₄ to C cycloalkyl ₅ C ₇ to C ₅ aralkyl, Cr to C ₆

R ⁸⁵ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ independently of one another for hydrogen, methyl, ethyl,

Isopropyl, d- to C ₆ -alkoxy, fluorine, chlorine, bromine, cyano, nitro, d- to C -alkoxycarbonyl, mono- or di-Ci to C ₄ -alkylamino, Cr to

C ₄ -alkanoyloxy or 2 adjacent radicals form a butadiene bridge,

R ^{89 represents} O, NH, Nd to NC ₃ alkyl,

R ^{90 represents} O, Nd to C ₆ alkyl or NC ₆ to C ₁₀ aryl,

R ^{91 represents} hydrogen, cyano or (C = R ⁹³ ) R ⁹⁴ ,

X6 stands for CR ⁹⁸ R "R ¹⁰⁰ , CR ¹⁰¹ = O, CR ¹⁰² = S, CR ¹⁰³ = NR ¹⁰⁴ or C _≡ N,

R ^{93 represents} O, S or = NR ⁹⁵ ,

R ⁹⁴ for d- to C ₆ - alkoxy, Cr to C ₆ - alkyl, Cr to C ₆ alkanoyloxy, d- to C ₆ alkylthio, C ₆ - to Cι ₀ aryloxy, C ₆ - to Cι ₀ -Arylcarbonylamino , Amino, Nd- to C _ö -alkylamino, di-N-Cr to C ₆ -alkylamino, Nd- to C ₆ -alkyl-NC ₆ - to Cι ₀ -arylamino, R ^{95 represents} hydrogen, Cr to C ₆ alkyl, d to C ₆ alkenyl, C ₄ to C ₇ cycloalkyl, C to C ₁₅ aralkyl, Cj to C ₆ alkoxycarbonyl, aryl,

R ^{98 represents} hydrogen, bromine, chlorine, methoxy or ethoxy,

R ¹⁰⁰ for leaving groups such as bromine, chlorine, iodine, cyano, tosylate, triflate,

Cr to C ₆ alkanoyloxy, d to C ₆ alkylthio or methoxy if R ^{99 is} methoxy or ethoxy if R ^{99 is} ethoxy,

R ¹⁰¹ , R ¹⁰² and R ¹⁰³ for d- to C ₆ -alkoxy, chlorine, bromine, iodine, d- to C ₆ -

Alkanoyloxy, Cr to C ₆ alkylthio, C ₆ to Cio aryloxy, C ₆ to C ₁₀ arylcarbonylamino and

R ¹⁰⁴ for hydrogen, d- to C ₆ -alkyl, d- to C ₆ -alkenyl, d- to C ₆ -alkynyl, C ₄ - to C ₇ -cycloalkyl, C ₇ - to C ₁₅ -aralkyl, d- to C ₆ -

Alkoxycarbonyl, aryl or hetaryl, where the hetaryl radical can contain up to 3 heteroatoms and the aryl or hetaryl radical can be substituted by up to 3 nonionic radicals.

Optical data carrier according to Claim 1 or 2, characterized in that a compound of the formula (VI) is used as the light-absorbing compound

is used,

wherein

X ^{1 represents} NR ¹ ,

R ^{1 is} hydrogen, C_ to C ₆ alkyl, C to C ₆ alkenyl, d to C ₆ -

Alkynyl, C - to C ₇ -cycloalkyl, C ₇ - to -CC ₅ aralkyl, d- to C ₆ - alkoxycarbonyl, aryl or hetaryl, the hetaryl radical being up to

R ^{111 represents} hydrogen, methyl, bromine, amino, N-methylamino, dimethylamino, methoxy, ethoxy, -S-CH ₃ ,

R ¹¹² for cyano, Cr to C ₆ - alkoxycarbonyl, C ₆ - to Cι ₀ -aryloxycarbonyl,

Cr to Cg alkanoyloxycarbonyl, mono- or di-d to C ₆ -,

Alkylaminocarboxylic acid amide, mono- or diarylaminocarboxylic acid amide, monoaryl-mono- Cr to Cö-alkylaminocarboxylic acid amide,

Carboxamide,

Ring A stands for a 5-9 membered partially unsaturated, aromatic or quasi-aromatic ring which can contain 1-4 heteroatoms or carbonyl groups and / or benzene or naphthane fused and / or substituted by nonionic radicals and

X ^{6 represents} cyano, d- to C ₆ -alkoxycarbonyl, C ₆ - to C ₁₀ -aryloxycarbonyl or d- to C ₆ -alkanoyloxycarbonyl.

7. Use of light-absorbing compounds which have a chemical arrangement and which cyclize thermally to form 5-, 6- or 7-rings in the information layer of write-once optical data carriers, the light-absorbing compounds having an absorption maximum λ _ma χ in the range from 350 to 460 nm.

8. Use according to claim 7, characterized in that the dyes that cyclize thermally in the information layer of write-once optical data carriers are written and read with blue laser light.

9. A method for producing the optical data carrier according to claim 1, which is characterized in that a preferably transparent substrate, optionally already coated with a reflection layer, with the dyes which cyclize thermally, optionally in combination with suitable binders and additives and, if appropriate, suitable Solvents coated and optionally provided with a reflection layer, further intermediate layers and optionally a protective layer or another substrate or a cover layer.

10. Optical data carrier according to claim 1 described with blue light, in particular blue laser light.

11. Compounds of the formula (III)

wherein

R, 45 represents hydrogen, bromine, chlorine, d to C ₄ -alkyl, d-- to C-alkoxy, cyano, d to C ₄ -alkoxycarbonyl, mono- or di C ₁ to C -alkylamino,

R ⁴⁶ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ independently of one another for hydrogen, methyl, ethyl, Cr to C ₆ -alkoxy, fluorine, chlorine, bromine, cyano, nitro, d- to C ₄ -alkoxycarbonyl, mono- or di- d to C ₄ alkylamino,

R> 5Ö represents hydrogen, methyl, cyano, Cr to C ₆ -alkoxycarbonyl, formyl, bromine, chlorine,

R 51 represents hydrogen, methyl, bromine, amino, N-methylamino, dimethylamino, methoxy, ethoxy, -S-CH ₃ ,

R is cyano, Cr to C ₆ alkoxycarbonyl, C ₆ to Cio-aryloxycarbonyl, Cr to C ₆ alkanoyloxycarbonyl and

X ^{6 represents} cyano, d- to C ₆ -alkoxycarbonyl, C ₆ - to Cio-aryloxycarbonyl, d- to C ₆ -alkanoyloxycarbonyl or -CH ₂ -O-SO ₂ -pC ₆ H -CH ₃ .

12. Compounds of the formulas (la) or (Ila)

wherein

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ?, χ8 _s χ _{5 n UI1} dm have the meaning given in claim 2.

X ^{6a represents} CR ⁶ R ⁷ , CO, CS, C = NR ¹² or C = NH,

in which

R ⁶ , R ⁷ and R ^{12 have} the meaning given in claim 2.

13. Optical data carriers containing a compound of the formula (Ia) or (Ila) according to claim 12 in the information layer as a light-absorbing compound.